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FIELD OF THE INVENTION
[0001] The present invention relates to long-arm stitchers and, more particularly, to a control system for long-arm stitchers and the like.
RELATED ART
[0002] Conventional long-arm sewing machines are generally used for quilting and/or sewing fabrics that are not easily moved through a sewing machine. As such, a long-arm sewing machine is designed to move with respect to a workpiece that is held stationary on a frame. However, the workpieces generally include two outer layers and a filler material that is sewn between the outer layers. Often, the filler being stitched into the workpiece is uneven, thereby adding to difficulties for a stitch regulator to properly control a velocity of the stitcher with respect to the workpiece. Moreover, the stitch design of the workpiece may include several different stitch types and/or a stitch pattern that is not straight, thereby complicating the ability to control the stitch pattern. Accordingly, the velocity of stitcher movement with respect to the workpiece must be varied during stitching to maintain a proper stitch length or number of stitches per inch of the workpiece.
[0003] Typically, a stitch regulator is controlled by optical encoders that monitor the stitch pattern as it is being stitch into the workpiece. However, such encoders must be positioned adjacent the workpiece and may resultantly interfere with the stitching operation. In addition, optical encoders are costly and require a significant amount of assembly time. The assembly also generally includes harnesses and cabling to properly install the optical encoder.
[0004] As such, it is desirable to control a stitch regulator utilizing a less costly and more easily assembled system that does not interfere with the stitching process.
SUMMARY OF THE INVENTION
[0005] In one embodiment, a control system for a stitcher is provided that includes a motor driving the stitcher, and a stitch regulator in communication with and capable of altering a velocity of the motor. A controller is in communication with the stitch regulator; and at least one accelerometer is in communication with the controller to determine an acceleration of the stitcher with respect to a workpiece. A signal representing the acceleration of the stitcher with respect to the workpiece is communicated to the controller; and the operation of the stitch regulator is modified as necessary based on the signal.
[0006] In another embodiment, a stitcher is provided that includes a needle to stitch a workpiece, a motor to operate the needle, and a stitch regulator in communication with and capable of controlling a speed of the motor. A controller is in communication with the stitch regulator. The stitcher also includes at least one accelerometer in communication with the controller to determine an acceleration of the stitcher with respect to the workpiece. A signal representing the acceleration of the stitcher with respect to the workpiece is utilized to adjust the operation of the needle as necessary.
[0007] In a further embodiment a method of operating a stitcher is provided. The method includes providing a stitch regulator for controlling the operation of the stitcher, and providing an accelerometer in communication with the stitch regulator. An acceleration of the stitcher with respect to a workpiece is measured with the accelerometer, and a signal representing the acceleration of the stitcher is sent to the stitch regulator. The method further includes integrating the signal representing the acceleration of the stitcher to determine a velocity of the stitcher with respect to the workpiece, and controlling the stitch regulator utilizing the velocity of the stitcher with respect to the workpiece.
[0008] Although the present invention is described with respect to a long-arm stitcher, one of ordinary skill in the art would recognize that the present invention also has applicability with standard sewing machines and could be used in both a commercial and/or household setting. Further areas of applicability of the present invention will become apparent from the detailed description provided hereinafter. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] The present invention will become more fully understood from the detailed description and the accompanying drawings, wherein:
[0010] FIG. 1 is a perspective view of a prior art long-arm stitcher.
[0011] FIG. 2 is a perspective view of the stitcher shown in FIG. 1 having an accelerometer.
[0012] FIG. 3 is an algorithm of a method of operating the stitcher shown in FIG. 2 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0013] The following description of the preferred embodiment(s) is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses.
[0014] FIG. 1 illustrates a standard long-arm stitcher 10 including a base 12 , an arm 14 , and a take up lever box 16 . Although the present invention is described with respect to a long-arm stitcher, one of ordinary skill in the art would recognize that the present invention is also applicable to standard sewing machines. Moreover, the present invention is capable of operating with both commercial and household long-arm stitchers and sewing machines. The arm 14 is coupled to the base 12 at a back end 18 of the stitcher 10 . A first portion 20 of the arm 14 extends upward from the base 12 , and a second portion 22 of the arm 14 extends from the first portion 20 substantially parallel to the base 12 . The take up lever box 16 is disposed on the arm 14 at a stitching end 24 of the stitcher 10 that is opposite the back end 18 . The stitching end 24 of the stitcher 10 forms a workspace 26 where a fabric is stitched by an operator of the stitcher 10 . The stitching end includes a needle bar 28 having a needle 30 inserted therein and a hopping foot 32 each extending downward toward a needle plate 34 disposed on the base 12 . The needle plate 34 is attached to a square throat plate 36 . The throat plate 36 is configured to be removed to provide access to a rotary hook assembly (not shown) positioned within the base 12 below the throat plate 36 .
[0015] During operation, the needle bar 28 moves up and down thereby moving the needle 30 to form a stitch in the fabric. The needle bar 28 can be adjusted up or down to provide a proper machine timing height. A small hole in the needle plate 34 restricts movement of the thread as the stitch is formed. The hopping foot 32 raises and lowers with the movement of the needle 30 to press and release the fabric as the stitch is formed. The hopping foot 32 is designed to be used with rulers and templates and has a height that can be adjusted for proper stitch formation. A control box 48 is provided to control the operation of the stitcher 10 .
[0016] The control box 48 includes a stitch regulator 50 that controls a speed of the needle 30 . Specifically, the needle speed is controlled to accommodate varying thicknesses of the workpiece and varying stitch types. The speed is further controlled to accommodate a stitch pattern that may not be linear.
[0017] FIG. 2 illustrates the stitcher 10 having at least one accelerometer 52 positioned on the second portion 22 of the arm 14 to measure an acceleration of the stitcher 10 . As will be appreciated by one of ordinary skill in the art, the at least one accelerometer 52 may be positioned at any location on stitcher 10 . In one embodiment, the accelerometer 52 measures a piezoelectric effect utilizing microscopic crystal structures that become stressed by accelerative forces, thereby causing a voltage to be generated. The voltage is used then used to determine acceleration. Alternatively, the accelerometer 52 may sense changes in capacitance between two microstructures in the accelerometer 52 . Specifically, if an accelerative force moves one of the structures, the capacitance changes. The change in capacitance is then converted to a voltage that is used to determine acceleration. In other embodiments, the accelerometer 52 may utilize hot air bubbles or light. In the exemplary embodiment, the at least one accelerometer 52 is one of a single two-axis accelerometer or includes two separate accelerometers, namely an x-axis accelerometer and a y-axis accelerometer. Accordingly, the accelerometer 52 is capable of measuring the acceleration of stitcher 10 in any of the x-axis and the y-axis. In the exemplary embodiment, the accelerometer 52 is a high accuracy, dual-axis digital inclinometer and accelerometer, model number ADIS16209, from Analog Devices; however, it will be appreciated that any off-the-shelf accelerometer would be acceptable for use with the stitcher 10 .
[0018] The accelerometer 52 is electronically coupled to the stitch regulator 50 and is configured to control the stitch regulator 50 based on the algorithm 100 shown in FIG. 3 . Specifically, at step 102 , the stitcher 10 is moved to a zero motion position and the accelerometer 52 is calibrated while the stitcher 10 is stationary. The stitcher 10 is then operated, at step 104 , to stitch a pattern in the workpiece. During the operation, the stitch regulator 50 controls a number of stitches per inch that are stitched into the workpiece.
[0019] At step 106 , a signal indicative of the stitcher's acceleration with respect to the workpiece is received from the accelerometer 52 . The signal is filtered with a low pass filter and sampling losses are removed therefrom, at step 108 , to determine an acceleration of the stitcher 10 in both the x-axis and the y-axis. While the present invention is described with respect to both the x-axis and the y-axis, as will be appreciated by one of ordinary skill in the art, the signal may only be indicative of the stitcher's acceleration in one of the x-axis or the y-axis. At step 110 , the acceleration signal is integrated to provide a vector velocity of the stitcher 10 in the x-axis and the y-axis, wherein the vector velocities include both a magnitude and a direction. The vector velocity in the x-axis and the vector velocity in the y-axis are summed, at step 112 , to provide a vector sum having both a magnitude and direction indicative of a velocity of the stitcher 10 with respect to the workpiece.
[0020] At step 114 , it is determined whether a position of the stitcher 10 is also desired. If the position is not desired 116 , the velocity of the stitcher 10 is used to determine a correction of the stitch regulator 50 , at step 118 . The stitcher 10 is then operated, at step 104 , to stitch a pattern in the workpiece, wherein the stitch regulator 50 controls the number of stitches per inch based on the velocity correction.
[0021] If the position of the stitcher 10 is desired 120 , the stitcher velocity is integrated, at step 122 , to provide a vector position of the stitcher 10 in the x-axis and the y-axis, wherein the vector positions include both a magnitude and a direction. The vector position in the x-axis and the vector position in the y-axis are summed, at step 124 , to provide a vector sum having both a magnitude and direction indicative of a position of the stitcher 10 with respect to the workpiece. The velocity and position of the stitcher 10 is then used to determine a correction of the stitch regulator 50 , at step 126 . The stitcher 10 is then operated, at step 104 , to stitch a pattern in the workpiece, wherein the stitch regulator 50 controls the number of stitches per inch based on the velocity and position corrections.
[0022] Accordingly, the present invention provides a means to regulate a speed of stitcher needle 30 utilizing the acceleration and position of the stitcher in the x-axis and/or y-axis. Specifically, by determining the acceleration of the stitcher 10 , a velocity and displacement of the stitcher 10 is determined and input into the stitch regulator 50 . As such, the needle 30 can be regulated based on a velocity and/or displacement of the stitcher 10 with respect to a workpiece, thereby enabling automatic correction of a stitch pattern.
[0023] As various modifications could be made to the exemplary embodiments, as described above with reference to the corresponding illustrations, without departing from the scope of the invention, it is intended that all matter contained in the foregoing description and shown in the accompanying drawings shall be interpreted as illustrative rather than limiting. Thus, the breadth and scope of the present invention should not be limited by any of the above-described exemplary embodiments, but should be defined only in accordance with the following claims appended hereto and their equivalents.
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A stitcher is provided that includes a needle to stitch a workpiece, a motor to operate the needle, and a stitch regulator in communication with and capable of controlling a speed of the motor. A controller is in communication with the stitch regulator. The stitcher also includes at least one accelerometer in communication with the controller to determine an acceleration of the stitcher with respect to the workpiece. A signal representing the acceleration of the stitcher with respect to the workpiece is utilized to adjust the operation of the needle as necessary.
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BACKGROUND OF THE INVENTION
This invention relates to improvements in hats and caps, and is especially concerned with unique means for retaining hard hats in position on a worker's head when bending over and looking down.
On construction projects of even modest size the regulations of the United States Department of Labor Occupational Safety and Health Administration (OSHA) specify that virtually all workers on the project must wear hard shell safety hats. This regulation is strictly enforced by most all employers in the construction industry and workers found hatless have been fined by the employer for a first violation and summarily fired upon a second violation.
Carpenters and welders, for example, find it necessary on such projects to work in a downwardly facing attitude such as when nailing down a floor or welding seams along a horizontal surface. Their hard hats tend to fall from their heads repeatedly and chin straps are believed unsatisfactory by many workers as being too confining for holding the hard hat in place. Straps extending downwardly along the back of the head in the nape of the neck region are available and are constructed substantially as disclosed in the Bowers Jr. U.S. Pat. No. 3,354,468 issued Nov. 28, 1967. That patent discloses a nape strap formed from flexible material and extends generally along the rear or back of the head band and is shiftable from a raised position where it is tucked away next to the head band to a lowered position of engaging the nape area. This construction is not entirely satisfactory in the field because the unsupported flexible character of the nape strap permits it to work itself upwardly on the head such as when jostling forces are created by the carpenter in a floor nailing operation. Frictional forces between the nape strap and the back of the head above have not proved satisfactory for maintaining the nape strap in a holding relationship with the wearer's head.
Nape straps in combination with chin straps were disclosed in the Alesi U.S. Pat. No. 3,814,043 issued Nov. 26, 1957, and in the Mickel U.S. Pat. No. 3,852,821 issued Dec. 10, 1974. There is in those disclosures no indication of the problem of maintaining the weighty helmet on the head with the nape strap arrangement alone when doing jostling type physical work. Those patents both disclose the suitability of cooperation between the chin strap and the rearwardly positioned nape strap arrangement.
SUMMARY AND OBJECT OF THE INVENTION
In general this invention is for an improved head band which fits into a hard shell safety hat for securely retaining the unit on a worker's head when bending over and looking down. The head band is formed of material conformable to the human head and includes means for supporting it with respect to the hard shell of the hat. A nape strap which is formed of flexible material for conforming to the contour of the nape area of the human head is connected on the left and right side portion of the head band and at least one strut member of relatively stiff material extends downwardly from the rear portion of the head band to a medial section of the nape strap to position positively the nape strap on the head and preferably in the base of the skull area.
An object of the invention is to provide an improved head band for a hard hat which serves to retain the hard hat securely on the head of the workman when bending over and working in a downwardly facing position.
Another object of the invention is to provide a head band structure as described above wherein means are included for locating positively a nape strap in a region low on the head so that the associated hard hat may be held securely on the wearer's head.
Another object of the invention is to provide an improved head band with a positively positioned nape strap which head band arrangement is adaptable to hard hats of different designs.
Another object of the invention is to provide a hard hat and nape strap arrangement which is comfortable to the heads of a wide spectrum of wearers for securing the safety hat in position during vigorous physical work when the head is in a downwardly facing attitude.
These and other objects of the invention will be clearly understood from the drawings which illustrate the invention and the description of it below.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side elevational view of a workman wearing a hard hat, portions of which are broken away to show clearly the head band structure of the present invention;
FIG. 2 is a rear view of the structure and head of the person shown in FIG. 2,
FIG. 3 is a side view on a smaller scale showing a workman in a bent over working position looking downwardly with the head band arrangement of the present invention holding the hard hat securely to his head.
DETAILED DESCRIPTION OF THE INVENTION
An improved head band 10 for a hard shell safety hat 11 is clearly shown in FIGS. 1 and 2 of the drawings in its proper position upon a worker's head 12. The hard hat 11 includes a generally semi-spherical outer shell 13 formed from a high impact plastic material and may be of conventional construction found in the field. To this end the interior of the shell 13 is equipped with circumferentially spaced apart mounting lugs (not shown) for connection with a cooperative fastener (not shown) of a suspension harness 14 which is connected to the head band 10. The construction of the suspension harness 14 and the manner of mounting the head band to the shell 13 may take any of the conventional arrangements found in the field today. It is pointed out here that the head band 10 is adaptable to a large number of suspension harnesses in use.
The head band 10 is connected to the suspension harness 14 at four or more locations, for example, by means of a button 16 fixed to the suspension harness and which extends through an elongated slot 17 in the head band. Two or more spaced slots 17 may be positioned on the width of the head band for adjusting the head band with respect to the suspension harness so that a variety of head sizes and shapes may be accommodated.
The head band extends completely around the wearer's head and for the purposes of this disclosure, locations on the head band will sometimes be referred to by clock positions where the front portion of the head band is considered as the 12 O'clock position and the rear portion opposite it, the 6 O'clock position and so forth. As shown in FIG. 2, adjustment means are provided in the rear 6 O'clock position of the head band and may include a knobbed button 18 selectively positioned in one of a plurality of holes 19 in the ends of the head band to provide adjustability for differing head sizes.
A nape strap 21 formed of flexible material such as webbing, plastic or other suitable material is mounted to the head band 10 at about the 3 O'clock and 9 O'clock positions, as shown in FIGS. 1 and 3. In other words, on opposite sides of the wearer's head at the above-the-ears position. The nape strap 21 droops downwardly in somewhat of a catenary like curve, and has a length ample to extend below the base of the skull and into the nape of the neck area and ideally to engage under the protuberant portion of the rear of the human skull to prevent tipping of the hard hat when the wearer is in the position as illustrated in FIG. 3. Adjustment means are provided on at least one end, and preferably on both ends, of the nape strap 21 and this may take the form of a plurality of snap fasteners 22 with the female portion mounted to the nape strap and the male portion of the head band 10. Snap fasteners sold under the trademark, "DOT" have proved satisfactory in affording adjustability of the nape strap with respect to the head band.
Two relatively stiff strut members 26 and 27 extend from the head band 10 to the nape strap 21, as best shown in FIG. 2. The struts 26, 27 may be formed from a relatively stiff plastic material such as nylon or some other plastic material which can be formed to hold a slight curve so as to accommodate the curvature of the human head. On the head band and on the nape strap 21 the ends of the struts 26, 27 are fixedly secured as by rivets 28 or by a button like fastener (not shown) so as to maintain the nape strap spaced downwardly from the head band. The fastener locations of the struts on the head band are approximately at the 5 O'clock and 7 O'clock positions. The struts diverge outwardly toward the nape strap to about the 4 O'clock and 8 O'clock positions. This arrangement assures that the sides of the head are engaged by the nape strap 21 so that the entire head band and nape strap arrangement will nest firmly but comfortably against the wearer's head for holding the hard shell hat in a secured fashion.
Other arrangements of the relatively stiff strut members will come to mind of those skilled in the field having knowledge of the purpose for retaining the nape strap in a low position on the head.
It has been found that a safety hard hat equipped with a head band arrangement of the disclosure is effective for holding the hard hat on the head of a workman such as a carpenter nailing down a floor as exemplified by FIG. 3. The jostling motion generated in the hammering does not cause the hat to fall unto the floor 129. This arrangement avoids the need for a chin strap which is considered uncomfortable by many workmen.
From the above it is seen that the present invention provides a hat construction of attachement which fully accomplishes the intended objects set out above and is adapted to meet the practical conditions of adjustment in the field by the workmen and installation of the head band unit on a variety of different hard hats.
The present invention is described in detail by way of illustrating it, but it should be understood that certain changes and modifications may be made within the scope of this invention and within the scope of claims which follow below.
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A head band for a hard hat and including a nape strap of a material conforming to the head and held away from the head band against the nape area by two stiff strut members.
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CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims priority to copending U.S. provisional application entitled, “Hand Antiseptic Alarm,” having Serial No. 60/215,328, filed Jun. 30, 2000, which is entirely incorporated herein by reference.
TECHNICAL FIELD
[0002] The present invention is generally related to hand hygiene. More particularly, the invention is related to a system and method for alerting a person of the requirement of washing his/her hands when entering or leaving an area of probable contamination, for reducing the incidence of hospital-acquired infections, food handling contamination, and for reducing other situations in which the acquired contamination of a person's hands is likely to be passed to other personnel.
BACKGROUND OF THE INVENTION
[0003] The incidence of hospital acquired (nosocomial) infection is approximately 8% of all hospital in-patients. Nosocomial infections are transmitted by direct or indirect contact between hospital staff and patients. Nosocomial infections are a direct result of inadequate hand hygiene by healthcare workers. It is widely recognized in the infectious diseases specialty that hand hygiene is the simplest and most dollar effective means of preventing these hospital acquired infections. Studies have demonstrated that enforcement of hand hygiene results in a roughly 50% decrease in nosocomial infection rate.
[0004] However, hand hygiene is very difficult to enforce and compliance by hospital staff and visitors is uniformly lax. In 1997, an article in the New England Journal of Medicine studied the hand-washing rate by hospital staff. Even though the physician, nurses and other staff knew that they were under scrutiny, only 35 to 40% of staff washed their hands regularly in between direct or indirect patient contact. A similar study in Annals of Internal Medicine reported hand-washing compliance in 48% of nurses and 35% of physicians. More alarmingly, respiratory therapists washed their hands on only 12% of occasions, and radiology technicians only 8%.
[0005] In addition to hospital staff and visitor hand hygiene, there is a need for improving hand hygiene in other public activities, particularly in commercial food handling and food preparation, for reducing the risk of contamination of food consumed by other people.
[0006] Thus, a heretofore unaddressed need exists in the industry to reduce nosocomial an other infections.
SUMMARY OF THE INVENTION
[0007] Briefly described, the present invention comprises a system and apparatus for alerting a person entering or leaving an area to clean his or her hands. The system includes a bi-directional sensor (e.g. a passive infrared sensor) having first and second sensors spaced horizontally from each other so that the movement of a person passing the sensor is detected and the direction of movement is detected. An alarm, such as a lamp or a sound emitting device, or both, is located on one or more antiseptic dispenser units located in proximity to the sensor. The alarms on the dispenser can be actuated in response to the detection of movement of a person passing the sensor. Activation of the dispenser unit (e.g. by depressing the dispenser lever) simultaneously dispenses an aliquot of disinfectant onto the individuals hands and simultaneously de-activates the alarm system.
[0008] For example, when a person moves through the entrance into a hospital room where a patient is being cared for, the sensor detects the movement of the person into the room. Activation of the sensor causes the alarms on the dispenser to be actuated, alerting the person to decontaminate their hands. Once the person activates the dispenser lever, disinfectant is released onto the persons hands, and the alarm is simultaneously de-activated. In addition, or in the alternative, each sensor may be communicatively coupled to one or more dispenser systems. For example, one dispenser system may be located inside the room, while another dispenser system is located outside of the room. This configuration allows for hand decontamination upon both entry and/or exit of the room.
[0009] Another feature of the invention is that an alcohol based aerosolized foam or antiseptic solution can be used to clean a persons hands. Alcohol based foams or solutions can be used without the need for a sink or basin. Therefore, this embodiment would avoid the need to have a nearby wash basin and can be used in areas that do not have a wash basin.
[0010] Although a primary use of the invention is anticipated to be in health care facilities, other uses can be made of the invention, such as in food handling and food preparation facilities, where hand washing is desirable in certain areas. The invention can be used to demand hand washing before an event, as when the food handler enters the food handling area, or to demand hand washing after an event, as when a person exits a contaminated area.
[0011] Another advantage of the invention is that the hand antiseptic system is designed so that it is applicable to use in all hospital room layouts. Further, the hand antiseptic system is bi-directional in that the system is capable of determining if one or more individuals are entering or exiting the particular area. Another advantage is that the hand antiseptic system is capable of sensing multiple targets (two or more individuals entering/exiting the area) and ensuring that each individual decontaminates their hands.
[0012] Other systems, methods, features, and advantages of the present invention will be or become apparent to one with skill in the art upon examination of the following drawings and detailed description. It is intended that all such additional systems, methods, features, and advantages be included within this description, be within the scope of the present invention, and be protected by the accompanying claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] The invention can be better understood with reference to the following drawings. The components in the drawings are not necessarily to scale, emphasis instead being placed upon clearly illustrating the principles of the present invention. Moreover, in the drawings, like reference numerals designate corresponding parts throughout the several views.
[0014] [0014]FIG. 1 is a schematic diagram of the components of the hand antiseptic system.
[0015] [0015]FIG. 2 is a schematic diagram of a computer that is implemented in the hand antiseptic system as shown in FIG. 1.
[0016] [0016]FIG. 3 is a plan view of a room, such as a hospital room, that implements the hand antiseptic system that is shown in FIG. 1.
DETAILED DESCRIPTION
[0017] Referring now in more detail to the drawings, in which liken numerals indicate like parts throughout the several views, FIG. 1 illustrates an embodiment of the hand antiseptic system 10 . The embodiment illustrated in FIG. 1 includes a bi-directional sensor system 14 and a dispensing system 16 . The bi-directional sensor system 14 includes, but is not limited to, one or more sensors 20 A and 20 B, a computer 25 , an alarm selector 22 , an alarm mode selector 24 , a low power light 26 , and an adjustment light 28 . The dispensing system 16 can include, but is not limited to, an audible alarm 30 , a visual alarm 32 , a dispensing detector 34 , and a dispensing lever 36 . The bi-directional sensor system 14 and the dispensing systems 16 are communicatively coupled 40 . Communicatively coupled 40 means that the bi-directional sensor system 14 and a dispensing system 16 can communicate information with one another. This communication can be accomplished via a direct wire connection or through an appropriate wireless communications system, both of which are well known in the art.
[0018] The sensors 20 A and 20 B of the bi-directional sensor system 14 are each capable of sensing infrared energy, or other appropriate energy. The sensing of energy by the sensors 20 A and 20 B can indicate that targets are passing the sensors 20 A and 20 B. Generally, the sensors 20 A and 20 B can sense energy in areas that are usually horizontally spaced from each other so that as the targets pass through each area, the sensors 20 A and 20 B are triggered sequentially. The computer 25 of the bi-directional sensor system 14 logically understands the sequential triggering of the sensors 20 A and 20 B to mean that a person has entered/exited the particular area of interest. The sensors 20 A and 20 B include, but are not limited to, passive infrared sensors, photoelectric proximity sensors, photoelectric (“beam break”) sensors, laser sensors, electromagnetic sensors, ultrasonic sensors, and combinations thereof. Each of these sensors 20 A and 20 B can be bi-directional. More particularly, the sensors 20 A and 20 B can be Visonic CLIP 3™ sensors. These types of sensors 20 A and 20 B are well known in the art and will not be discussed in any more detail hereinafter.
[0019] As shown in FIG. 1, the bi-directional sensor system 14 includes an alarm selector 22 and an alarm mode selector 24 . Generally, the selectors 22 and 24 are four-way selector switches that allow the user to select the functional setup of the bi-directional sensor system 14 . The alarm selector 22 allows the user to select the direction of alarm activation; alarm set for individuals entering the room only (A), exiting the room only (B), or both (AB). The alarm selector 22 has an arrow to indicate both the position of the switch and, in two settings, the direction of the movement that will activate the alarm. The fourth or down position of the alarm selector 22 is the “off” switch. The alarm mode selector 24 allows the user to select the nature of the alarm system; audible alarm only (X), visual alarm only (Y), or both audible and visible alarm (XY). The fourth position of the alarm mode selector 24 is the “off” position. Alternatively, the fourth position of the alarm mode selector 24 can be a position that connects to a remote location for alerting a person, such as an attendant at a nurse station of a hospital.
[0020] In the event the system is battery powered, the bi-directional sensor system 14 can includes a low power light 26 (FIG. 1) and an equilibrating light 28 . The low power light 26 indicates that the bi-directional sensor system 14 is on and is low on power. The equilibrating light 28 indicates that the sensors 20 A and 20 B of the bi-directional sensor system 14 are adjusting to the energy (e.g. background infrared energy) of the particular area that the bi-directional sensor system 14 is located.
[0021] The dispensing system 16 includes an audible alarm 30 and a visual alarm 32 . The audible alarm 30 indicates that the individual has not disinfected his/her hands. The audible alarm 30 can have various audible alarms, such as, an alarm for an individual or a group of people in the form of a “beep” or pre-recorded message. The visual alarm 32 indicates that the individual has not disinfected his/her hands. The visual alarm 32 can have various blinking modes for particular situations. Generally, once the sensors 20 A and 20 B of the bi-directional sensor system 14 have been triggered the visual alarm 32 is actuated first, then after a pre-determined period of time the audible alarm 30 is actuated. If the audible alarm 40 is not de-activated after a pre-determined time period, the audible alarm 30 is automatically de-activated by a timer to reduce disruption to the patient. Generally, one or more circuits are used to actuate the alarms 20 and 22 and these will be discussed below.
[0022] The dispensing system 16 includes an antiseptic substance that can be dispensed via the dispensing lever 36 . Pressing the dispenser lever 36 dispenses an aliquot of antiseptic substance to a pre-determined location. The dispensing lever 36 can be a mechanically actuated lever system or a sensor actuated system. Mechanical and sensor actuation systems are well known in the art and will not be expounded upon here. Actuating the dispensing lever 36 de-activates the visual and/or audible alarms 32 and 30 , which are discussed in more detail below.
[0023] Generally, one or more circuits can be used to interconnect the sensors 20 A and 20 B, the alarms 30 and 32 , and the dispenser lever 36 . One function of the circuit is to turn the appropriate alarm 30 and/or 32 on upon the occurrence of a particular event, such as a person triggering the sensors 20 A and 20 B by walking through the path of the sensors into or out of a particular area. Another function of the circuit is to turn the appropriate alarm 30 and/or 32 off upon the occurrence of a particular event, such as a person actuating the dispensing lever 36 . More particularly, upon triggering one or both of the alarms 30 and 32 , a gate in a holding circuit is closed, which connects a power source, such as a battery, to one or both alarms 30 and 32 , thereby enabling one or both alarms 30 and 32 . Alternatively, upon de-activating one or both of the alarms 30 and 32 by actuating the dispensing lever 36 , the gate in the holding circuit is opened, which disconnects the power source to one or both alarms 30 and 32 , thereby disabling one or both alarms 30 and 32 . One skilled in the art of electronics could construct numerous circuit configurations that function to operate the hand antiseptic system 10 and any circuit that can accomplish that function is thereby included herein.
[0024] As indicated above, the dispenser system 16 contains a supply of an antiseptic substance or other appropriate cleansing foam, gel, or solution. One embodiment consists of a dispenser system 16 that can accommodate an alcohol based aerosolized foam (e.g. Alcare™ Steris Inc., or E-Z Scrub™ Becton-Dickinson) or antiseptic solution (CalStat™, Steris Inc.). This embodiment would avoid the need for a nearby faucet, hand-sink, or hand-dryer. The dispenser system 16 can be secured to a wall by screw recesses, doublebacked adhesive tape, or other appropriate attaching mechanism.
[0025] One embodiment of the hand antiseptic system 10 includes a digital camera (still or moving) that is capable of storing an image of individuals entering or exiting the particular area of interest. If the hand antiseptic system 10 is utilized, the image is deleted. If the hand antiseptic system 10 is not utilized, the image is stored for the purpose of identification. Still another embodiment includes an identification system such as a radio frequency identification (RFID) system. Generally, the identification system functions to identify and/or track personnel. More specifically, RFID allows real time identification and tracking of personnel. The system consists of two basic elements: the passive transponder (the ID tag) and the reader. The reader emits a low-frequency magnetic field via an antenna. When a transponder passes within range, it is excited, causing it to transmit its ID code back to the reader. Transmission and reception can occur simultaneously. The tag is incorporated into the ID badges of healthcare workers entering/exiting the particular area of interest. This can also be used to identify individuals not utilizing the hand antiseptic system.
[0026] The hand antiseptic system 10 may also include a “sleep” mode, which inactivates the hand antiseptic system 10 for a predetermined time (e.g. 30-60 seconds). A small wireless transmitter could activate the “sleep” mode. The “sleep key” is carried by a few individuals who enter the room, but never have patient contact (e.g. meal deliveries). This feature permits selected individuals time to enter the particular area of interest, perform their task (e.g. leave the food tray) and leave, without activating the alarm.
[0027] Replaceable batteries can power the bi-directional sensor system 14 and the dispenser system 16 , which precludes the need for an external electrical supply. Alternatively a DC converter unit could supply a constant power source from a nearby AC electrical outlet.
[0028] The bi-directional sensory system 14 includes a computer 25 to operate various functions of the hand antiseptic system 10 . The computer 25 shown in FIG. 2 may include a processor 50 , memory 52 , and one or more input and/or output (I/O) devices 54 (or peripherals) that are communicatively coupled via a local interface 53 . In addition, the computer 25 can be communicatively coupled to one or more sensors 20 A and 20 B and one or more dispenser systems 16 . The local interface 53 can be, for example but not limited to, one or more buses or other wired or wireless connections, as is known in the art. The local interface 53 may have additional elements, which are omitted for simplicity, such as controllers, buffers (caches), drivers, repeaters, and receivers, to enable communications. Further, the local interface may include address, control, and/or data connections to enable appropriate communications among the aforementioned components.
[0029] The processor 50 is a hardware device for executing software that can be stored in memory 52 . The processor 50 can be any custom made or commercially available processor, a central processing unit (CPU), an auxiliary processor among several processors associated with the computer 25 , a semiconductor based microprocessor (in the form of a microchip or chip set), a macroprocessor, or generally any device for executing software instructions.
[0030] The memory 52 can include any one or combination of volatile memory elements (e.g., random access memory (RAM, such as DRAM, SRAM, SDRAM, etc.)) and nonvolatile memory elements (e.g., ROM, hard drive, tape, CDROM, etc.). Moreover, the memory 52 may incorporate electronic, magnetic, optical, and/or other types of storage media. Note that the memory 52 can have a distributed architecture, where various components are situated remote from one another, but can be accessed by the processor 50 .
[0031] The software in memory 52 may include one or more separate programs, each of which comprises an ordered listing of executable instructions for implementing logical functions. In the example of FIG. 2, the software in the memory 52 includes the infrared sensor system 51 . The sensor program 51 is a source program, executable program (object code), script, or any other entity comprising a set of instructions to be performed.
[0032] The I/O devices 54 may include input devices, for example but not limited to, a keyboard, mouse, scanner, microphone, etc. Furthermore, the I/O devices 54 may also include output devices, for example but not limited to, a printer, display, etc. Finally, the I/O devices 54 may further include devices that communicate both inputs and outputs, for instance but not limited to, a modulator/demodulator (modem; for accessing another device, system, or network), a radio frequency (RF) or other transceiver, a telephonic interface, a bridge, a router, etc.
[0033] If the computer 25 is a PC, workstation, or the like, the software in the memory 52 may further include a basic input output system (BIOS) (omitted for simplicity). The BIOS is a set of essential software routines that initialize and test hardware at startup, and support the transfer of data among the hardware devices. The BIOS is stored in ROM so that the BIOS can be executed when the computer 25 is activated.
[0034] When the computer 25 is in operation, the processor 50 is configured to execute software stored within the memory 52 , to communicate data to and from the memory 52 , and to generally control operations of the computer 25 pursuant to the software. The sensor program 51 is read by the processor 25 , perhaps buffered within the processor 50 , and then executed.
[0035] When the sensor program 51 is implemented in software, as is shown in FIG. 2, it should be noted that the sensor program 51 can be stored on any computer readable medium for use by or in connection with any computer related system or method. In the context of this document, a computer readable medium is an electronic, magnetic, optical, or other physical device or means that can contain or store a computer program for use by or in connection with a computer related system or method. The infrared system 51 can be embodied in any computer-readable medium for use by or in connection with an instruction execution system, system, or device, such as a computer-based system, processor-containing system, or other system that can fetch the instructions from the instruction execution system, system, or device and execute the instructions. In the context of this document, a “computer-readable medium” can be any means that can store, communicate, propagate, or transport the program for use by or in connection with the instruction execution system, system, or device. The computer readable medium can be, for example but not limited to, an electronic, magnetic, optical, electromagnetic, infrared, or semiconductor system, system, device, or propagation medium. More specific examples (a nonexhaustive list) of the computer-readable medium would include the following: an electrical connection (electronic) having one or more wires, a portable computer diskette (magnetic), a random access memory (RAM) (electronic), a read-only memory (ROM) (electronic), an erasable programmable read-only memory (EPROM, EEPROM, or Flash memory) (electronic), an optical fiber (optical), and a portable compact disc read-only memory (CDROM) (optical). Note that the computer-readable medium could even be paper or another suitable medium upon which the program is printed, as the program can be electronically captured, via for instance optical scanning of the paper or other medium, then compiled, interpreted or otherwise processed in a suitable manner if necessary, and then stored in a computer memory.
[0036] In an alternative embodiment, where the sensor program 51 is implemented in hardware, the infrared sensor system can implemented with any or a combination of the following technologies, which are each well known in the art: a discrete logic circuit(s) having logic gates for implementing logic functions upon data signals, an application specific integrated circuit (ASIC) having appropriate combinational logic gates, a programmable gate array(s) (PGA), a field programmable gate array (FPGA), etc.
[0037] The sensor program 51 operates various features of the hand antiseptic system 10 . The function of the sensor program 51 include, but are not limited to, determining if the sensors 20 A and 20 B have been triggered, determining the sequence that the sensors 20 A and 20 B were triggered, determining if the dispensing lever 36 has been actuated, determining the number of times the dispensing lever 36 has been actuated, determining the number of targets entering/exiting the area of interest, determining which dispensing system 16 to communicate with, and other operations that enable the hand antiseptic system 10 to function properly.
[0038] [0038]FIG. 3 is a plan view of one embodiment of the hand antiseptic system 10 . A sensitive area 60 (e.g. a hospital room or intensive care room) and a second area 62 (e.g. hallway or other room) are separated by a wall with an entrance 63 that typically includes a door 64 . The hand antiseptic system 10 can be used to ensure hand decontamination upon movement through the entrance 63 from one area to another. In the embodiment illustrated in FIG. 3, the hand antiseptic system 10 includes a bi-directional sensor system 14 and two dispensing systems 16 A and 16 B. One dispensing system 16 A is on one side of the entrance 63 , while the other dispensing system 16 B is on the other side of the entrance. Other embodiments can include one or more bi-directional sensor systems 14 and one or more dispensing systems 16 . The bi-directional sensor system 14 typically is located inside the sensitive area 60 near the entrance 63 to the sensitive area 60 . The bi-directional sensor system 14 can be located on a wall, as is shown in FIG. 3, or located on the ceiling.
[0039] [0039]FIG. 3 also depicts the two dispensing systems 16 A and 16 B in two different areas 60 and 62 . In this embodiment, dispensing system 16 A is located in the sensitive area 60 and is used by individuals entering the sensitive area 60 , while dispensing system 16 B is located in the second area 12 for individuals exiting the sensitive area 60 and entering the second area 62 .
[0040] Generally, the bi-directional sensor system 14 includes two sensors 20 A and 20 B (e.g. passive infrared sensors) positioned serially. Each sensor 20 A and 20 B is capable of sensing infrared energy in sensor areas 70 A and 70 B. An individual entering the sensitive area 60 passes through the second sensor area 70 B, which triggers the second sensor 20 B. Then the individual passes through the first sensor area 70 A, which triggers the first sensor 20 A. This sequence of triggering the sensors 20 B and 20 A indicates that the individual is entering into the sensitive area 60 . More particularly, the sensor program 51 of the computer 25 , based upon the triggering sequence, is capable of determining that an individual is entering the sensitive area 60 and communicates this to dispenser system 16 A. Conversely, an individual exiting the sensitive area 60 passes thought the first sensor area 70 A, which triggers the first sensor 20 A. Then the individual passes through the second sensor area 70 B, which triggers the second sensor 20 B. This triggering sequence of the sensors 20 A and 20 B indicates that the individual is exiting the sensitive area 60 and moving into the second area 62 . More particularly, the sensor program 51 of the computer 25 , based upon the triggering sequence, is capable of determining that an individual is exiting the sensitive area 60 and communicates this to dispenser system 16 B.
[0041] The following is an example of how the hand antiseptic system 10 can operate when an individual enters the sensitive area 60 . This scenario would occur when a patient with indwelling devices, such as central lines, are uniquely susceptible to external infection from the hospital environment, and these individuals require protection from external pathogens. In this scenario, hand decontamination is required upon entry to the sensitive area 60 . The alarm selector 22 is set for targets entering the sensitive area 60 . The visual alarm 32 on the dispensing system 16 A is actuated once both sensors 20 B and 20 A of the bi-directional sensor system 14 are triggered by an individual entering the sensitive area 60 of a patient. Upon actuation, the visual alarm 32 blinks for a pre-determined time period (e.g. five seconds). More specifically, the computer 25 instructs the bi-directional sensor system 14 to communicate with the dispensing system 16 A to trigger the visual alarm 32 to blink for a pre-determined time period. The visual alarm 32 can be de-activated when the dispensing sensor 34 on the dispensing system 16 A is actuated. The dispensing sensor 34 can be actuated by triggering (e.g. depressing) the dispenser lever 36 . Upon actuation of the dispensing sensor 34 , the visual alarm 32 is de-activated.
[0042] If the visual alarm 32 is not de-activated within the predetermined time period, the audible alarm 30 is activated to alert the individual to decontaminate their hands. The audible alarm 30 audibly alerts (e.g. beep or play a recorded message) the individual that their hands need to be decontaminated using the dispenser system 16 A. Like the visual alarm 32 , the audible alarm is de-activated when dispensing sensor 34 on the dispensing system 16 A is actuated. The dispensing sensor 34 can be actuated by triggering the dispenser lever 36 . Upon actuation of the dispensing sensor 34 , the audible alarm 30 and the visual alarm 32 are de-activated.
[0043] The following is an example of how the hand antiseptic system 10 can operate when an individual exits the sensitive area 60 and goes into the second area 62 . This scenario would occur when a patient with active wound infections represent a potentially catastrophic source of cross-infection to other patients, and strict hand decontamination is required by all personnel exiting the sensitive area, to prevent spread of infection to other individuals. This is particularly important in the setting of infection by antibiotic resistant organisms, such as methicillin resistant staphylococcus aureus (MRSA) or vancomycin resistant enterococcus (VRE). The alarm selector 22 is set for targets exiting the sensitive area 60 . In this scenario, the visual alarm 32 on the dispensing system 16 B is actuated once both sensors 20 A and 20 B on the bi-directional sensor system 14 are triggered by an individual exiting the sensitive area 60 of a patient. Upon actuation, the visual alarm 32 blinks for a pre-determined time period (e.g. five seconds). More specifically, the computer 25 instructs the bi-directional sensor system 14 to communicate with the dispensing system 16 B to trigger the visual alarm 32 to blink for a pre-determined time period. The visual alarm 32 can be de-activated when the dispensing sensor 34 on the dispensing system 16 B is actuated. The dispensing sensor 34 can be actuated by triggering (e.g. depressing) the dispenser lever 36 . Upon actuation of the dispensing sensor 34 , the visual alarm 32 is de-activated.
[0044] If the visual alarm 32 is not de-activated within the predetermined time period, the audible alarm 30 is activated to audibly alert the individual to decontaminate their hands. Like the visual alarm 32 , the audible alarm is de-activated when the dispensing sensor 34 on the dispensing system 16 B is actuated. The dispensing sensor 34 can be actuated by triggering the dispenser lever 36 . Upon actuation of the dispensing sensor 34 , the audible alarm 30 and the visual alarm 32 are de-activated.
[0045] The examples above illustrate how the hand antiseptic system 10 can be used for an individual entering or exiting a sensitive area 60 . Another example would combine the use of the hand antiseptic system 10 for both entering and exiting the sensitive area 60 in a manner similar to the previous two examples. This scenario would occur when strict isolation precautions are required for immuno-compromised patients, such as bone marrow transplants or other transplant patients. This scenario would require hand decontamination on both entry and exit to the sensitive area 60 . In this scenario the alarm selector 22 is set for targets entering and exiting the sensitive area 60 . The hand antiseptic system 10 operates in a manner similar to the previous examples except that once the individual who has entered the sensitive area 60 has de-activated the alarm 32 and/or 30 , the hand antiseptic system 10 resets the sensors 20 A and 20 B. The resetting occurs so that the hand antiseptic system 10 can determine when the individual is exiting the sensitive area 60 and appropriately alert the individual upon leaving the sensitive area 60 to decontaminate their hands. In another example where the sensitive area 60 is empty, with no patient currently being treated, the hand antiseptic system 10 could be inactivated by turning the alarm selector 22 to the “off” position.
[0046] Another embodiment of the hand antiseptic system 10 provides the capability of determining the number of individual entering/exiting the sensitive area 60 and generating an appropriate visual and/or audible alarm 32 and 30 , which depends upon the number of individuals entering/exiting the sensitive area 60 . In general, if “n” number of individuals enter/exit the sensitive area 60 , then “n” number of visual and/or audible alarms can be activated. More specifically, in the event a single individual is identified, a single, repeating visible stimulus (“blink”) and/or audible stimulus (a “beep”) is generated. Alternatively, in the event that two individuals are identified, two repeating visual and/or audible stimuli are generated. The hand antiseptic system 10 can be further modified to determine the number of times the dispenser lever 36 of the dispenser system 16 A and 16 B is depressed. The computer 25 of the bi-directional sensor system 14 is capable of determining the number of individuals detected and the number of individuals having decontaminated their hands. The computer 25 then derives a “net” number of individuals that need to decontaminate their hands, and generates a visual and/or audible alarm 32 and 30 to indicate that a certain number of individuals need to decontaminate their hands. For example, if one individual is identified, a single actuation of the dispenser lever 36 can de-activate the alarm completely. If two individuals are identified, a single activation of the dispenser lever 36 can alter the visual and/or audible alarm 32 and 30 into an appropriate visual and/or audible alarm 32 and 30 indicating that only one individual still needs to decontaminate their hands. A second activation of the dispenser lever 36 can de-activate the alarm completely. A one-to-one ratio of people entering/exiting the sensitive area 60 and decontaminating their hands is therefore provided. In this manner, full compliance with hand decontamination by all individuals entering/leaving the sensitive area 60 can be achieved.
[0047] Many variations and modifications may be made to the hand antiseptic system and method 10 without departing substantially from the spirit and principles of the invention. All such modifications and variations are intended to be included herein within the scope of this disclosure and the invention and protected by the following claims.
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A pair of sensors ( 20 A and 20 B) are mounted at the entrance to a germ sensitive area. When a person enters the area the sensors are activated in sequence, indicating the direction of movement of the person. An indicator, such as a light or sound alarm is mounted upon an antiseptic dispenser, located within the area. The alarm is actuated by the movement and is de-activated once antiseptic is dispensed from the unit. Likewise when the person moves out of the germ sensitive area, the alarm on a dispenser unit located outside the area is energized and is de-activated upon dispensing of antiseptic.
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GOVERNMENT RIGHTS
The United States Government has rights in this invention pursuant to Contract No. W-7405-ENG-36 between the United States Department of Energy and the University of California for the management and operation of Los Alamos National Laboratory.
FIELD OF THE INVENTION
The present invention generally relates to computer communication networks, and more particularly to collecting high-resolution information about all traffic traversing a single network link. Specifically, this invention pertains to a system for high-speed high-accuracy capture of network traffic that combines efficient commodity-based hardware in an architecture that hides disk latency and bandwidth.
BACKGROUND OF THE INVENTION
Computer networks are becoming an integral part of daily lives through technologies such as the Internet, wireless personal digital assistants, ad-hoc wireless and mobile networks. The potential for using these networks to assist in illegal or terrorist-based activities is very large. The ability to monitor network traffic and police computer networks is critically important.
Network speeds have been increasing at an incredible rate, doubling every 3-12 months. This is even faster than one version of the remarkably accurate “Moore's Law” observation made in 1965 that states that processing power doubles every 18-24 months. However, while network speeds have been increasing exponentially, disk and bus bandwidth have only increased linearly. The disparity between network, CPU, and disk speeds will continue to increase problematically. Most analysts agree that there are enough new manufacturing methods, designs, and physics available in the near future that these trends will continue for some years to come. One issue fueling this trend is that networks are increasingly optical while computers are primarily electronic.
The implications of these trends are critically important. Conventional methods will not suffice to capture network traffic in the future. As research technology becomes conventional technology, tcpdump/libpcap style processing will have neither the requisite processing power nor the disk bandwidth available to handle fully saturated network links. Any such single-machine design, no matter how well implemented, will be unable to “keep up” with the network. For example, field tests of tcpdump/libpcap running on a 400-MHz machine over a Gigabit Ethernet (GigE) backbone showed that tcpdump could monitor traffic at speeds of no more than 250 Mbps with accuracy of no greater than milliseconds. At times of high network utilization (e.g., approximately 85%), over half of the packets were lost because this system could not handle the load. In addition, because few network traffic monitoring systems are available, many vendors offer custom hardware solutions with proprietary software. These systems are very expensive.
It is possible to address disk and accessory bandwidth by using redundant arrays of independent disks (RAID) systems as network-attached storage (NAS) and the memory integrated network interface (MINI) paradigm, but both systems are currently somewhat expensive. Memory bandwidth issues have been addressed by dynamic random access memory chip technology such as RAMBUS or simple increases of processor cache size, but these techniques have failed to live up to their potential. These approaches in combination with highly tuned commercial-off-the-shelf (COTS) monitors and a specialty monitor have been tested. Unfortunately, this approach is expensive and still susceptible to the growing disparity between network, CPU, and disk speeds.
Most limitations in current network monitoring methodologies are due to compromises in scalability, user level versus kernel level tasks, and monitor reliability. They compromise scalability by forcing the use of a single machine or processor rather than symmetric multiprocessing (SMP) or cluster systems. However, at projected network speeds the collection task for a single machine can require so much processing power that too little remains to actually do anything useful with the data.
The user level/kernel level compromise gives up efficiency, real-time monitoring, and timer resolution for ease of use. Most currently available network monitoring approaches are user level applications tied to their operating system's performance; these approaches depend upon system calls such as gettimeofday( ). Conversely, a dedicated operating system (OS) operates at kernel level and uses lower-level hardware calls such as rdtsc( ) (read-time stamp counter).
Reliability compromises are a misguided attempt to reduce cost but introduce issues with many implementations that fail to keep up with network speeds, fail to maintain a count of dropped packets, crash or hang during use.
The performance of currently available network traffic monitoring systems can be illustrated by tcpdump, libpcap, and remote monitoring (RMON) systems. Tcpdump is an invaluable, easy-to-use, portable, free tool for network administrators. It is designed as a user interface application relying upon functionality contained in the lower-level libpcap library, which has also been successfully used with other applications. Unfortunately, by nature tcpdump and libpcap have limitations due to decisions made concerning the compromises previously discussed. In particular, libpcap executes on a single machine, uses system calls to perform timestamps, and can be unreliable.
Furthermore, libpcap suffers from efficiency problems pandemic to implementations of traffic collection at user level. The operating system performs the required packet copy in the network stack (for transparency); this can double the time required to process a packet. The exact method used by libpcap and other tools varies by operating system but always involves a context switch into kernel mode and a copy of memory from the kernel to the user level library. This “call-and-copy” approach is repeated for every packet observed in Linux (or other operating systems), while other implementations use a ring buffer in an attempt to amortize costs over multiple packets. At high network speeds, the overhead of copying each individual packet between kernel and user space becomes so excessive that as much as 50% of the aggregate network traffic is dropped when using tcpdump/libpcap over a gigabit Ethernet link.
Remote monitoring (RMON) devices contain some traffic-collection functionality as well as some management functionality. These devices provide a superset of the functionality of tcpdump/libpcap but work in much the same way. Although the management software provides a nice interface to the hardware RMON device, it also introduces substantial overhead that limits the fidelity of packet timestamps to the order of seconds. This fidelity is a thousand times worse than tcpdump. RMON devices have several additional limitations.
First, the packet-capture mode of the RMON device often silently drops packets. Second, the data-transfer mode of the RMON device requires an active polling mechanism from another host to pull data across. Finally, the RMON devices themselves hang or crash often, e.g., every 36-72 hours.
Thus, there is need for a new, specialized network traffic monitoring methodology that is scalable, efficient, reliable, and inexpensive. The need for such a system has heretofore remained unsatisfied.
SUMMARY OF THE INVENTION
The present invention satisfies this need, and presents a system and associated method for collecting high-speed network traffic. The present system simultaneously addresses the issues of scalability, performance, cost, and adaptability with respect to network monitoring, collection, and other network tasks. The present system scales to gigabit-per-second (Gbps) speeds and achieves these speeds while taking measurements that are up to nine orders of magnitude more accurate than commercial offerings and up to two orders of magnitude less expensive than commercial offerings. In addition to network monitoring, the present system can also be configured as a real-time network intrusion detection system or a wide-area network emulator.
The methodology and apparatus for the present system comprises two specially configured commodity parts: the operating system and the architecture/apparatus. The present system uses a dedicated operating system for traffic collection to maximize efficiency, scalability, and performance. This operating system operates as close to the hardware as possible and avoids running extraneous services that would compete with traffic collection for resources.
One feature of the present system is that the monitoring software runs entirely in kernel space. Consequently, no context switches are required and buffer copying is minimized, eliminating the need to copy data to/from kernel space to user space. In addition, the present system allows for variable packet-size capture and real-time processing of data. Another aspect of the present system utilizes the cycle-counter register to ensure high-fidelity timestamps. This approach to timestamping provides accuracy and precision that is thousands of times better than current state-of-the-art.
A scalable infrastructure and apparatus for the present system is provided by splitting the work performed on one host onto multiple hosts. The first host, or “packet monitor” captures packets, collects the relevant data from the packets, and forwards the collected packet data to multiple other hosts, or “data processors”. The data processors either save, display, or process the data further such as required for intrusion detection.
This architectural separation allows tasks to be pipelined and handled concurrently. For instance, after the packet monitor captures, filters, and forwards data from the first packet, the packet monitor can then move onto a second packet. Meanwhile, the first packet is being processed by an data processor, e.g., recorded to disk. This parallel processing of packets multiplies the rate at which traffic can be recorded compared to present technology—doubling with two machines, tripling with three, and so forth.
Furthermore, to hide data processor limitations, such as the slow speed of disk writes, the present system can perform the disk writes to the data processors in parallel. For example, given a packet monitor and four data processors, a different packet can be processed by each of the data processors. The present system records four packets in parallel while the packet monitor captures a fifth packet. Such a scenario can theoretically increase the traffic-monitoring rate by a factor of five.
The present system performs as well or better than current commercial network collection systems at a fraction of the cost.
The present system can be used in any computing system that communicates over a network. Examples include high-performance computing environments, supercomputers, PC-computing clusters, Internet-based environments, web-server clusters, digital library clusters, institutional networks, Cyber-Security, and middleboxes or proxy servers. The Internet infrastructure can leverage the present system to perform monitoring and network intrusion detection among other tasks.
BRIEF DESCRIPTION OF THE DRAWINGS
The various features of the present invention and the manner of attaining them will be described in greater detail with reference to the following description, claims, and drawings, wherein reference numerals are reused, where appropriate, to indicate a correspondence between the referenced items, and wherein:
FIG. 1 is a schematic illustration of an exemplary operating environment in which a high-speed network traffic collecting system of the present invention can be used;
FIG. 2 is a diagram of the high-level architecture of the preferred embodiment of the high-speed network traffic collecting system of FIG. 1 ;
FIG. 3 is a diagram of high-level architecture of the second embodiment of the high-speed network traffic collecting system of FIG. 1 ;
FIG. 4 is a diagram of high-level architecture of the third embodiment of the high-speed network traffic collecting system of FIG. 1 ; and
FIG. 5 is a process flow chart illustrating a method of operation of the high-speed network traffic collecting system of FIGS. 1 and 2 .
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The following definitions and explanations provide background information pertaining to the technical field of the present invention, and are intended to facilitate the understanding of the present invention without limiting its scope:
API (application program interface): A specific method prescribed by a computer operating system or by another application program by which a programmer writing an application program can make requests of the operating system or another application.
DMA: (Direct Memory Access/Addressing) A method of transferring data from one memory area to another without having to go through the central processing unit.
Ethernet: The most common type of local area network, originally sending its communications through radio frequency signals carried by a coaxial cable at 1 Mbps. This cable was shared (hubbed) among many machines and each one could transmit over the link. The second and third generation used Category 5 twisted-pair copper cable, while today, the fourth-generation 10 Gigabit Ethernet uses optical fiber and is a point-to-point (switched) computer communication network. Network communication software protocols used with Ethernet systems vary, but include Novell Netware and TCP/IP.
IP: (Internet Protocol) The network layer protocol in the TCP/IP communications protocol suite (the “IP” in TCP/IP). IP contains a network address and allows routing of messages to a different network or subnet.
Kernel: The central part of an operating system that performs the most basic functions, such as coordinating use of computer memory (RAM), disks, or low-level network access.
Linux: An Open Source implementation of UNIX created by Linus Torvalds that runs on many different hardware platforms including Intel, Sparc®, PowerPC, and Alpha Processors.
PCI bus: (Peripheral Component Interconnect) A peripheral bus commonly used in PCs, Macintoshes and workstations. PCI provides a high-speed data path between the CPU and peripheral devices such as video, disk, network, etc.
RMON: (Remote MONitoring) Extensions to the Simple Network Management Protocol (SNMP) that provide comprehensive network monitoring capabilities. In standard SNMP, the device must be queried to obtain information. The RMON extensions allow proactive decisions; an administrator can set alarms on a variety of traffic conditions including specific types of errors.
SMP: Symmetric Multi-Processing. A computer system that has two or more processors connected in the same chassis, managed by one operating system, sharing the same memory, and having equal access to input/output devices. Application programs may run on any or all processors in the system; assignment of tasks is decided by the operating system. One advantage of SMP systems is scalability; additional processors can be added as needed.
TCP: Transmission Control Protocol. The most common Internet transport layer protocol, defined in STD 7, RFC 793. This communications protocol is used in networks that follow U.S. Department of Defense standards. It is based on the Internet Protocol as its underlying protocol; TCP/IP means Transmission Control Protocol over Internet Protocol. TCP is connection-oriented and stream-oriented, providing for reliable communication over packet-switched networks.
UDP: User Datagram Protocol. A communications protocol for the Internet network layer, transport layer, and session layer, which makes it possible to send a datagram message from one computer to an application running in another computer. Like TCP (Transmission Control Protocol), UDP is used with IP (the Internet Protocol). Unlike TCP, UDP is connectionless and does not guarantee reliable communication; the application itself must process any errors and check for reliable delivery.
FIG. 1 illustrates an exemplary high-level architecture of a network traffic collection system 100 comprising a system 10 that utilizes a high-speed high-fidelity kernel machine. System 10 includes a software programming code or computer program product that is typically embedded within, or installed on a computer. Alternatively, system 10 can be saved on a suitable storage medium such as a diskette, a CD, a hard drive, or like devices.
System 100 comprises two parts, each running on separate hosts. The first part is system 10 comprising the highly efficient dedicated traffic collection operating system 15 installed on host computer 20 with network tap 25 . The second part is the user level machine 30 , comprising user level tools and scripts 35 , installed on host computer 40 . The user level machine(s) 30 further process, save, or display the collected traffic. A dedicated network link 45 connects the user level machine 30 with system 10 .
System 10 uses kernel code running as close to the hardware as possible to maximize efficiency, scalability, and performance in critical areas. As a dedicated system, it avoids extraneous services competing for resources and decreasing security. Furthermore, running entirely in kernel space means that no context switches are required, and buffer copying is kept to a minimum, e.g., data no longer has to be copied from kernel space to user space. System 10 utilizes the cycle-counter register to provide high-fidelity timestamps with accuracy and precision thousands of times better than implementations of other approaches.
User level machine 30 maximizes usability and expressive power by performing less time-critical tasks such as saving to disk. The ability of the kernel level code in traffic collection operating system 15 to stripe across multiple user level machines makes efficiency less of an issue and enables complex analysis in real-time using clusters of machines.
The high-level architecture of system 100 is shown in more detail in FIG. 2 , presenting a logical view of the hardware configuration and the method for shared processing among multiple hosts. System 10 first collects traffic from the raw network link 205 via a network tap 25 . The network interface card 210 then collects traffic from the tapped network link 215 and passes the data over the peripheral PCI bus 220 to the main memory/CPU 225 .
The main memory/CPU 225 gathers the appropriate packet headers. These packet headers are passed back over the accessory PCI bus 230 and network interface card 235 onto a dedicated network link 45 to one or more data processors such as data processor 240 , 245 , 250 , and so forth for display and/or storage.
System 10 comprises the network interface card 210 , the peripheral PCI bus 220 , the main memory/CPU 225 , the accessory PCI bus 230 and the network interface card 235 . Any on-board processor on the network interface card (NIC) 235 can be utilized by system 10 to provide even better performance.
With the adoption of a dedicated traffic collection operating system 15 for system 10 , the display and storage of data traffic become the bottlenecks in traffic collection rather than first-level collection and analysis. To address those bottlenecks, system 10 is designed to have multiple, independent PCI busses and a motherboard with bandwidth capable of operating these buses concurrently at full speed. That is, the chipset does not become a new bottleneck as the prior bottleneck is removed.
The simplest configuration scales well beyond current techniques, but all the traffic still passes through a single host. To scale even further, e.g., 10 Gbps, the 64-bit/66-MHz PCI bus limitation of 4.2 Gbps must be avoided. A second embodiment of the present system is shown in FIG. 3 , illustrating a configuration with multiple taps to reach even higher network speeds. System 300 is generally similar in design and function to system 10 with exception that network traffic collection configurations containing system 300 are duplicated and attached in parallel to the same raw network link 205 , as shown by network traffic collection configurations 305 , 310 , 315 . Packet headers are passed to one data processor 240 as shown in FIG. 2 or multiple data processors 320 as shown in FIG. 3 .
Placing network traffic collection configurations 305 , 310 , 315 in parallel removes the requirement that all traffic move through a single host. However, this approach only works if the following conditions hold:
1. Each network tap 25 can be configured to split off only a given subset of traffic, or each network interface card 210 is capable of processing link-level packet headers at full link speed.
2. The union of the sets of traffic that systems 305 , 310 , 315 (and so forth) handle covers the original set of traffic.
3. There exists a globally synchronized clock.
The first condition is true when multiple wavelengths are used on a single optical fiber. Such a scenario is becoming more common as the cost of dense wavelength division multiplexing (DWDM) falls. In this case, each network tap 25 splits a single wavelength or set of wavelengths from the fiber in raw network link 205 for processing.
The second condition generally follows if the network tap 25 has been properly installed. Subsets of traffic collected by each system 300 need not be disjoint (although this is desirable); post-processing of the collected traffic can remove duplicates based on the collected headers and accurate timestamps.
The third condition can be addressed by the network time protocol (NTP). However, NTP only provides clock accuracy on the order of a millisecond. If data sets are not entirely disjoint (some packets with their associated timestamps are seen in multiple data sets) or if a hardware interface is dedicated solely to synchronization and management, then highly accurate synchronization can be provided.
The first and second embodiments of the present system focus on the use of commercially available hardware to perform network-monitoring tasks. However, the speed of core network links may outstrip commercially available hardware. For even faster network collection, a third embodiment connects the network tap 25 to a switch's uplink input. Switch hardware can then demultiplex the input to multiple copies of system 10 operating in parallel.
FIG. 4 shows how system 400 might be implemented in hardware analogous to a network switch, possibly using a commercially available switch with predefined routes to appropriately split traffic. System 400 is generally similar in design and function to system 10 with the exception that instead of a switch uplink, network tap 25 copies traffic off raw network link 205 . Instead of a true many-to-many switch fabric, the third embodiment requires only a simplified one-to-many demultiplexer 405 .
The one-to-many demultiplexer 405 connects to lower-speed network links (just as a switch would) to which many copies of system 10 can be connected using port mirroring. Port or interface mirroring is a technique by which the traffic from one or more interfaces on a network switch (the mirrored interfaces) is copied to another port (the mirroring interface). This provides a mechanism to transparently observe traffic passing over the mirrored interfaces by observing traffic over the mirroring interface. Alternatively, simple chips could implement system 400 functionality and be integrated with this network traffic collection configuration, leaving only the data processors 320 separate.
While quite different from the tcpdump/libpcap style of collecting traffic, the architecture of the third embodiment is somewhat similar to the RMON specification. The third embodiment differs from RMON in two fundamental ways. First, system 400 pushes data to the data processors; using an RMON specification the data processors must poll the RMON device for data, i.e., pull the data from the RMON. Second, the individual network probe of the RMON is replaced in the third embodiment with an explicitly parallel methodology.
For current network speeds, system 10 of the first embodiment suffices for gigabit Ethernet. System 10 is implemented on Intel-based x86 hardware. The software portion of system 10 is derived from a Linux 2.4 kernel with the init( ) function replaced by code that implements the core functions of system 10 . The invention may be implemented on any type of hardware (not only x86) that has a network link; similarly Linux was used only to minimize implementation time—the invention only requires a way to receive packets, process them, and send them.
This approach leverages a pre-existing code base for scheduler, virtual memory, device drivers, hardware probing, etc. This was done to minimize implementation time; the invention can be implemented with any operating system or hardware. The kernel for system 10 is the absolute minimum required to manage low-level hardware tasks and provide a useful application programming interface (API). The API of the stripped-down kernel is used to program system 10 . Other implementations of system 10 may provide their own device drivers and memory handling to avoid the current use of Linux code.
The core sequence of events for any implementation of the method 500 of system 10 is described in the process flow chart of FIG. 5 . At block 505 , the kernel of system 10 initializes, probes hardware, and calls system 10 as the sole thread of execution. During the initial boot-up process, all the low level BIOS calls are performed by the kernel in system 10 before any traffic collection code is called. At block 510 , system 10 parses the kernel command line for options. The ability to parse kernel command-line arguments allows system 10 to accept boot-time configuration information such as IP addresses or modes. System 10 then brings up network interfaces and waits for link negotiation at block 515 . At block 520 , system 10 calls a “mode” function; in this case, traffic collection. The “mode” function allows use of the framework of system 10 for performing related tasks such as network flooding for testing or for enabling “application layer” functionality that is logically separate from system 10 .
System 10 then executes the following operations: receive a packet at block 525 and timestamp the packet at block 530 . Timestamps are performed either as packets enter the network stack on the host main memory/CPU 225 . This implicitly assumes that there is a fairly constant delay between packet arrival from the raw network link 215 and the time it enters the network stack via a DMA by the network interface card 235 and a host interrupt. Timestamps may also be performed by the network interface card 210 .
System 10 collects information about the packet at block 535 . This information includes the 64-bit timestamp, length “off-the-wire”, and Ethernet information such as addresses of source and destination in addition to type of service or 802.3 length. System 10 also collects IP information such as addresses of source and destination, lengths of packet and header, and protocol number. TCP/UDP information collected by system 10 includes ports of source and destination in addition to length of UDP packet or TCP header. This information collected at block 535 is the minimal but most useful subset of data available. To check validity of packets, some redundancy is included with lengths. In practice, this information resolves to about 42 bytes of data per packet. Consequently, system 10 is collecting about 6.5% of the total traffic given a 650-byte average packet size. The type of information collected can be changed as required for various applications of system 10 ; for example whole packets may be collected, or simply the first 68 bytes to be analagous to tcpdump/libpcap.
The remaining data is sent to the user level host computer 35 for saving or further analysis. To minimize the overhead of sending packets on the outgoing link, system 10 buffers the results at block 540 until a packet is filled. System 10 verifies the status of the output buffer at block 545 . If the output buffer is full, system 10 selects an interface at block 550 . At block 555 , system 10 enqueues the packet for sending; the device driver sends the packet asynchronously. For 42-byte data collection per input packet and 1500-byte Ethernet MTU, system 10 sends the results from about 34 input packets per output packet.
At decision block 560 , system 10 verifies that the abort condition is not present. If ctrl-alt-del has been pressed or a specially formatted link-level “reboot” packet has been received by system 10 , system 10 proceeds to block 565 and stops the network traffic collection process. Otherwise, system 10 returns to block 525 and repeats blocks 525 through 560 until the process is aborted. Since system 10 runs on general-purpose hardware, one could conceive of incurring security risks by placing such a machine on a network backbone. The passive nature of system 10 and the inability to modify parameters without a reboot currently addresses this problem.
It is to be understood that the specific embodiments of the invention that have been described are merely illustrative of certain application of the principle of the present invention. Numerous modifications may be made to the high-speed and high-fidelity system and method for collecting network traffic invention described herein without departing from the spirit and scope of the present invention.
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A system is provided for the high-speed and high-fidelity collection of network traffic. The system can collect traffic at gigabit-per-second (Gbps) speeds, scale to terabit-per-second (Tbps) speeds, and support additional functions such as real-time network intrusion detection. The present system uses a dedicated operating system for traffic collection to maximize efficiency, scalability, and performance. A scalable infrastructure and apparatus for the present system is provided by splitting the work performed on one host onto multiple hosts. The present system simultaneously addresses the issues of scalability, performance, cost, and adaptability with respect to network monitoring, collection, and other network tasks. In addition to high-speed and high-fidelity network collection, the present system provides a flexible infrastructure to perform virtually any function at high speeds such as real-time network intrusion detection and wide-area network emulation for research purposes.
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BACKGROUND OF THE INVENTION
One of the conventional manners of attaching wheel covers made of plastics to the disc wheel rims of the vehicle comprises attaching a wire ring from inside to circular stopper ribs arranged integral along the circumferential rim of the wheel cover on the backside thereof to resiliently urge the circular stopper ribs outward. An example of this approach is disclosed in U.S. Pat. No. 4,027,919 another approach disclosed, e.g., in U.S. Pat. No. 2,746,805, involves inwardly curving a part of such a wire ring to produce a spring force. A further approach proposed by the applicant of the present invention as a Japanese Utility Model Application Sho No. 60-66209 comprises arranging a plurality of outer and inner stopper ribs along the circumferential rim of the wheel cover on the backside thereof and inserting a plate spring between the outer and inner stopper ribs, respectively, wherein the spring pressure of each of the plate springs is adjusted to hold the wheel cover onto the wheel rim.
However, engagement between the wheel covers and rims becomes inferior relatively soon because of deterioration of the plastics of which the stopper ribs on the backside of the wheel covers are made. In addition, the spring pressure of the wire ring and those of the plate springs are likely to become deteriorated. Further, it is difficult to adjust them to have an appropriate spring pressure. Therefore, any successful and satisfactory arrangement has not been proposed yet to attach the wheel covers made of plastics to the wheel rims.
SUMMARY OF THE INVENTION
The present invention relates to a wheel cover made of synthetic resin and, more particularly, it relates to a cover attaching arrangement.
The present invention is intended to usually apply a certain pre-loaded bias force between outer and inner prop-like ribs arranged integral along the circumferential rim of the plastic-made wheel cover on the backside thereof. Namely, a plurality of outer and inner prop-like ribs are arranged integral along the circumferential rim of the wheel cover on the backside thereof and a spring which can be expanded wider than the interval between the outer and inner ribs is fitted between the outer and inner ribs, whereby the interval between the outer and inner ribs is maintained at value no greater than a predetermined value so as to store a portion of the pre-loaded biasing force of the spring acting between the outer and inner ribs.
When the wheel cover is to be attached to the wheel rim, the outer and inner ribs are forcedly and resiliently fitted together with the springs into the hump portion of the wheel rim and when the outer and inner ribs are thus fitted, they are re-sprung together with the springs to generate the necessary retaining forces. When the wheel cover is to be detached from the disc wheel, the wheel cover is removed from the hump portion to again the preloaded biasing force is again provided between the outer and inner ribs.
The first object of the present invention is to provide a wheel cover made of synthetic resin and having a preloaded biassing force generating mechanism and capable of being reliably fixed to the wheel rim.
The second object of the present invention is to provide a wheel cover which can be applied to the wheel rim even when the wheel rim has any dimensional error.
The third object of the present invention is to provide a wheel cover which can be easily attached to and detached from the wheel rim.
The fourth object of the present invention is to provide a wheel cover which can be kept easily detachable over a long time period of use.
The fifth object of the present invention is to provide a wheel cover lower in cost and more reasonable in function.
These and other objects as well as merits of the present invention can be achieved by a wheel cover of the present invention and an example of the wheel cover will be described in detail with reference to the accompanying drawings.
It should be understood that various changes and modification within the spirit of the present invention are covered by claims attached hereto.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a perspective view showing a part of an example of the wheel cover according to the present invention.
FIG. 2 is a sectional view taken along a line II-II' in FIG. 1 and showing the wheel cover fitted into the wheel rim of the disc wheel.
FIGS. 3a and 3b are perspective views showing the main portions of other examples of the wheel cover according to the present invention.
FIG. 4a is a perspective view showing another example of the spring which is used with the wheel cover of the present invention.
FIG. 4b is a sectional view showing the spring in FIG. 4a arranged between outer and inner ribs.
FIG. 5 is a sectional view showing the wheel cover in FIGS. 4a and 4b attached to the disc wheel.
DETAILED DESCRIPTION OF THE INVENTION
As shown in FIG. 1, a plurality of inner and outer prop-like stopper ribs 1 and 2, 2' are formed integral along the circumferential rim of a wheel cover (H) on the back side thereof and arms 3, 3' for interconnecting the inner and outer stopper ribs 1 and 2, 2' are provided between the inner and outer stopper ribs 1 and 2, 2'. The foremost end of each of the arms 3 and 3' is formed to have a hook (a) or (a') and the arms 3 and 3 are engaged with each other at their hooks (a) and (a').
A U-shaped spring 4 is fitted, its opened side up, between the inner and outer stopper ribs 1 and 2, 2'. The interval between the inner and outer stopper ribs 1 and 2, 2' is made smaller than the extent to which the opened side of the spring 4 can be left expanded when it is not fitted between the inner and outer stopper ribs 1 and 2, 2'. And this spring 4 is forcedly fitted between the inner and outer stopper ribs 1 and 2, 2'. Both sides of the thus-fitted spring 4 urge the inner faces of the inner and outer stopper ribs 1 and 2, 2' to lengthen the interval a little between the inner and outer stopper ribs 1 and 2, 2'. The arms 3 and 3' are thus engaged with each other at their hooks (a) and (a') to keep the interval certain between the inner and outer stopper ribs 1 and 2, 2'. A substantial pre-loaded biassing force is thus stored which acts between the inner and outer stopper ribs 1 and 2, 2' to enable the interval between the inner and outer stopper ribs to be shortened when force is applied from outside to the inner and outer stopper ribs 1 and 2, 2' and to restore its original length when the force is removed. The force of the spring which tends to open outward is stopped when the arms 3 and 3' are engaged with each other at their hooks (a) and (a'). Namely, the hooks (a) and (a') stop the inner and outer stopper ribs 1 and 2, 2' from opening outward, thereby keeping the interval between the inner and outer stopper ribs certain.
When the wheel cover (H) is to be fitted into a hump portion (d) along the rim of a disc wheel (D) (see FIG. 2), the outer stopper ribs 2, 2' are forced inward against the spring 4 and after the wheel cover is thus fitted onto the disc wheel (D), the outer stopper ribs 2, 2' are spread into the hump portion (d) to completely fix the wheel cover onto the disc wheel.
When the wheel cover (H) is to be detached from the disc wheel (D), the wheel cover (H) is removed from the hump portion (d) according to the same action as seen in the cover fitting process and the certain pre-loaded biassing force is again maintained between the inner and outer stopper ribs 1 and 2, 2'.
FIG. 3a shows another example of the wheel cover wherein both sides 5 between inner and outer stopper ribs 1 and 2 are of simple bellow type and these bellow-like sides and the inner and outer stopper ribs are made as a single unit. FIG. 3b shows a further example of the wheel cover wherein both sides 5' between inner and outer stopper ribs 1 and 2 are of more complicated bellow type.
When the spring 4 is fitted between the inner and outer stopper ribs 1 and 2 in the case of these examples shown in FIGS. 3a and 3b, the pre-loaded spring force is applied to the inner and outer stopper ribs 1 and 2, as seen in FIG. 1. The U-shaped spring 4 used has a spring width larger than the interval between the inner and outer stopper ribs 1 and 2.
FIGS. 4a and 4b show another spring 4' wherein a projection (f) extends horizontal from the center of a half wing (e) at the upper opened end thereof and the foremost end of the projection (f) is bent downward to engage another half wing (g) of the spring 4'. When the spring 4' is fitted between the inner and outer stopper ribs 1 and 2, 2', as shown in FIG. 4b, the pre-loaded biassing force can be provided between the inner and outer stopper ribs 1 and 2, 2' by the pre-loaded spring force of the compressed spring 4' (see FIG. 5). In this case, however, the arms 3 and 3' shown in FIG. 1 and the bellow-type sides 5 and 5' shown in FIGS. 3a and 3b are not necessarily needed.
When the spring 4' is fitted between the inner and outer stopper ribs 1 and 2, 2', it is kept spread to have a certain spring width and when force is applied from outside to thus-assembled ribs, however, it is forced inward to shorten its spring width and restored again to have the certain spring width when the force is removed. When these springs 4' are fitted between the inner and outer stopper ribs 1 and 2, 2' and the wheel cover (H) is then fitted into the hump portion along the rim of the disc wheel (D) (see FIG. 5), the outer stopper ribs 2 and 2' are forced inward against the springs 4' and they are then spread into the hump portion (d) to completely fix the wheel cover (H) onto the disc wheel (D). When the wheel cover is to be detached from the disc wheel, the outer stopper ribs 2 and 2' are forced inward against the springs 4' and released from the hump portion (d). The pre-loaded force of the spring 4' is again stored or maintained between the inner and outer stopper ribs 1 and 2, 2' by the spring 4' itself.
The springs shown in FIGS. 1 through 3b may be formed as a coiled line spring, a torsion spring or the like.
An additional effect of the present invention is that even when springs each having a small spring constant or force are used, large and reliable force can be obtained by the pre-loaded biassing force providing mechanism of the wheel cover to fix the cover onto the disc wheel.
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A wheel cover provided with a pre-loaded spring mechanism wherein a plurality of inner and outer prop-like stopper ribs are arranged integral along the circumferential rim of the wheel cover on the backside thereof, said wheel cover being made of synthetic resin, and a spring which can be expanded wider than the interval between the inner and outer stopper ribs is fitted between the inner and outer stopper ribs, whereby the interval between the inner and outer stopper ribs can be usually kept certain to provide a pre-loaded spring force for fixing the wheel cover to the rim of a disc wheel.
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CROSS-REFERENCE TO RELATED APPLICATION
[0001] The present application claims priority of Korean Patent Application Number 10-2011-0130203 filed Dec. 7, 2011, the entire contents of which application is incorporated herein for all purposes by this reference.
BACKGROUND OF INVENTION
[0002] 1. Field of Invention
[0003] The present invention relates to a control knob for a vehicle, and more particularly, to a control knob for a vehicle, with an improved outward appearance.
[0004] 2. Description of Related Art
[0005] In general, a vehicle is equipped with a shift lever to select each gear. Further, when the shift lever is manipulated by a driver, a selecting cable and a shifting cable connected to the bottom of the shift lever are moved in connection to perform selecting and shifting of gears.
[0006] A control knob is installed on the shift lever. Here, the control knob denotes a handgrip installed on the end of the shift lever. Further, the control knob is formed to improve the grip feel of the shift lever. Moreover, as a decorative element inside a vehicle, the outward appearance of a control knob is important.
[0007] A control knob may be produced by applying dual injection molding according to the intent of the producer. Here, dual injection molding is a forming method in which two materials are used to produce an integrally and/or monolithically formed item. In such dual injection molding, a mold designed to be capable of dual injection molding is used which uses an injection molding machine with a structure in which two injection molding devices, a rotating device installed on a moving plate, and a core or a slide structure are used. Further, one material is injected in a primary cavity, and another material is injected into a secondary cavity to produce a formed item in which two materials are integrally formed.
[0008] In dual injection molding, because the primary cavity and the secondary cavity are precisely replaced, there are few restrictions as to the shape and the range of products to which the process may be applied. As described above, two materials are simultaneously extruded in dual injection molding. Accordingly, costs may be reduced and designs may be diversified when compared to a related art forming method which requires that two components are formed through two extrusion processes, followed by secondary processing such as bonding or painting.
[0009] However, for a control knob produced by dual injection molding, a boundary line may be formed between two different materials or an abrupt change in color may occur, which may deteriorate the outward appearance of the control knob.
[0010] The information disclosed in this Background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
SUMMARY OF INVENTION
[0011] Various aspects of the present invention provide for a control knob for a vehicle having the advantages of an improved outward appearance.
[0012] Various aspects of the present invention provide for a control knob for a vehicle, which is produced by dual injection molding of two different materials, is installed on one end of a shift lever, and functions as a handgrip, the control knob including an opaque portion formed of an opaque material which is one of the two materials, a transparent portion formed of a transparent material which is the other of the two materials, an overlapping portion at which the opaque portion and the transparent portion overlap, and a coated portion formed of paint applied to portions of the transparent portion that do not overlap with the opaque portion, wherein a boundary surface between the opaque portion and the transparent portion is formed in a slope such that a refractive index of light passing through the transparent portion from the overlapping portion is close to a refractive index of light passing through the transparent portion from the coated portion.
[0013] The overlapping portion may be formed by a portion of a top surface of the opaque portion overlapping a portion of an undersurface of the transparent portion.
[0014] A boundary line formed to be externally exposed by the boundary surface may be formed at a side surface of the overlapping portion.
[0015] The coated portion may be formed on an undersurface of the transparent portion.
[0016] The boundary surface between the opaque portion and the transparent portion may be formed sloped as a gradually curved surface.
[0017] The boundary surface between the opaque portion and the transparent portion may be formed in a slope, such that a thickness of the transparent portion from the overlapping portion gradually changes along the boundary surface.
[0018] As described above, according to various aspects of the present invention, a boundary line between two different materials may be formed in a portion that is not visible. Further, abrupt differences in color due to light refraction may be prevented. Thus, it is possible to improve the outward appearance. In addition, customer satisfaction may be improved.
[0019] The methods and apparatuses of the present invention have other features and advantages which will be apparent from or are set forth in more detail in the accompanying drawings, which are incorporated herein, and the following Detailed Description, which together serve to explain certain principles of the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0020] FIG. 1 is a perspective view of an exemplary control knob for a vehicle according to the present invention.
[0021] FIG. 2 is a top plan view of an exemplary control knob for a vehicle according to the present invention.
[0022] FIG. 3 is a cross-sectional view of an overlapping portion viewed from direction A-A in FIG. 2 according to the present invention.
[0023] FIG. 4 is a cross-sectional view of an overlapping portion viewed from direction A-A in FIG. 2 according to the present invention.
[0024] FIG. 5 is a diagram illustrating an exemplary case in which the thickness of a transparent portion forming an overlapping portion is uniform.
DETAILED DESCRIPTION
[0025] Reference will now be made in detail to various embodiments of the present invention(s), examples of which are illustrated in the accompanying drawings and described below. While the invention(s) will be described in conjunction with exemplary embodiments, it will be understood that present description is not intended to limit the invention(s) to those exemplary embodiments. On the contrary, the invention(s) is/are intended to cover not only the exemplary embodiments, but also various alternatives, modifications, equivalents and other embodiments, which may be included within the spirit and scope of the invention as defined by the appended claims.
[0026] FIG. 1 is a perspective view of a control knob for a vehicle according to various embodiments of the present invention. Further, FIG. 2 is a top plan view of a control knob for a vehicle according to various embodiments of the present invention.
[0027] Referring to FIGS. 1 and 2 , a control knob 10 includes an opaque portion 20 , a transparent portion 30 and an overlapping portion 40 . Further, the opaque portion 20 and the transparent portion 30 are integrally formed through dual injection molding. Here, dual injection molding is a forming method that uses two different materials to produce an integrally and/or monolithically formed item, a method that is otherwise conventional, so that a detailed description thereof will not be provided.
[0028] In various embodiments of the present invention, one opaque material and one transparent material are used as the two different materials.
[0029] The opaque portion 20 is formed of the opaque material. Further, the opaque portion 20 may be formed in a curved plate shape so as to improve grip feel for a driver. In addition, a portion of the plate of the opaque portion 20 is formed as an empty space.
[0030] A plurality of coupling protrusions 24 is formed on the undersurface of the opaque portion 20 . Further, the coupling protrusions 24 are formed so as to couple the control knob 10 to a shift lever. Specifically, the shift lever may receive the coupling protrusions 24 so as to be coupled.
[0031] The transparent portion 30 is formed of the transparent material. Further, the transparent portion 30 is formed in the empty space and is formed in a single curved shape together with the opaque portion 20 . In addition, text, a drawing, etc. may be applied to the transparent portion to show a gear pattern or display a design. A paint of the same color as the opaque portion 20 may be applied to the transparent portion 30 .
[0032] An overlapping portion 40 is a portion in which the opaque portion 20 and the transparent portion 30 are stacked and overlapped. Further, the overlapping portion 40 is formed where a portion of the top surface of the opaque portion 20 contacts a portion of the undersurface of the transparent portion 30 . Therefore, a portion at which the boundary between the opaque portion 20 and the transparent portion 30 is externally exposed may be formed at a side surface.
[0033] FIG. 3 is a cross-sectional view of an overlapping portion viewed from direction A-A in FIG. 2 according to various embodiments of the present invention.
[0034] As shown in FIG. 3 , the overlapping portion 40 includes an opaque boundary surface 22 , a transparent boundary surface 32 , and a boundary line 42 .
[0035] The opaque boundary surface 22 is the top surface of the opaque portion 20 at the overlapping portion 40 . Further, the transparent boundary surface 32 is the undersurface of the transparent portion 30 at the overlapping portion 40 . Thus, the opaque boundary surface 22 and the transparent boundary surface 32 contact to form the overlapping portion 40 . The opaque boundary surface 22 and the transparent boundary surface 32 may be formed in mutually corresponding shapes.
[0036] The boundary line 42 is a portion at which the boundary between the opaque portion 20 and the transparent portion 30 is externally exposed. Further, the boundary line 42 is formed at a side surface of the overlapping portion 40 at which the opaque boundary surface 22 contacts the transparent boundary surface 32 .
[0037] When this boundary line 42 is externally exposed, the outward appearance of the control knob 10 may be deteriorated. Further, when the boundary line 42 is exposed at the side surface of the control knob 10 , the outward appearance may be improved over exposure at the top surface. In addition, when the boundary line 42 is formed at the side surface of the control knob 10 , when the control knob 10 is coupled with the shift lever, the boundary line 42 may be covered by a portion of the shift lever so as not to be visible.
[0038] FIG. 3 illustrates a coated portion 50 formed on the transparent portion 30 except for the overlapping portion 40 .
[0039] A coated portion 50 is formed by paint being applied to a portion of the undersurface of the transparent portion 30 that is not the transparent boundary surface 32 . Specifically, the coated portion 50 denotes a layer of paint having a certain thickness. Further, paint of the same color as the opaque portion 20 is used for the coated portion 50 . The top surface of the coated portion 50 contacting the undersurface of the transparent portion 30 is a coated portion boundary surface 52 . The transparent portion 30 contacting the coated portion 50 may be formed of a uniform thickness.
[0040] The arrows in FIGS. 3 , 4 , and 5 schematically illustrate the refraction of light. The color of the opaque portion 20 and the coated portion 50 may be perceived differently according to differences in the refractive indices of light. Further, because the materials of the opaque portion 20 and the coated portion 50 are different, the refractive indices thereof are different.
[0041] In various embodiments of the present invention, the opaque boundary surface 22 is formed in a slope in order to prevent colors from being perceived differently due to the difference in refractive indices of the opaque portion 20 and the coated portion 50 . In addition, the opaque boundary surface 22 is formed in a downward slope in a direction from the boundary line 42 toward the coated portion 50 . Further, the transparent boundary surface 32 is formed in a sloped shape corresponding to the opaque boundary surface 22 .
[0042] FIG. 4 is a cross-sectional view of an overlapping portion viewed from direction A-A in FIG. 2 according to various embodiments of the present invention.
[0043] Hereinafter, the overlapping portion 40 according to various embodiments of the present invention will be described in detail with reference to FIG. 4 . Further, repetitive descriptions of constituent elements in FIG. 4 that are the same as those in FIG. 3 will not be provided.
[0044] In various embodiments of the present invention, the opaque boundary surface 22 is formed as a gradually sloped surface in order to prevent colors from being perceived differently due to the difference in refractive indices of the opaque portion 20 and the coated portion 50 . Further, the opaque boundary surface 22 is formed in a downward slope in a direction from the boundary line 42 toward the coated portion 50 . The opaque boundary surface 22 may be formed as a convex curved surface. Further, the transparent boundary surface 32 is formed in a sloped shape corresponding to the opaque boundary surface 22 .
[0045] One will appreciate that the shape of the opaque boundary surface 22 in FIGS. 3 and 4 may be modified and applied to prevent colors of the opaque portion 20 and the coated portion 50 from being perceived differently. That is, the thickness of the transparent portion 30 at the top of the opaque boundary surface 22 may be formed to gradually widen in a downward direction from the boundary line 42 toward the coated portion 50 . In addition, the refractive index of light may be formed differently according to the thickness of the transparent portion 30 . Therefore, an abrupt change in refractive index at the boundary between the opaque portion 20 and the coated portion 50 may be prevented.
[0046] FIG. 5 is a diagram illustrating a case in which the thickness of a transparent portion forming an overlapping portion is uniform.
[0047] When the thickness of the transparent portion 30 forming the overlapping portion 40 is formed uniformly, the refractive index of light at the boundary between the opaque portion 20 and the coated portion 50 changes abruptly. Accordingly, an abrupt change in color may be perceived between the opaque portion 20 and the coated portion 50 .
[0048] As described above, according to various embodiments of the present invention, the boundary line 42 of two different materials is produced in a portion that is not visible. Further, an abrupt difference in color due to the refraction of light may be prevented. Therefore, outward appearance may be improved. In addition, customer satisfaction may be improved.
[0049] For convenience in explanation and accurate definition in the appended claims, the terms top, and etc. are used to describe features of the exemplary embodiments with reference to the positions of such features as displayed in the figures.
[0050] The foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. They are not intended to be exhaustive or to limit the invention to the precise forms disclosed, and obviously many modifications and variations are possible in light of the above teachings. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and their practical application, to thereby enable others skilled in the art to make and utilize various exemplary embodiments of the present invention, as well as various alternatives and modifications thereof. It is intended that the scope of the invention be defined by the Claims appended hereto and their equivalents.
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A control knob for a vehicle has an improved outward appearance by forming a boundary line between two different materials in a portion that is not visible and preventing abrupt differences in color due to light refraction. The control knob is produced by dual injection molding of two different materials, is installed on one end of a shift lever, and functions as a handgrip. The control knob includes an portion of opaque and transparent materials, an overlapping portion opaque and transparent materials, and a coated portion formed of paint applied to portions of the transparent portion that do not overlap with the opaque portion. A boundary surface between the opaque and transparent portions is such that a refractive index of light passing through the transparent portion from the overlapping portion is close to a refractive index of light passing through the transparent portion from the coated portion.
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STATEMENT AS TO RIGHTS TO INVENTIONS MADE UNDER FEDERALLY SPONSORED RESEARCH AND DEVELOPMENT
This invention was made with Government support under Grant (Contract) Nos. DE-FC36-00GO10536 and DE-FG36-05GO15041 awarded by the United States Department of Energy. The Government has certain rights in this invention.
BACKGROUND OF THE INVENTION
Oxygenic photosynthesis depends on the absorption of sunlight by auxiliary light-harvesting pigments, which are incorporated within the holocomplexes of photosystem-I and photosystem-II. In each photosystem (PS), sizable arrays of chlorophylls and other accessory pigments (e.g., carotenoids) act cooperatively as antennae for the collection of light energy and as a conducting medium for excitation migration toward a photochemical reaction center (see, e.g., Emerson & Arnold, J Gen Physiol 15: 391-420, 1932; Emerson & Arnold, J Gen Physiol 16: 191-205, 1933; Gaffron & Wohl, Naturwissenschaften 24: 81-90, 1936; Melis, In, Oxygenic Photosynthesis: The Light Reactions ” (DR Ort, CF Yocum, eds), Kluwer Academic Publishers, Dordrecht, The Netherlands, pp. 523-538, 1996). Organized as distinct pigment-protein complexes and contained within PSI and PSII, these light-harvesting antennae perform the functions of light absorption and excitation energy transfer to a photochemical reaction center (see, e.g., Simpson and Knoetzel, In: Ort DR and Yocum CF (eds), Oxygenic Photosynthesis: The Light Reactions , pp. 493-506, Kluwer Academic Publishers, Dordrecht, The Netherlands, 1996; Pichersky and Jansson, In: Ort DR and Yocum CF (eds), Oxygenic Photosynthesis: The Light Reactions , pp. 507-521, Kluwer Academic Publishers, Dordrecht, The Netherlands, 1996). Up to 350 chlorophyll a (Chl a) and Chl b molecules can be found in association with PSII, whereas the Chl antenna size of PSI may contain up to 300 mainly Chl a molecules (Melis, Biochim. Biophys. Acta (Reviews on Bioenergetics) 1058: 87-106, 1991; Melis, In, Oxygenic Photosynthesis: The Light Reactions ” (DR Ort, CF Yocum, eds), Kluwer Academic Publishers, Dordrecht, The Netherlands, pp. 523-538, 1996). Some of these Chl molecules are contained within the PS-core complexes, which are highly conserved in all organisms of oxygenic photosynthesis. The PSII-core complex contains about 37 Chl a molecules, whereas the PSI-core complex contains 95 Chl a molecules (Glick & Melis, Biochim Biophys Acta 934: 151-155, 1988; Jordan et al., Nature 411(6840): 909-917, 2001; Zouni et al., Nature 409: 739-743, 2001; Ruban et al., Nature 421: 648-652, 2003). In green plants and algae, the remaining Chl a and Chl b antenna molecules are organized within 10 peripheral subunits of the so-called auxiliary chlorophyll a-b light-harvesting complex. There are six such subunits for PSII (Lhc b1-b6) and four for PSI (Lhc a1-a4) (Jansson et al., Plant Mol Biol Rep, 10: 242-253, 1992). These peripheral Lhc subunits are not essential for the process of photosynthesis. Indeed, when the chloroplast development is limited, stable assembly of the PSII-core and PSI-core complexes takes place in the absence of any Lhc proteins (Glick & Melis, 1988, supra).
A genetic tendency of photosynthetic organisms to assemble large arrays of light absorbing Chl antenna molecules in their photosystems is a survival strategy and a competitive advantage in the wild, where light is often limiting (Kirk, Light and photosynthesis in aquatic ecosystems, 2nd edn. Cambridge University Press, Cambridge, England, 1994). However, the Chl antenna size of the photosystems is not fixed but can vary substantially depending on developmental, genetic, physiological and even environmental conditions (Melis, 1991, supra). It is recognized in the field that a genetic regulatory mechanism dynamically modulates the Chl antenna size of photosynthesis (Anderson, Annu Rev Plant Physiol 37: 93-136, 1986; Escoubas et al., Proc. Nat. Acad. Sci. 92: 10237-10241, 1995; Melis, 1991 and 1996, both supra; Melis, Intl. J. Hydrogen Energy 27: 1217-1228, 2002; Melis, Chapter 12 in Artificial Photosynthesis: From Basic Biology to Industrial Application , A F Collins and C Critchley (eds.), Wiley-Verlag & Co., pp. 229-240, 2005). For example, the Chl antenna size is adjusted and optimized in response to the light intensity during plant growth (Ley and Mauzerall, Biochim Biophys Acta 680: 95-106, 1982; Sukenik et al., Biochim Biophys Acta 932: 206-215, 1988; Smith et al., Plant Physiol. 93: 1433-1440, 1990; LaRoche et al., Plant Physiol 97: 147-153, 1991; Maxwell et al., Plant Physiol 107: 687-694, 1995; Falbel et al., Plant Physiol. 112: 821-832, 1996; Webb and Melis, Plant Physiol. 107: 885-893, 1995; Ohtsuka et al., Plant Physiol. 113: 137-147, 1997; Tanaka and Melis, Plant Cell Physiol. 38: 17-24, 1997; Masuda et al., Plant Physiol. 128: 603-614, 2002). Physiological and biochemical consequences of the function of this molecular regulatory mechanism for the Chl antenna size are well understood. However, little is known about the genes and proteins and their mode of action in this regulation. The Chl antenna size regulatory mechanism is highly conserved and functions in all organisms of oxygenic and anoxygenic photosynthesis (Anderson, Annu Rev Plant Physiol 37: 93-136, 1986; Nakada et al., J Ferment Bioengin 80: 53-57, 1995; Escoubas et al., Proc. Nat. Acad. Sci. 92: 10237-10241, 1995; Huner et al., Trends in Plant Science, 3: 224-230, 1998; Yakovlev et al., FEBS Lett 512: 129-132, 2002; Masuda et al., Plant Physiol. 128: 603-614, 2002; Masuda et al., Plant Mol. Biol. 51: 757-771, 2003). Thus, identification of the relevant genes and elucidation of the genetic mechanism for the regulation of the Chl antenna size in Chlamydomonas reinhardtii can apply to all photosynthetic organisms.
Although a smaller Chl antenna size may compromise the ability of a plant, e.g., algae, to survive in the wild, in a high-density cultivation environment, a smaller chlorophyll antenna size would help to diminsh the over-absorption and wasteful dissipation of excitation energy by the first layer of leaves, cells or chloroplasts, and would also help diminish photoinhibiton of photosynthesis at the surface while permitting greater transmittance of light deeper into the culture. Such altered optical properties of the cells would result in greater photosynthetic productivity and enhanced solar conversion efficiency by the high-density culture.
Previous work (Masuda et al. 2003, supra; Polle et al., Planta 217: 49-59, 2003, Melis, 2005, supra) described the isolation of tla1, a Chlamydomonas reinhardtii DNA insertional mutant having a truncated light-harvesting chlorophyll antenna size (Polle et al, 2003, supra). Although these studies identified a mutant that had reduced antenna size, there was no teaching of whether the phenotype was associated with increased or suppressed tla1 expression. Accordingly, there is a need for further elucidation of mechanism of Tla1-mediated changes in chlorophyll antenna size.
BRIEF SUMMARY OF THE INVENTION
The current invention is based on the discovery that suppression of Tla1 expression results in reduced chlorophyll antenna size. Thus, in one aspect, the invention provides a method of decreasing chlorophyll antenna size in a plant, e.g., green algae, the method comprising: inhibiting expression of a Tla1 nucleic acid in the plant by introducing into the plant an expression cassette comprising a promoter operably linked to a polynucleotide, or a complement thereof, that specifically hybridizes to a nucleic acid that has at least 70% identity, often at least 80%, 90%, or 95% identity, to at least 200 contiguous nucleotides of a sequence encoding SEQ ID NO:2; and selecting a plant with decreased chlorophyll antenna size compared to a plant in which the expression cassette has not been introduced. The promoter may be inducible or constitutive. In some embodiments the polynucleotide is operably linked to the promoter in the antisense orientation; in other embodiments, the polynucleotide is operably linked to the promoter in the sense orientation.
In some embodiment, the polynucleotide introduced into the plant, e.g., green algae, is an siRNA. In other embodiments, the polynucleotide is an antisense RNA.
The nucleic acid to which the polynucleotide hybridizes can encode a polypeptide of SEQ ID NO:2. In particular embodiments, the nucleic acid is SEQ ID NO:3 or SEQ ID NO:1.
Often the plant, e.g., green algae, into which the nucleic acid is introduced, is selected from Chlamydomonas reinhardtii, Scenedesmus obliquus, Chlorella vulgaris, Botryococcus braunii, Botryococcus sudeticus, Dunaliella salina , or Haematococcus pluvialis.
The invention also provides a plant comprising an expression cassette comprising a polynucleotide, or a complement thereof, that specifically hybridizes to a nucleic acid that has at least 70% percent identity, often at least 80%, 90%, or 95% identity, to at least 200 contiguous nucleotides of a sequence encoding SEQ ID NO:2. In preferred embodiments, the plant is a green algae, e.g., Chlamydomonas reinhardtii, Scenedesmus obliquus, Chlorella vulgaris, Botryococcus braunii, Botryococcus sudeticus, Dunaliella salina , or Haematococcus pluvialis.
The invention additionally provides a method of enhancing yields of photosynthetic productivity under high-density growth conditions, the method comprising cultivating a Tla1-suppressed plant of the invention, e.g., green algae such as Chlamydomonas reinhardtii, Scenedesmus obliquus, Chlorella vulgaris, Botryococcus braunii, Botryococcus sudeticus, Dunaliella salina , or Haematococcus pluvialis , under bright sunlight and high density growth conditions.
Additionally, the invention provides a method of enhancing H 2 production, the method comprising suppressing Tla1 gene expression in a green algae, e.g., Chlamydomonas reinhardtii, Scenedesmus obliquus , or Chlorella vulgaris , to be used for H 2 production; and cultivating the algae under conditions in which H 2 is produced.
The invention further provides a method of enhancing bio-oil or bio-diesel production, the method comprising suppressing Tla1 gene expression in a green algae, e.g., Botryococcus braunii or Botryococcus sudeticus to be used for bio-oil or bio-diesel production; and cultivating the algae under conditions in which bio-oil or bio-diesel is produced.
Further, the invention provides a method of enhancing beta-carotene, lutein or zeaxanthin production, the method comprising suppressing Tla1 gene expression in a green algae, e.g., Dunaliella salina , to be used for beta-carotene, lutein or zeaxanthin production; and cultivating the algae under conditions in which beta-carotene, lutein or zeaxanthin is produced.
In other embodiments, the invention provides a method of enhancing astaxanthin production, the method comprising suppressing Tla1 gene expression in a green algae, e.g., Haematococcus pluvialis , to be used for astaxanthin production; and cultivating the algae under conditions in which astaxanthin is produced.
In another aspect, the invention provides a method of screening for plants, preferably, green algae, that show enhanced yield of photosynthetic productivity, the method comprising: introducing a mutation into a population of plants, e.g., green algae; and screening for inhibition of Tla1 gene expression, wherein inhibition of Tla1 gene expression is determined by measuring the level of Tla1 mRNA or Tla1 protein. Preferably the plants, e.g., green algae, are selected from Chlamydomonas reinhardtii, Scenedesmus obliquus, Chlorella vulgaris, Botryococcus braunii, Botryococcus sudeticus, Dunaliella salina , or Haematococcus pluvialis.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 . (A) Map of plasmid pJD67 insertion in the tla1 mutant genomic DNA. There is a single plasmid insert, containing the ARG7.8 gene. An approximately 2.3 kb segment of the 5′ end and 9 base pairs at the 3′ end of the pJD67 were deleted upon plasmid insertion. About 6 kb of C. reinhardtii genomic DNA in the tla1 mutant was also deleted from the site of plasmid insertion. Probes for screening tla1 partial genomic libraries to clone 5′- and 3′insert flanking regions are shown by the SalI-SalI and NdeI-NdeI restriction sites on the map. (B) Gene structure of the tla1 mutant and wild type C. reinhardtii in the pJD67 plasmid insertion locus: 104 bp of 5′ UTR, a total coding region of 642 bp (coding region of exon 1 with 198 bp and coding region of exon 2 with 444 bp), a single intron of 116 bases and 1.26 kb of 3′ UTR, encoding a protein of 213 amino acids.
FIG. 2 . Genomic DNA map showing the Tla1 gene structure in: (A) the host CC425 strain, (B) the tla1 mutant, and (C) the Tla1 complementing plasmid containing the ble gene. Note that the tla1-complements will have both the mutant gene shown in (B) and the wild type gene shown in (C). Dotted rectangles denote the promoter region of the Tla1 gene; Small hatched rectangles denote the 5′ UTR of the Tla1 gene; Long-hatched rectangles denote the 3′ UTR of the Tla1 gene. Thick black arrows and black lines denote the Tla1 exons and introns, respectively. Primers 1, 2, 3, 4, 5, 6, 7, 8 and 9 were used for PCR analysis and are denoted by small black arrows on the genomic DNA map (see Table 1).
FIG. 3 . PCR analysis of wild type and tla1 mutant. The presence of transcripts of the Tla1 gene was tested by RT-PCR with primers from different regions of the Tla1 cDNA. Total RNA was isolated from TBP-grown Chlamydomonas reinhardtii wild type and tla1 mutant cultures. The down stream PCR primer, “primer 5” was designed from the exon 2 region of the Tla1 gene and were the same for all lanes in this experiment. Lanes 1, 2: upstream primer “primer 2” was designed from the 5′ UTR region (“primer 2”-GCCTGCCACAACCTCAGACCAAGAGACG; SEQ ID NO:15); expected product size of 454 bp). Lanes 4-6: upstream primers were designed from the exon 1 region of the Tla1 gene (“primer 3”-GGGCCCTTCAGCTGCTCCGCTGACCAAACC); SEQ ID NO:10). Lanes 4, 5: expected product size of 409 bp., Lane 6: genomic DNA was isolated from the tla1 mutant and used as a template for the PCR reaction; expected product size of 525 bp, i.e., larger than those of lanes 4, 5, due to the presence of a 116 bp intron, existing between exons 1 and 2. The 1.5% agarose gel was also loaded with M markers (Lane 3) containing a 1 kb DNA ladder (Promega, Madison, Wis.). The PCR products in lane 4 and 5 aligned at the 396 bp marker. The PCR products in lane 6 aligned at a position slightly higher than the 506-517 bp markers.
FIG. 4 . 5′ RACE DNA sequence analysis of wild type (cw15) and tla1 mutant and sequence comparison with the 3′ end of pJD67. Upper panel: DNA sequence obtained from the 5′ RACE of the wild type (SEQ ID NO:16). Unshaded nucleotides represent the 5′ UTR of the cDNA sequence amplified from the WT-Tla1 gene transcripts. The ATG start codon is denoted in bold characters. Exon 1 nucleotides are shown in shaded upper case characters. Middle panel: DNA sequence obtained from the 5′ RACE of the tla1 mutant (SEQ ID NO:17). The underlined lower case letters represent the apparent 5′ UTR sequence amplified from the tla1 mutant. Exon 1 nucleotide sequences are shown in shaded upper case characters. Lower panel: 3′ end DNA sequence of plasmid pJD67 (SEQ ID NO:18). Shaded upper case characters correspond to the DNA sequence of the ARG7.8 gene, whereas lower case characters correspond to the 3′ end of the vector sequence. Rearrangements in that portion of the plasmid are shown in bold characters, as follows: the last 9 plasmid bases “a t t a a a g c t” were deleted during the plasmid insertion.
FIG. 5 . Mapping of BAC clone 39e16 and subcloning of full length Tla1 gene for tla1 mutant complementation experiments. Southern blot analysis of the DNA from BAC clone 39e16 and subsequent DNA sequencing of subclones provided information on size and locus of a 3.7 kb Apa I-Apa I DNA fragment and a 3 kb Pst I-Pst I fragment. The 2 kb overlapping segment of the Pst I-Pst I fragment was removed. The remainder Pst I-Pst I piece was ligated onto the Apa I-Apa I DNA fragment and cloned in pBluescript to yield the 4.7 kb full length Tla1 gene on a single plasmid for use in complementation experiments.
FIG. 6 . TAP-Agar plate showing wild type (WT), tla1 mutant and complemented strains of the latter. Mutant strains were complemented with a copy of the wild type Tla1 gene. The phenotype of the tla1 mutant showed a faint green coloration, indicative of the low-level chlorophyll concentration in the cells, whereas the WT and putative complements 1, 2 and 3 were of about the same dark green coloration, indicating a greater Chl/cell.
FIG. 7 . PCR analysis using genomic DNA of wild type and tla1 complements. (A)PCR product of 593 bp obtained with “primer 1” and “primer 4” (Tla1 promoter/Exon-2) primers. (B) PCR product of 684 bp obtained with “primer 7” and “primer 4” (pJD67 3′ end/Tla1 Exon-2) primers. (C) PCR product of 436 bp obtained with “primer 8” and “primer 9” (Ble gene) primers. (D) PCR product of 939 bp obtained with “primer 1”and “primer 6” (Tla1 promoter/3′UTR) primers. (E) RT-PCR analysis of tla1 complements. PCR product of 823 bp obtained when “primer 1” and “primer 6” (Tla1 5′UTR/3′UTR) specific primers were used. “0”, “W”, “T”, “1”, “2” and “S” stand for zero DNA, wild type, tla1 mutant, tla1-comp1, tla1-comp2 and pSP124s plasmid containing the Ble gene, respectively.
FIG. 8 . Overexpression and purification of recombinant Tla1 protein. A 12.5% SDS-PAGE gel stained with Coomassie blue showing: (A) Un-induced (lane 1) and induced (lane 2) E. coli cells expressing the recombinant 6*His-Tla1 protein. 20 μg of total E. coli cell protein extracts were loaded on each lane. “M” denotes unstained Benchmark low molecular weight markers. (B) Purified 6*His-Tla1 protein fractions (lanes 1 and 2). 35 μg of purified recombinant protein was loaded in each lane. “M” denotes the Benchmark pre-stained low molecular weight markers
FIG. 9 . Immune serum titer and Tla1 protein immuno-detection in wild type and tla1 mutant. (A) A Western blot of isolated recombinant Tla1 protein (6*His-Tla1), probed with Tla1-specific antibodies. Lanes 1, 2 and 3 contain 20 ng, 20 pg and 2 pg of purified recombinant Tla1 protein, respectively. (B) SDS-PAGE stained with Coomassie blue showing the total protein profile of wild type (W) and tla1 mutant (T) of C. reinhardtii . Lanes were loaded on an equal-Chl basis (6 nmol Chl per lane). “M” stands for the Benchmark pre-stained low molecular weight markers. (C) Western blot analysis of wild type (W) and tla1 (T) total cell protein extracts from C. reinhardtii , probed with Tla1-specific polyclonal antibodies. Lanes were loaded on an equal-Chl basis (6 nmol Chl per lane).
FIG. 10 . SDS-PAGE and Western blot analysis of wild type, tla1 mutant and tla1 complemented strains. (A) SDS-PAGE of C. reinhardtii total cell protein extracts from wild type (W), tla1 mutant (T), and tla1 complements comp1 (lane 1) and comp2 (lane 2). Lanes were loaded on an equal-Chl basis (4 nmol Chl per lane). “M” stands for the unstained Benchmark low molecular weight markers. (B) Western blot analysis of C. reinhardtii total cell protein extracts from wild type (W), tla1 mutant (T), and tla1 complements, tla1-comp1 (lane 1) and tla1-comp2 (lane 2), probed with Tla1-specific polyclonal antibodies.
FIG. 11 . Hydropathy plot of the Tla1 deduced amino acid sequence. The X-axis plots the 213 amino acids of the Tla1 protein, whereas the Y-axis plots the respective amino acid hydropathy index. Positive hydropathy index corresponds to hydrophobic domains of the protein whereas a negative hydropathy index corresponds to hydrophilic polypeptide domains.
FIG. 12 . (A) Alignment of Tla1-like proteins from different organisms. The alignment of the Tla1 deduced amino acid sequence of C. reinhardtii is compared to that of similar proteins from A. thaliana (SEQ ID NO:19), O. sativa (SEQ ID NO:20), H. sapiens CGI 112 protein, (SEQ ID NO:21), and D. melanogaster (SEQ ID NO:22 ). Four polypeptide domains with high sequence conservation can be deduced from this comparison. The alignment was done on the basis of the ClustalW web-based software (http://www.ch.embnet.org/software/ClustalW.html). (B) Phylogenetic comparison of putative Tla1 homologue proteins encoded by genes from a variety of organisms. The phylogenetic tree of the above-shown proteins was based on the deduced amino acid sequences ((http://www.ebi.ac.uk/clustalw).
FIG. 13 shows an alignment of Tla1 protein sequences (SEQ ID NOS:20,23,19 and 2, respectively) in plants and algae. Conserved domains in C. reinhardtii Tla1 protein×SEQ ID NOS:24-28.
DETAILED DESCRIPTION OF THE INVENTION
Definitions
The terms “nucleic acid” and “polynucleotide” are used synonymously and refer to a single or double-stranded polymer of deoxyribonucleotide or ribonucleotide bases read from the 5′ to the 3′ end. A nucleic acid of the present invention will generally contain phosphodiester bonds, although in some cases, nucleic acid analogs may be used that may have alternate backbones, comprising, e.g., phosphoramidate, phosphorothioate, phosphorodithioate, or O-methylphophoroamidite linkages (see Eckstein, Oligonucleotides and Analogues: A Practical Approach, Oxford University Press); and peptide nucleic acid backbones and linkages. Other analog nucleic acids include those with positive backbones; non-ionic backbones, and non-ribose backbones. Thus, nucleic acids or polynucleotides may also include modified nucleotides, that permit correct read through by a polymerase. “Polynucleotide sequence” or “nucleic acid sequence” may include both the sense and antisense strands of a nucleic acid as either individual single strands or in a duplex. As will be appreciated by those in the art, the depiction of a single strand also defines the sequence of the complementary strand; thus the sequences described herein also provide the complement of the sequence. Unless otherwise indicated, a particular nucleic acid sequence also implicitly encompasses conservatively modified variants thereof (e.g., degenerate codon substitutions) and complementary sequences, as well as the sequence explicitly indicated. The nucleic acid may be DNA, both genomic and cDNA, RNA or a hybrid, where the nucleic acid may contain combinations of deoxyribo- and ribo-nucleotides, and combinations of bases, including uracil, adenine, thymine, cytosine, guanine, inosine, xanthine hypoxanthine, isocytosine, isoguanine, etc
The phrase “nucleic acid sequence encoding” refers to a nucleic acid that codes for an amino acid sequence of at least 5 contiguous amino acids within one reading frame. The amino acid need not necessarily be expressed when introduced into a cell or other expression system, but may merely be determinable based on the genetic code. For example, the sequence ATGATGGAGCATCAT (SEQ ID NO:29) encodes MMEHH. (SEQ ID NO:30). Thus, a polynucleotide may encode a polypeptide sequence that comprises a stop codon or contains a changed frame so long as at least 5 contiguous amino acids within one reading frame. The nucleic acid sequences may include both the DNA strand sequence that is transcribed into RNA and the RNA sequence. The nucleic acid sequences include both the full length nucleic acid sequences as well as fragments from the full length sequences. It should be further understood that the sequence includes the degenerate codons of the native sequence or sequences which may be introduced to provide codon preference in a specific host cell.
The term “promoter” or “regulatory element” refers to a region or sequence determinants located upstream or downstream from the start of transcription that are involved in recognition and binding of RNA polymerase and other proteins to initiate transcription. A “plant promoter” is a promoter capable of initiating transcription in plant cells. Such promoters need not be of plant origin, for example, promoters derived from plant viruses, such as the CaMV35S promoter, can be used in the present invention.
As used herein, the term “algal regulatory element” or “algae promoter” refers to a nucleotide sequence that, when operatively linked to a nucleic acid molecule, confers e expression upon the operatively linked nucleic acid molecule in unicellular green algae. It is understood that limited modifications can be made without destroying the biological function of a regulatory element and that such limited modifications can result in algal regulatory elements that have substantially equivalent or enhanced function as compared to a wild type algal regulatory element. These modifications can be deliberate, as through site-directed mutagenesis, or can be accidental such as through mutation in hosts harboring the regulatory element. All such modified nucleotide sequences are included in the definition of an algal regulatory element as long as the ability to confer expression in unicellular green algae is substantially retained.
The term “suppressed” or “decreased” encompasses the absence of Tla1 protein in a plant, e.g., algae, as well as protein expression that is present but reduced as compared to the level of Tla1 protein expression in a wild type plant, e.g., algae. The term “suppressed” also encompasses an amount of Tla1 protein that is equivalent to wild type levels, but where the protein has a reduced level of activity in comparison to wild type plants. Generally, at least a 20% decrease in Tla1 activity, amount, chlorophyll antenna size or the like is preferred, with at least about 50% or at least about 75% being particularly preferred.
A polynucleotide sequence is “heterologous to” a second polynucleotide sequence if it originates from a foreign species, or, if from the same species, is modified by human action from its original form. For example, a promoter operably linked to a heterologous coding sequence refers to a coding sequence from a species different from that from which the promoter was derived, or, if from the same species, a coding sequence which is different from any naturally occurring allelic variants.
A “Tla1 polynucleotide” is a nucleic acid sequence substantially similar to SEQ ID NO:1 or SEQ ID NO:3, or that encodes a polypeptide that is substantially similar to SEQ ID NO:2. Tla1 polynucleotides may comprise (or consist of) a region of about 15 to about 3,000 or more nucleotides, sometimes from about 20, or about 50, to about 2,000 nucleotides and sometimes from about 200 to about 600 nucleotides, which hybridizes to SEQ ID NO:1 or SEQ ID NO:3, or the complements thereof, under stringent conditions, or which encodes a Tla1 polypeptide or fragment of at least 15 amino acids thereof. Tla1 polynucleotides can also be identified by their ability to hybridize under low stringency conditions (e.g., Tm ˜40° C.) to nucleic acid probes having the sequence of SEQ ID NO:1 or SEQ ID NO:3. Such Tla1 nucleic acid sequence can have, e.g., about 25-30% base pair mismatches or less relative to the selected nucleic acid probe. SEQ ID NOs:1 and 3 are exemplary Tla1 polynucleotide sequences. The term “Tla1 polynucleotide” encompasses antisense as well as sense nucleic acids.
A “Tla1 polypeptide” is an amino acid sequence that is substantially similar to SEQ ID NO:2, or a fragment or domain thereof. A full-length Tla1 protein is 213 amino acids. The majority of the amino acid residues are hydrophilic, suggesting that it is a soluble cytosolic protein. A single hydrophobic domain is present. The domain comprises 27 amino acids between residues 42 and 69 (with reference to SEQ ID NO:2). The hydrophobic domain is highly conserved in diverse organisms.
As used herein, a homolog or ortholog of a particular Tla1 gene (e.g., SEQ ID NO:1) is a second gene in the same plant type or in a different plant type, which has a polynucleotide sequence of at least 50 contiguous nucleotides which are substantially identical (determined as described below) to a sequence in the first gene. It is believed that, in general, homologs or orthologs share a common evolutionary past.
An “expression cassette” refers to a nucleic acid construct, which when introduced into a host cell, results in transcription and/or translation of a RNA or polypeptide, respectively. Antisense constructs or sense constructs that are not or cannot be translated are expressly included by this definition.
In the case of both expression of transgenes and inhibition of endogenous genes (e.g., by antisense, or sense suppression) one of skill will recognize that the inserted polynucleotide sequence need not be identical and may be “substantially identical” to a sequence of the gene from which it was derived. As explained below, these variants are specifically covered by this term.
In the case where the inserted polynucleotide sequence is transcribed and translated to produce a functional polypeptide, one of skill will recognize that because of codon degeneracy a number of polynucleotide sequences will encode the same polypeptide. These variants are specifically covered by the term “polynucleotide sequence from” a Tla1 gene. In addition, the term specifically includes sequences (e.g., full length sequences) substantially identical (determined as described below) with a Tla1 gene sequence. A “polynucleotide sequence from” a Tla1 gene can encode a protein that retains the function of a Tla1 polypeptide in contributing to chlorophyll antenna size.
In the case of polynucleotides used to inhibit expression of an endogenous gene, the introduced sequence need not be perfectly identical to a sequence of the target endogenous gene. The introduced polynucleotide sequence will typically be at least substantially identical (as determined below) to the target endogenous sequence. Thus, an introduced “polynucleotide sequence from” a Tla1 gene may not be identical to the target Tla1 gene to be suppressed, but is functional in that it is capable of inhibiting expression of the target Tla1 gene.
Two nucleic acid sequences or polypeptides are said to be “identical” if the sequence of nucleotides or amino acid residues, respectively, in the two sequences is the same when aligned for maximum correspondence as described below. The term “complementary to” is used herein to mean that the sequence is complementary to all or a portion of a reference polynucleotide sequence.
Optimal alignment of sequences for comparison may be conducted by the local homology algorithm of Smith and Waterman Add. APL. Math. 2:482 (1981), by the homology alignment algorithm of Needle man and Wunsch J. Mol. Biol. 48:443 (1970), by the search for similarity method of Pearson and Lipman Proc. Natl. Acad. Sci . (U.S.A.) 85: 2444 (1988), by computerized implementations of these algorithms (GAP, BESTFIT, BLAST, FASTA, and TFASTA in the Wisconsin Genetics Software Package, Genetics Computer Group (GCG), 575 Science Dr., Madison, Wis.), or by inspection.
“Percentage of sequence identity” is determined by comparing two optimally aligned sequences over a comparison window, wherein the portion of the polynucleotide sequence in the comparison window may comprise additions or deletions (i.e., gaps) as compared to the reference sequence (which does not comprise additions or deletions) for optimal alignment of the two sequences. The percentage is calculated by determining the number of positions at which the identical nucleic acid base or amino acid residue occurs in both sequences to yield the number of matched positions, dividing the number of matched positions by the total number of positions in the window of comparison and multiplying the result by 100 to yield the percentage of sequence identity.
The term “substantial identity” in the context of polynucleotide sequences means that a polynucleotide comprises a sequence that has at least 50% sequence identity. Alternatively, percent identity can be any integer from 40% to 100%. Exemplary embodiments include at least: 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 99%. compared to a reference sequence using the programs described herein; preferably BLAST using standard parameters, as described below. Accordingly, Tla1 sequences of the invention include nucleic acid sequences that have substantial identity to SEQ ID NO:1, or a portion of SEQ ID NO:1 such as the coding region of SEQ ID NO:1, or SEQ ID NO:3.
Tla1 polypeptide sequences of the invention include polypeptide sequences having substantial identify to SEQ ID NO:2. One of skill will recognize that these values can be appropriately adjusted to determine corresponding identity of proteins encoded by two nucleotide sequences by taking into account codon degeneracy, amino acid similarity, reading frame positioning and the like. Substantial identity of amino acid sequences for these purposes normally means sequence identity of at least 50%. Preferred percent identity of polypeptides can be any integer from 50% to 100%, e.g., at least 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 99%, an sometimes at least 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74% and 75%. Polypeptides which are “substantially similar” share sequences as noted above except that residue positions which are not identical may differ by conservative amino acid changes. Conservative amino acid substitutions refer to the interchangeability of residues having similar side chains. For example, a group of amino acids having aliphatic side chains is glycine, alanine, valine, leucine, and isoleucine; a group of amino acids having aliphatic-hydroxyl side chains is serine and threonine; a group of amino acids having amide-containing side chains is asparagine and glutamine; a group of amino acids having aromatic side chains is phenylalanine, tyrosine, and tryptophan; a group of amino acids having basic side chains is lysine, arginine, and histidine; and a group of amino acids having sulfur-containing side chains is cysteine and methionine. Preferred conservative amino acids substitution groups are: valine-leucine-isoleucine, phenylalanine-tyrosine, lysine-arginine, alanine-valine, aspartic acid-glutamic acid, and asparagine-glutamine.
Another indication that nucleotide sequences are substantially identical is if two molecules hybridize to each other, or a third nucleic acid, under stringent conditions. Stringent conditions are sequence dependent and will be different in different circumstances. Generally, stringent conditions are selected to be about 5° C. lower than the thermal melting point (Tm) for the specific sequence at a defined ionic strength and pH. The Tm is the temperature (under defined ionic strength and pH) at which 50% of the target sequence hybridizes to a perfectly matched probe. Typically, stringent conditions will be those in which the salt concentration is about 0.02 molar at pH 7 and the temperature is at least about 60° C.
In the present invention, mRNA encoded by Tla1 genes of the invention can be identified in Northern blots under stringent conditions using cDNAs of the invention or fragments of at least about 100 nucleotides. For the purposes of this disclosure, stringent conditions for such RNA-DNA hybridizations are those which include at least one wash in 0.2× SSC at 63° C. for 20 minutes, or equivalent conditions. Genomic DNA or cDNA comprising genes of the invention can be identified using the same cDNAs (or fragments of at least about 100 nucleotides) under stringent conditions, which for purposes of this disclosure, include at least one wash (usually 2) in 0.2× SSC at a temperature of at least about 50° C., usually about 55° C., for 20 minutes, or equivalent conditions.
A Tla1 gene for use in the invention can also be amplified using PCR techniques. For example, a Tla1 gene of the invention may be amplifiable by the primer set: (5′ TACGGGAATTTGCGGAACCTC 3′; (SEQ ID NO:4) and” (5′ AACACACACCCCGCACT 3′; (SEQ ID NO:7).
The term “isolated”, when applied to a nucleic acid or protein, denotes that the nucleic acid or protein is essentially free of other cellular components with which it is associated in the natural state. It is preferably in a homogeneous state and may be in either a dry or aqueous solution. Purity and homogeneity are typically determined using analytical chemistry techniques such as polyacrylamide gel electrophoresis or high performance liquid chromatography. A protein which is the predominant species present in a preparation is substantially purified. In particular, an isolated gene is separated from open reading frames which flank the gene and encode a protein other than the gene of interest.
Introduction
The present invention provides methods of suppressing Tla1 gene expression in plants, e.g., green algae. Plants having suppressed Tla1 gene expression exhibit decreases in the size of chlorophyll antenna. Such plants are useful for many purposes. For example, Tla1 suppression can be used to enhance plant growth and photosynthetic productivity. In embodiments where the plant is a green algae, such Tla1-suppressed plants can be used, e.g., in mass culture for production of various nutrients or pharmaceuticals, for production of H 2 , for production of lipid/hydrocarbons, for carbon sequestration, for waste-water treatment and aquatic pollution amelioration, for flu gas treatment and atmospheric pollution amelioration, for biomass generation, and for other purposes.
A Tla1 nucleic acid that is targeted for suppression in this invention encodes a Tla1 protein that is substantially similar to SEQ ID NO:2, or a fragment thereof. For example, such Tla1 proteins have one or more conserved domains, designated with reference to SEQ ID NO:2: amino acid positions 9-33, amino acid positions 41-70, amino acid positions 75-129, amino acid positions 135-163, or amino acid positions 177-200. Other exemplary plant Tla1-related polynucleotide sequences are from Oryza sativa (Accession No. CX102072), Zea mays (Accession No. EB673149), and Arabidopsis thaliana (Accession No. DR308999). Examples of conserved regions of these proteins are shown in FIG. 13 . 1. Other exemplary Tla1-related sequences include those from Solanum tuberosum (potato) (Accession No. . . CV500710); Gossypium arboreum (Accession No. BG44500); Helianthus annuus (Accession No. BQ967999); Nicotiana tabacum (tobacco) (Accession No. EB678062); Triticum aestivum (wheat) (Accession No. CV065526); Hordeum vulgare (barley) (Accession No. AL504185); and Glycine max (soybean) (Accession No. BM107844).
The invention employs various routine recombinant nucleic acid techniques. Generally, the nomenclature and the laboratory procedures in recombinant DNA technology described below are those well known and commonly employed in the art. Many manuals that provide direction for performing recombinant DNA manipulations are available, e.g., Sambrook & Russell, Molecular Cloning, A Laboratory Manual (3rd Ed, 2001); and Current Protocols in Molecular Biology (Ausubel et al., eds., 1994-1999).
TLA1 Nucleic Acid Sequences
Isolation or generation of Tla1 polynucloetide sequence can be accomplished by a number of techniques. For instance, oligonucleotide probes based on the sequences disclosed here can be used to identify the desired polynucleotide in a cDNA or genomic DNA library from a desired plant species. Such a cDNA or genomic library can then be screened using a probe based upon the sequence of a cloned Tla1 gene, e.g., SEQ ID NO:1 or 3. Probes may be used to hybridize with genomic DNA or cDNA sequences to isolate homologous genes in the same or different plant species.
Alternatively, the nucleic acids of interest can be amplified from nucleic acid samples using amplification techniques. For instance, PCR may be used to amplify the sequences of the genes directly from mRNA, from cDNA, from genomic libraries or cDNA libraries. PCR and other in vitro amplification methods may also be useful, for example, to clone nucleic acid sequences that code for proteins to be expressed, to make nucleic acids to use as probes for detecting the presence of the desired mRNA in samples, for nucleic acid sequencing, or for other purposes.
Appropriate primers and probes for identifying a Tla1 gene from plant cells, e.g., algae, can be generated from comparisons of the sequences provided herein. For a general overview of PCR see PCR Protocols: A Guide to Methods and Applications. (Innis, M, Gelfand, D., Sninsky, J. and White, T., eds.), Academic Press, San Diego (1990). Exemplary primer pairs are: “primer 1” (5′ TACGGGAATTTGCGGAACCTC 3′; (SEQ ID NO:4) and “primer 6” (5′ AACACACACCCCGCACT 3′; (SEQ ID NO:7) set out in Table 1 hereinbelow. Exemplary amplification reaction conditions are: 20 mM Tris HCl, pH 8.4, 50 mM potassium chloride, 2.5 mM magnesium chloride, 0.25 mM dATP, 0.25 mM dCTP, 0.25mM dGTP, 0.25 mM dTTP, 0.6 μM primers, and 2.5 units Taq polymerase/PCR reaction. An exemplary thermal cycling program is 94° C. for 3 min., 35 cycles of 95° C. for 45 sec, 55° C.-59° C. for 30 sec, 72° C. for 130 sec, followed by 72° C. for 10 min.
The genus of Tla1 nucleic acid sequences for use in the invention includes genes and gene products identified and characterized by techniques such as hybridization and/or sequence analysis using exemplary nucleic acid sequences, e.g., SEQ ID NOs:1 and 3, and protein sequences, e.g., SEQ ID NO:2.
Preparation of Recombinant Vectors
To use isolated sequences in the above techniques, recombinant DNA vectors suitable for transformation of plant cells, e.g., green algae cells, are prepared. Techniques for transforming a wide variety of higher plant species are well known and described in the technical and scientific literature. See, for example, Weising et al. Ann. Rev. Genet. 22:421-477 (1988). For example, a DNA sequence encoding a sequence to suppress Tla1 expression (described in further detail below), will preferably be combined with transcriptional and other regulatory sequences which will direct the transcription of the sequence from the gene in the intended cells of the transformed plant.
Regulatory sequences include promoters, which may be either constitutive or inducible, or where a higher plant is involved, tissue-specific. For example, a plant promoter fragment may be employed that is constitutive, i.e., it will direct expression of the gene under most environmental conditions and states of cell differentiation. Examples of constitutive promoters include the cauliflower mosaic virus (CaMV) 35S transcription initiation region, the 1′- or 2′-promoter derived from T-DNA of Agrobacterium tumafaciens , the CaMV 19S promoter; the Figwort mosaic virus promoter; actin promoters, and the nopaline synthase (nos) gene promoter. Other constitutive promoter include promoters such as the Arabidopsis actin gene promoter (see, e.g., Huang (1997) Plant Mol. Biol. 1997 33:125 139); alcohol dehydrogenase (Adh) gene promoters (see, e.g., Millar (1996) Plant Mol. Biol. 31:897 904); ACT11 from Arabidopsis (Huang et al. Plant Mol. Biol. 33:125-139 (1996)), Cat3 promoter from Arabidopsis (Zhong et al., Mol. Gen. Genet. 251:196-203 (1996)), the promoter from the gene encoding stearoyl-acyl carrier protein desaturase from Brassica napus (Solocombe et al. Plant Physiol. 104:1167-1176 (1994)), GPc1 promoter from maize (Martinez et al. J. Mol. Biol. 208:551-565 (1989)), Gpc2 promoter from maize (Manjunath et al., Plant Mol. Biol. 33:97-112 (1997)), and other transcription initiation regions from various plant genes known to those of skill. Chimeric regulatory elements, which combine elements from different genes, also can be useful for e expressing a nucleic acid molecule encoding a Tla polynucleotide.
Alternatively, a plant promoter can be used to direct expression of Tla1 nucleic acid under the influence of changing environmental conditions. Examples of environmental conditions that may effect transcription by inducible promoters include anaerobic conditions, elevated temperature, or the presence of light. Plant promoters that are inducible upon exposure to chemicals reagents, such as herbicides or antibiotics, are also used to express Tla1 nucleic acids. For example, the maize In2 2 promoter, activated by benzenesulfonamide herbicide safeners, can be used (De Veylder (1997) Plant Cell Physiol. 38:568 577). Other useful inducible regulatory elements include copper-inducible regulatory elements (Mett et al., Proc. Natl. Acad. Sci. USA 90:4567-4571 (1993); Furst et al., Cell 55:705-717 (1988)); tetracycline and chlor-tetracycline-inducible regulatory elements (Gatz et al., Plant J. 2:397-404 (1992); Röder et al., Mol. Gen. Genet. 243:32-38 (1994); Gatz, Meth. Cell Biol. 50:411-424 (1995)); ecdysone inducible regulatory elements (Christopherson et al., Proc. Natl. Acad. Sci. USA 89:6314-6318 (1992); Kreutzweiser et al., Ecotoxicol. Environ. Safety 28:14-24 (1994)); heat shock inducible regulatory elements (Takahashi et al., Plant Physiol. 99:383-390 (1992); Yabe et al., Plant Cell Physiol. 35:1207-1219 (1994); Ueda et al., Mol. Gen. Genet. 250:533-539 (1996)); and lac operon elements, which are used in combination with a constitutively expressed lac repressor to confer, for example, IPTG-inducible expression (Wilde et al., EMBO J. 11:1251-1259 (1992)). An inducible regulatory element also can be, for example, a nitrate-inducible promoter, e.g., derived from the spinach nitrite reductase gene (Back et al., Plant Mol. Biol. 17:9 (1991)), or a light-inducible promoter, such as that associated with the small subunit of RuBP carboxylase or the LHCP gene families (Feinbaum et al., Mol. Gen. Genet. 226:449 (1991); Lam and Chua, Science 248:471 (1990)), or a light.
In one example, a promoter sequence that is responsive to light may be used to drive expression of a Tla1 nucleic acid construct that is introduced into Chlamydomonas that is exposed to light (e.g., Hahn, Curr Genet 34:459-66, 1999; Loppes, Plant Mol Biol 45:215-27, 2001; Villand, Biochem J 327:51-7), 1997. Other light-inducible promoter systems may also be used, such as the phytochrome/PIF3 system (Shimizu-Sato, Nat Biotechnol 20): 1041-4, 2002). Further, a promoter can be used that is also responsive to heat can be employed to drive expression in algae such as Chlamydomonas (Muller, Gene 111:165-73, 1992; von Gromoff, Mol Cell Biol 9:3911-8, 1989). Additional promoters, e.g., for expression in algae such as green microalgae, include the RbcS2 and PsaD promoters (see, e.g., Stevens et al., Mol. Gen. Genet. 251:23-30, 1996; Fischer & Rochaix, Mol Genet Genomics 265:888-94, 2001).
In some embodiments, the promoter may be from a gene associated with photosynthesis in the species to be transformed or another species. For example such a promoter from one species may be used to direct expression of a protein in transformed algal cells or cells of another photosynthetic marine organism. Suitable promoters may be isolated from or synthesized based on known sequences from other photosynthetic organisms. Preferred promoters are those for genes from other photosynthetic species that are homologous to the photosynthetic genes of the algal host to be transformed. For example, a series of light harvesting promoters from the fucoxanthing chlorophyll binding protein have been identified in Phaeodactylum tricornutum (see, e.g., Apt, et al. Mol Gen. Genet. 252:572-579, 1996). In other embodiments, a carotenoid chrlophyll binding protein promoter, such as that of peridinin chlorophyll binding protein, can be used.
In some embodiments, promoters are identified by analyzing the 5′ sequences of a genomic clone corresponding to the Tla1 genes described here. Sequences characteristic of promoter sequences can be used to identify the promoter. Sequences controlling eukaryotic gene expression have been extensively studied and include basal elements such as CG-rich regions, TATA consensus sequences etc. In plants, further upstream, there is typically a promoter element with a series of adenines surrounding the trinucleotide G (or T) N G. J. Messing et al., in GENETIC ENGINEERING IN PLANTS, pp. 221-227 (Kosage, Meredith and Hollaender, eds. (1983)).
A number of methods are known to those of skill in the art for identifying and characterizing promoter regions in plant genomic DNA (see, e.g., Jordano, et al., Plant Cell, 1:855 866 (1989); Bustos, et al., Plant Cell, 1:839 854 (1989); Green, et al., EMBO J. 7, 4035 4044 (1988); Meier, et al., Plant Cell, 3, 309 316 (1991); and Zhang, et al., Plant Physiology 110:1069 1079 (1996)). A promoter can be additionally evaluated by testing the ability of the promoter to drive expression in plant cells, e.g., green algae, in which it is desirable to introduce a Tla1 expression construct.
The vector comprising Tla1 nucleic acid sequences will typically comprise a marker gene that confers a selectable phenotype on plant or algae cells. Such markers are known. For example, the marker may encode biocide resistance, particularly antibiotic resistance, such as resistance to zeocin, kanamycin, G418, bleomycin, hygromycin, or herbicide resistance, such as resistance to chlorosluforon or Basta. In some embodiments, selectable markers for use in Chlamydomonas can be markers that provide spectinomycin resistance (Fargo, Mol Cell Biol 19:6980-90, 1999), kanamycin and amikacin resistance (Bateman, Mol - Gen Genet 263:404-10, 2000), zeomycin and phleomycin resistance (Stevens, Mol Gen Genet 251:23-30, 1996), and paramomycin and neomycin resistance (Sizova, Gene 277:221-9, 2001).
Tla1 nucleic acid sequences of the invention can be expressed recombinantly in plant cells, e.g., green algae, or other host cell expression systems, such as bacteria, yeast, and the like, to increase levels of Tla1 polypeptides. As appreciated by one of skill in the art, expression constructs can be designed taking into account such properties as codon usage frequencies of the organism in which the Tla1 nucleic acid is to be expressed. Tla1 polypeptides can be used, e.g., for the production of antibodies to monitor Tla1 expression. Alternatively, antisense or other Tla1 constructs are used to suppress Tla1 levels of expression.
A variety of different expression constructs, such as expression cassettes and vectors suitable for transformation of plant cells can be prepared. Techniques for transforming a wide variety of plant species are well known and described in the technical and scientific literature. See, e.g., Weising et al. Ann. Rev. Genet. 22:421-477 (1988). For example, a Tla1 nucleic acid construct can be directly introduced into a plant or algae cell by microparticle bombardment, or using a glass bead method (e.g., Kindle, Proc. Natl. Acad. Sci. USA 87:1228-1232, 1990). Alternatively, e.g., when transfecting higher plants, the DNA constructs may be combined with suitable T-DNA flanking regions and introduced into a conventional Agrobacterium tumefaciens host vector. The virulence functions of the Agrobacterium tumefaciens host will direct the insertion of the construct and adjacent marker into the plant cell DNA when the cell is infected by the bacteria. Other techniques are also known. For example, the introduction of DNA constructs using polyethylene glycol precipitation is described in Paszkowski et al. EMBO J. 3:2717-2722 (1984). Electroporation techniques are described in Fromm et al., Proc. Natl. Acad. Sci. USA 82:5824 (1985). Ballistic transformation techniques are described in Klein et al., Nature 327:70-73 (1987).
In some embodiments, Tla1 nucleic acid constructs are introduced into algae, e.g., green algae. As noted above, the nuclear, mitochondrial, and chloroplast genomes can be transformed through a variety of known methods (see, e.g., Kindle, J Cell Biol 109:2589-601, 1989; Kindle, Proc Natl Acad Sci USA 87:1228-32, 1990; Kindle, Proc Natl Acad Sci USA 88:1721-5, 1991; Shimogawara, Genetics 148:1821-8, 1998; Boynton, Science 240:1534-8, 1988; Boynton, Methods Enzymol 264:279-96, 1996; Randolph-Anderson, Mol Gen Genet 236:235-44, 1993).
Suppression of Tla1 Expression
The invention provides methods for generating a plant having a reduced chlorophyll antenna size by suppressing expression of a nucleic acid molecule encoding Tla1. In a transgenic plant of the invention, a nucleic acid molecule, or antisense constructs thereof, encoding a Tla1 gene product can be operatively linked to an exogenous regulatory element. The invention provides, for example, a transgenic plant characterized by reduced chlorophyll antenna size having an expressed nucleic acid molecule encoding a Tla1 gene product, or antisense construct thereof, that is operatively linked to an exogenous constitutive regulatory element. In one embodiment, the invention provides a transgenic plant that is characterized by small chlorophyll antenna size due to suppression of a nucleic acid molecule encoding a Tla1 polypeptide. Such a plant typically comprises an expression cassette stably transfected into the plant cell, such that that Tla1 polypeptide expression is inhibited constitutively or under certain conditions, e.g., when an inducible promoter is used.
Tla1 nucleic acid sequences can be used to prepare expression cassettes useful for inhibiting or suppressing Tla1 expression. A number of methods can be used to inhibit gene expression in plants. For instance, siRNA, antisense, or ribozyme technology can be conveniently used. For example, in Chlamydomonas , antisense inhibition can be used to decrease expression of a targeted gene (e.g., Schroda, Plant Cell 11:1165-78, 1999). Alternatively, an RNA interference construct can be used (e.g., Schroda, Curr Genet. 49:69-84, 2006, Epub 2005 Nov. 25).
For antisense expression, a nucleic acid segment from the desired Tla1 gene is cloned and operably linked to a promoter such that the antisense strand of RNA will be transcribed. The expression cassette is then transformed into plants, e.g., algae, and the antisense strand of RNA is produced. The antisense nucleic acid sequence transformed into plants will be substantially identical to at least a portion of the endogenous gene or genes to be repressed. The sequence, however, does not have to be perfectly identical to inhibit expression. Thus, an antisense or sense nucleic acid molecule encoding only a portion of Tla1 can be useful for producing a plant in which Tla1 expression is suppressed. The vectors of the present invention can be designed such that the inhibitory effect applies to other proteins within a family of genes exhibiting homology or substantial homology to the target gene.
For antisense suppression, the introduced sequence also need not be full length relative to either the primary transcription product or fully processed mRNA. Generally, higher homology can be used to compensate for the use of a shorter sequence. Furthermore, the introduced sequence need not have the same intron or exon pattern, and homology of non-coding segments may be equally effective. Normally, a sequence of between about 30 or 40 nucleotides and about full length nucleotides should be used, though a sequence of at least about 100 nucleotides is preferred, a sequence of at least about 200 nucleotides is more preferred, and a sequence of at least about 500 nucleotides is especially preferred. SEquences can also be longer, e.g., 1000 or 2000 nucleotides are greater in length.
Catalytic RNA molecules or ribozymes can also be used to inhibit expression of Tla1 genes. It is possible to design ribozymes that specifically pair with virtually any target RNA and cleave the phosphodiester backbone at a specific location, thereby functionally inactivating the target RNA. In carrying out this cleavage, the ribozyme is not itself altered, and is thus capable of recycling and cleaving other molecules, making it a true enzyme. The inclusion of ribozyme sequences within antisense RNAs confers RNA cleaving activity upon them, thereby increasing the activity of the constructs.
A number of classes of ribozymes have been identified. One class of ribozymes is derived from a number of small circular RNAs that are capable of self-cleavage and replication in plants. Ribozymes, e.g., Group I introns, have also been identified in the chloroplast of green algae (see, e.g., Cech, Annu Rev Biochem 59:543-568, 1990; Bhattacharya, Molec Biol and Evol 13:978-989, 1996; Erin, et al., Amer J Botany 90:628-633, 2003; Turmel, et al., Nucl Acids Res. 21:5242-5250, 1993; and Van Oppen et al., Molec Biol and Evol 10:1317-1326, 1993). The design and use of target RNA-specific ribozymes is described, e.g., in Haseloff et al. Nature, 334:585-591 (1988).
Another method of suppression is sense suppression (also known as co-suppression). Introduction of expression cassettes in which a nucleic acid is configured in the sense orientation with respect to the promoter has been shown to be an effective means by which to block the transcription of target genes. For an example of the use of this method to modulate expression of endogenous genes see, Napoli et al., The Plant Cell 2:279-289 (1990); Flavell, Proc. Natl. Acad. Sci., USA 91:3490-3496 (1994); Kooter and Mol, Current Opin. Biol. 4:166-171 (1993); and U.S. Pat. Nos. 5,034,323, 5,231,020, and 5,283,184.
Generally, where inhibition of expression is desired, some transcription of the introduced sequence occurs. The effect may occur where the introduced sequence contains no coding sequence per se, but only intron or untranslated sequences homologous to sequences present in the primary transcript of the endogenous sequence. The introduced sequence generally will be substantially identical to the endogenous sequence intended to be repressed. This minimal identity will typically be greater than about 65%, but a higher identity might exert a more effective repression of expression of the endogenous sequences. Substantially greater identity of more than about 80% is preferred, though about 90% or 95% to absolute identity would be most preferred. As with antisense regulation, the effect should apply to any other proteins within a similar family of genes exhibiting homology or substantial homology.
For sense suppression, the introduced sequence in the expression cassette, needing less than absolute identity, also need not be full length, relative to either the primary transcription product or fully processed mRNA. This may be preferred to avoid concurrent production of some plants that are overexpressers. A higher identity in a shorter than full length sequence compensates for a longer, less identical sequence. Furthermore, the introduced sequence need not have the same intron or exon pattern, and identity of non-coding segments will be equally effective. Normally, a sequence of the size ranges noted above for antisense regulation is used.
Endogenous gene expression may also be suppressed by means of RNA interference (RNAi), which uses a double-stranded RNA having a sequence identical or similar to the sequence of the target TLA1 gene. RNAi is the phenomenon in which when a double-stranded RNA having a sequence identical or similar to that of the target gene is introduced into a cell, the expressions of both the inserted exogenous gene and target endogenous gene are suppressed. The double-stranded RNA may be formed from two separate complementry RNAs or may be a single RNA with internally complementary sequences that form a double-stranded RNA. The introduced double-stranded RNA is initially cleaved into small fragments, which then serve as indexes of the target gene in some manner, thereby degrading the target gene. RNAi is known to be also effective in plants (see, e.g., Chuang, C. F. & Meyerowitz, E. M., Proc. Natl. Acad. Sci. USA 97:4985 (2000); Waterhouse et al., Proc. Natl. Acad. Sci. USA 95:13959-13964 (1998); Tabara et al. Science 282:430-431 (1998)). For example, to achieve suppression of the expression of a DNA encoding a protein using RNAi, a double-stranded RNA having the sequence of a DNA encoding the protein, or a substantially similar sequence thereof (including those engineered not to translate the protein) or fragment thereof, is introduced into a plant of interest, e.g., green algae. The resulting plants may then be screened for a phenotype associated with the target protein and/or by monitoring steady-state RNA levels for transcripts encoding the protein. Although the genes used for RNAi need not be completely identical to the target gene, they may be at least 70%, 80%, 90%, 95% or more identical to the target gene sequence. See, e.g., U.S. Patent Publication No. 2004/0029283. The constructs encoding an RNA molecule with a stem-loop structure that is unrelated to the target gene and that is positioned distally to a sequence specific for the gene of interest may also be used to inhibit target gene expression. See, e.g., U.S. Patent Publication No. 2003/0221211.
The RNAi polynucleotides may encompass the full-length target RNA or may correspond to a fragment of the target RNA. In some cases, the fragment will have fewer than 100, 200, 300, 400, 500 600, 700, 800, 900 or 1,000 nucleotides corresponding to the target sequence. In addition, in some embodiments, these fragments are at least, e.g., 15, 20, 25, 30, 50, 100, 150, 200, or more nucleotides in length. In some cases, fragments for use in RNAi will be at least substantially similar to regions of a target protein that do not occur in other proteins in the organism or may be selected to have as little similarity to other organism transcripts as possible, e.g., selected by comparison to sequences in analyzing publicly-available sequence databases. Thus, RNAi fragments may be selected for similarity or identity with the N terminal region of the Tla1 sequences of the invention (i.e., those sequences lacking significant homology to sequences in the databases) or may be selected for identity or similarity to conserved regions of Tla1 proteins, e.g., the hydrophobic region.
Expression vectors that continually express siRNA in transiently- and stably-transfected cells have been engineered to express small hairpin RNAs, which get processed in vivo into siRNAs molecules capable of carrying out gene-specific silencing (Brummelkamp et al., Science 296:550-553 (2002), and Paddison, et al., Genes & Dev. 16:948-958 (2002)). Post-transcriptional gene silencing by double-stranded RNA is discussed in further detail by Hammond et al. Nature Rev Gen 2:110-119 (2001), Fire et al. Nature 391:806-811 (1998) and Timmons and Fire Nature 395:854 (1998).
One of skill in the art will recognize that using technology based on specific nucleotide sequences (e.g., antisense or sense suppression technology), families of homologous genes can be suppressed with a single sense or antisense transcript. For instance, if a sense or antisense transcript is designed to have a sequence that is conserved among a family of genes, then multiple members of a gene family can be suppressed. Conversely, if the goal is to only suppress one member of a homologous gene family, then the sense or antisense transcript should be targeted to sequences with the most variation between family members.
Screening for Plants Having Suppressed Tla1 Expression
The invention also provides methods of screening for plants, e.g., green algae, having reduced Tla1 gene expression. Such plants can be generated using the techniques described above to target Tla1 genes. In other embodiments mutagenized plants, e.g., algae, can be screened for reduced Tla1 gene expression.
Methods for introducing genetic mutations into plant genes and selecting plants with desired traits are well known. For instance, plant cells can be treated with a mutagenic chemical substance, according to standard techniques. Such chemical substances include, but are not limited to, the following: diethyl sulfate, ethylene imine, ethyl methanesulfonate and N-nitroso-N-ethylurea. Alternatively, ionizing radiation from sources such as, X-rays or gamma rays can be used. In other embodiments, insertional mutagenesis can be performed (see, e.g., Polle et al., Planta 217:49-59, 2003).
Alternatively, homologous recombination can be used to induce targeted gene modifications by specifically targeting a Tla1 gene in vivo to suppress expression (see, generally, Grewal and Klar, Genetics 146:1221-1238 (1997) and Xu et al., Genes Dev. 10:2411-2422 (1996)). Homologous recombination has been demonstrated in plants (Puchta et al., Experientia 50:277-284 (1994), Swoboda et al., EMBO J. 13:484-489 (1994); Offringa et al., Proc. Natl. Acad. Sci. USA 90:7346-7350 (1993); and Kempin et al. Nature 389:802-803 (1997)).
In applying homologous recombination technology to the genes of the invention, mutations in selected portions of Tla1 gene sequences (including 5′ upstream, 3′ downstream, and intragenic regions) such as those disclosed here are made in vitro and then introduced into the desired plant using standard techniques. Since the efficiency of homologous recombination is known to be dependent on the vectors used, use of dicistronic gene targeting vectors as described by Mountford et al., Proc. Natl. Acad. Sci. USA 91:4303-4307 (1994); and Vaulont et al., Transgenic Res. 4:247-255 (1995) are conveniently used to increase the efficiency of selecting for decreased Tla1 gene expression in transgenic plants. The mutated gene will interact with the target wild-type gene in such a way that homologous recombination and targeted replacement of the wild-type gene will occur in transgenic plant cells, resulting in suppression of Tla1 activity.
Alternatively, oligonucleotides composed of a contiguous stretch of RNA and DNA residues in a duplex conformation with double hairpin caps on the ends can be used. The RNA/DNA sequence is designed to align with the sequence of the target Tla1 gene and to contain the desired nucleotide change. Introduction of the chimeric oligonucleotide on an extrachromosomal T-DNA plasmid results in efficient and specific Tla1 gene conversion directed by chimeric molecules in a small number of transformed plant cells. This method is described in Cole-Strauss et al., Science 273:1386-1389 (1996) and Yoon et al., Proc. Natl. Acad. Sci. USA 93:2071-2076 (1996).
In other embodiments, insertional mutagenesis can be used to mutagenize a population of plants, e.g., green algae, that can subsequently be screened.
Plants, e.g., green algae, with mutations can be screened for decreased Tla1 gene expression. Such decreases are determined by examining levels of Tla1 gene or protein expression. Techniques for performing such an analysis are readily known in the art and include quantitative RT-PCR, northern blots, immunoassays, and the like. Tla1 expression can also be evaluated by analyzing a phenotypic endpoint such as chlorophyll antenna size and selecting plants having reduce chlorophyll antenna size relative to normal.
Plants that can be Targeted
Tla1 can be suppressed in any number of eukaryotic green plants where it is desirable to reduce the rate of light absorption. For example, crop plants, such as tobacco, soybeans, barley, maize, and others (see, e.g., Okabe, et al., J Plant Physiol. 60:150-156, 1977; Melis & Thielen, Biochim. Biophys. Acta 589:275-286, 1980; Ghirardi et al., Biochim. Biophys. Acta 851:331-339, 1986; Ghirardi & Melis, Biochim. Biophys. Acta 932:130-137, 1988; Droppa, et al., Biochim. Biophys. Acta 932:138-145, 1988; and Greene, et al., Plant Physiol. 87:365-370, 1988).
Uses of Tla1 Suppressed Algae
In some embodiments, Tla1 is suppressed in algae. Algae, alga or the like, refer to plants belonging to the subphylum Algae of the phylum Thallophyta. The algae are unicellular, photosynthetic, anoxygenic algae and are non-parasitic plants without roots, stems or leaves; they contain chlorophyll and have a great variety in size, from microscopic to large seaweeds. Green algae, which are single cell eukaryotic organisms of oxygenic photosynthesis endowed with chlorophyll a and chlorophyll b belonging to Eukaryota—Viridiplantae—Chlorophyta—Chlorophyceae, are often a preferred target. For example, Tla1 expression can be suppressed in C. reinhardtii , which is classified as Volvocales—Chlamydomonadaceae. Algae strains that are of particular interest for this invention are, e.g., Chlamydomonas reinhardtii, Scenedesmus obliquus, Chlorella vulgaris, Botryococcus braunii, Botryococcus sudeticus, Dunaliella salina , and Haematococcus pluvialis.
Algae can be used in high density photobioreactors (see, e.g., Lee et al., Biotech. Bioengineering 44:1161-1167, 1994; Chaumont, J Appl. Phycology 5:593-604, 1990), bioreactors for sewage and waste water treatments (e.g., Sawayama et al., Appl. Micro. Biotech., 41:729-731, 1994; Lincoln, Bulletin De L'institut Oceangraphique ( Monaco ), 12:109-115, 1993), elimination of heavy metals from contaminated water (e.g., Wilkinson, Biotech. Letters, 11:861-864, 1989), the production of β-carotene (e.g., Yamaoka, Seibutsu -Kogaku Kaishi, 72:111-114, 1994), the production of hydrogen (e.g., U.S. Patent Application Publication No. 20030162273), and pharmaceutical compounds (e.g., Cannell, 1990), as well as nutritional supplements for both humans and animals (Becker, 1993, “Bulletin De L'institut Oceanographique (Monaco), 12, 141-155) and for the production of other compounds of nutritional value.
Conditions for growing Tla1-suppressed algae for the exemplary purposes illustrated above are known in the art (see, e.g., the exemplary references cited herein).
EXAMPLES
Methodology
Growth of the Algae
Chlamydomonas reinhardtii strain cw15, the arginine-requiring CC425, the chlorophyll-deficient mutant tla1 and Tla1-complemented strains of the tla1 mutant were grown to the mid-exponential growth phase either in TAP [Tris Acetate Phosphate, pH 7.4], TAP+Arg (Sueoka, Proc. Natl. Acad. Sci. USA 46:83-91, 1960; Harris, The Chlamydomonas source book: A comprehensive guide to biology and laboratory use : Academic Press, San Diego, 1989), or in modified minimal media containing 40 mM Tris-HCl, pH 7.4, supplemented with 25 mM sodium bicarbonate with or without Arg (TBP medium, Polle et al., Planta 211:335-344, 2000) in flat 1-1 Roux bottles at 25° C. under continuous illumination of 200 μmol photons m-2 s-1 provided by cool-white fluorescent lamps. The cultures were stirred continuously to ensure a uniform illumination of the cells and to prevent settling.
Cell Count and Chlorophyll Determinations
Cell density was estimated upon counting the number of cells per ml culture using a Neubauer ultraplane hemacytometer. Pigments from intact cells were extracted in 80% acetone and cell debris removed by centrifugation at 10,000 g for 5 min. The absorbance of the supernatant was measured with a Shimadzu UV-160U spectrophotometer and the chlorophyll (a and b) concentration of the samples was determined according to Arnon, Plant Physiol 24:1-15, 1949, with equations corrected as in Melis et al. ( Photochem. Photobiol. 45:129-136, 1987).
Nucleic Acid Extractions
Genomic DNA was isolated using either Stratagene's (La Jolla, Calif.) DNA purification kit or a combination of QIAGEN's (Valencia, Calif.) DNeasy plant mini kit and phenol chloroform extraction (Davies et al. 1992). BAC DNA was isolated using QIAGEN's midi prep kit. Total RNA was isolated using either QIAGENS's Plant RNeasy Kit or the Trizol Reagent (Invitrogen, Carlsbad, Calif.).
Cloning of Plasmid Insert Flanking Sequences from the tla1 Mutant
Genomic DNA of the tla1 mutant was digested with Apa I (New England Biolab, Beverly, Mass.) and size-fractionated by 0.8% agarose gel electrophoresis. Restriction enzyme digestion yielded a DNA fragment of about 5 kb, containing about 2 kb of Chlamydomonas genomic DNA flanking the insertion and about 3 kb portion of the 5′ end of the pJD67 plasmid sequence (Polle et al. 2003, supra). Similarly, a 3.2 kb DNA fragment was identified, which contained about 2.2 kb of the 3′ end of the pJD67 plasmid sequences and about 1 kb of Chlamydomonas genomic DNA flanking the insertion (Polle et al. 2003, supra). Therefore, following agarose gel electrophoresis of Apa I-digested tla1 genomic DNA, fragments migrating in the 6-4 kb region were used for the construction of a 5′ insert flanking DNA library. Similarly, fragments migrating in the 4-3 kb region were used to construct a 3′ insert flanking DNA library.
The vector was digested with Apa I and treated with alkaline phosphatase (Promega, San Luis Obispo, Calif.) to avoid self-ligation of the plasmid. DNA fragments that migrated between the molecular weight markers of 4-6 kb and 3-4 kb were gel purified using QIAEX II gel extraction kit (QIAGEN, Valencia, Calif.) and were ligated into the pZero Kan+ vector (which includes a kanamycin resistance gene, Promega, San Luis Obispo, Calif.) for the construction of a partial genomic library containing insert-5′ and 3′ flanking sequences. Use of the Apa I restriction enzyme in the digestion of the tla1 genomic DNA proved useful not only in the spatial separation of the 5′-insert flanking sequences from the 3′-insert flanking sequences, but also in the separation of the insert flanking sequences from the endogenous copy of the ARG7.8 gene.
About 5000 E. coli colonies containing the partial genomic DNA libraries of the tla1 mutant were screened using appropriate DNA probes derived from the ARG7.8 gene (Polle et al. 2003, supra). The probe Sal I-Sal I (1.3 kb representing the 5′ end of the ARG7 structural gene) was used to screen a partial genomic library containing the 5′-insert flanking sequences. The probe Nde I-Nde I (0.75 kb) derived from the 3′ end of the ARG7 was used to screen a partial genomic library containing the 3′-insert flanking sequences ( FIG. 1 ).
Isolation of a BAC Clone
A DNA fragment containing the insert-3′ flanking sequence was subsequently used for screening a commercially available wild type Chlamydomonas reinhardtii BAC library, constructed in pBACmn vector and printed on nylon membrane referred to as a high-density filter (Incyte Genomics Inc, Palo Alto, Calif.).
Southern Blotting and RACE Analysis
For Southern blot analysis, 10 μg of genomic or BAC DNA was used for restriction digestion, separated on 0.8% agarose gels for Southern blot analyses. After separation of the DNA fragments, nucleic acids were either blotted onto a positively charged nylon membrane (NEN Life Science Products, Inc, Wellesley, Mass.) or DNA was purified from excised gel pieces in the region of appropriate molecular weight. The blotted membranes were hybridized with 32 P-labeled probes (Random oligonucleotides DNA Labeling System, Roche Diagnostic Corporation, Alameda, Calif.). The probe DNA was PCR-amplified using specific primers designed from the insert-3′ flanking sequence of the tla1 mutant. Both of these primers were derived from the coding region of the Tla1 gene.
Tla1-cDNAs were synthesized using 1 μg of total RNA isolated from either WT or tla1 mutant with “primer 5” (Table 1) designed from the coding-2 region of the Tla1 gene and an oligo dT anchor primer (Invitrogen, Carlsbad, Calif.). These cDNAs were used as templates for 5′ and 3′ RACE analyses using a kit from Boehringer, Mannheim (Germany).
TABLE 1 Exemplary PCR primers and expected product sizes in wild type, tla1 mutant and tla1 complemented strains. Expected products from strains tla1- tla1 com- Primers WT mutant plements “primer 1” 589 bp No 589 bp (5′TACGGGAATTTGCGGAACCTC genomic product genomic 3′; (SEQ ID NO: 4) DNA DNA and product product “primer 4” (5′TTGTTGTCCAGCACCAGCAC 3′); (SEQ ID NO: 5) probing for the 5′UTR of Tla1 “primer 7” No 681 bp 681 bp (5′CAACGCATATAGCGCTAGCAG C product genomic genomic 3′; (SEQ ID NO: 4) DNA DNA and product product “primer 4” (5′TTGTTGTCCAGCACCAGCAC 3′; (SEQ ID NO: 7) probing for the 3′end of pJD67 “primer 1” 939 bp No 939 bp (5′TACGGGAATTTGCGGAACCTC genomic product genomic 3′) DNA DNA and product; product; “primer 6” 823 bp 823 bp (5′AACACACACCCCGCACT 3′); cDNA cDNA probing for the full product product length Tla1 gene and transcript “primer 8” No No 436 bp (5′GGGACTTCGTGGAGGACG 3′) product product genomic ; SEQ ID NO: 8) and DNA “primer 9” product (5′GGTTAGTCCTGCTCCTCGG 3′; SEQ ID NO: 9) probing for the Ble gene “primer 3” 409 bp 40 bp 409 bp (5′ cDNA cDNA cDNA GGGCCCTTCAGCTGCTCCGCTGACC product product product AAACC 3′; SEQ ID NO: 10) and “primer 5” (5′GGGCCCGAACGGG TTGTCCGCCTGCGCCTTGC 3′; SEQ ID NO: 11) Probing for the Tla1 transcript “primer 2” 525 bp 525 bp 525 bp (5′GCTGCTCCGCTGACCAAA 3′) genomic genomic genomic ; SEQ ID NO: 12)and DNA DNA DNA “primer 5” product; product; product; (5′ 454 bp no cDNA 454 bp GGGCCCGAACGGGTTGTCCGCCTG cDNA product cDNA CGCCTTGC 3′; SEQ ID NO: 11 product product probing for the Tla1 transcript TCF (5′CGGGGTACCACTTTCAGCTGCTCCGCT 3′; SEQ ID NO: 13) and TCR (5′ CCAAGCTTCCTCTT TCCCCCCCACC 3′; SEQ ID NO: 14); cloning primers used for amplifying the cDNA coding for the full length Tla1, off the cDNA library for Tla1 over- expression. PCR product size is 750 bp.
Transformation of the tla1 Mutant
BAC clone 39e16 DNA was digested with restriction enzymes ApaI or PstI. An approximately 3.7 kb DNA fragment, derived upon Apa I digestion (Apa I-Apa I), and an about 3 kb DNA fragment, derived upon Pst I digestion (Pst I-Pst I) were subcloned. The 2 kb DNA overlap region between these two clones (p5′TlaApa-4 and p3′TlaPst-3-3) was removed upon Apa I digestion of the 3 kb p3′TlaPst-3-3 clone. Subsequently, the Apa I-Apa I fragment and the 3′ end of the Pst I-Pst I DNA fragment, which resulted from the ApaI digestion, were re-ligated to yield the complete 4.7 kb sequence of the Tla1 gene in pBluescript. The resulting pFTla-5 plasmid DNA was sequenced to confirm the correct coding sequence of the Tla1 gene.
The ble gene encoding zeocin resistance along with its RbcS2 promoter and terminator was excised from plasmid pSP124S (Stevens et al., Mol. Gen. Genet. 251:23-30, 1996) by Hind III digestion and inserted at the 5′ end of the Tla1 gene in tandem to generate plasmid pSK9.2BleFTla. This plasmid was linearized upon digestion with Kpn I and used to transform the tla1 mutant by the glass bead method (Debuchy et al., EMBO J. 8:2803-2809, 1989). Transformant colonies were selected for zeocin resistance on TAP agar plates in the presence of 5 μM zeocin. Zeocin-resistant colonies were further screened for tla1 complementation by visual inspection of the colony coloration. Zeocin-resistant colonies having dark green coloration were tested for the presence of the wild type Tla1 gene and Tla1 protein amount by PCR/RT-PCR and Western blot analysis, respectively.
PCR and RT-PCR Analysis
Strains with tla1 mutations complemented with the Tla1 gene (tla1-complements) were first tested by PCR to check for the presence of two distinct Tla1 genes (wild type and mutant) and of the Ble tag. PCR was applied to genomic DNA by using two different forward primers, namely a Tla1 5′ UTR specific primer (“primer 1”: 5′ TACGGGAATTTGCGGAACCTC 3′ (SEQ ID NO:4), Table 1) and a primer designed from the 3′ end of the pJD67 vector that was inserted just upstream of the start codon of the Tla1 gene (“primer 7”: 5′ CAACGCATATAGCGCTAGCAGC 3′(SEQ ID NO:6), Table 1). A reverse primer was defined from the second exon of the Tla1 gene (“primer 4”: 5′ TTGTTGTCCAGCACCAGCAC 3′(SEQ ID NO:5), Table 1). Upstream 5′ UTR specific primer “primer 1” and the down stream 3′ UTR specific PCR primer (“primer 6”: 5′ AACACACACCCCGGCACT 3′(SEQ ID NO:31), Table 1) were used to probe for the full-length Tla1 transcript. Tla1 5′UTR specific “primer 2” (5′ GCTGCTCCGCTGACCAAA 3′; SEQ ID NO:12) or Tla1 exon 1-specific “primer 3” (5′ GGGCCCTTCAGCTGCTCCGCTGACCAAACC 3′(SEQ ID NO:10), Table 1) were used in conjunction with the reverse “primer 5” (5′ GGGCCCGAACGGGTTGTCCGCCTGCGCCTTGC 3′; SEQ ID NO:11) defined from the second exon of the Tla1 gene to check for the presence of the Tla1 transcript in the tla1-complemented strains. Presence of the Ble tag was tested by PCR using a forward primer located in the second exon of the Ble gene (“primer 8”: GGGACTTCGTGGAGGACG 3′SEQ ID NO:8), Table 1) and a reverse primer located in the third exon of the Ble gene (“primer 9”: 5′ GGTTAGTCCTGCTCCTCGG 3′ (SEQ ID NO:9), Table 1). The one-step RT-PCR kit (QIAGEN, Valencia, Calif.) was used for RT-PCR experiments. Platinum Taq polymerase (Invitrogen, Carlsbad, Calif.) was used for the PCR amplification. A 1 kb plus DNA ladder was used as DNA size markers (Invitrogen, Carlsbad, Calif.).
Generation of Tla1 Protein Overexpression Constructs
An amplified Chlamydomonas cDNA core library obtained from the laboratory of Dr. James V. Moroney (Louisiana State University, Baton Rouge, La.) was used to amplify Tla1 cDNA for generating the Tla1 protein overexpression construct. This cDNA library has been generated by cloning the cDNA core library ( Chlamydomonas Genetics Center, Duke University) into the lambda ZapII vector (Stratagene, La Jolla, Calif.). In vivo excision of the pBluescript phagemid from the lambda ZapII vector, involving the Ex-Assist interference-resistant helper phage along with the SOLR strain of E. coli was used in the amplification of the cDNA core library.
The Tla1 cDNA sequence coding for the full length Tla1 protein was amplified from the cDNA library by PCR. The 5′ end PCR primer (TCF) has the sequence 5′-CGGGGTACCACTTTCAGCTGCTCCGCT-3′ (SEQ ID NO:13)(Table 1) and a KpnI site was incorporated at the 5′ end. The 3′ end PCR primer (TCR) has the sequence 5′-CCCAAGCTTCCTCTTTCCCCCCCACC-3′ (SEQ ID NO:32) and a HindIII site was incorporated at the 5′ end. Amplified Tla1 cDNAs were purified from the DNA gel using the QIAEX II gel extraction kit (QIAGEN, Valencia, Calif.) and were cloned into the pQE80L overexpression vector (QIAGEN, Valencia, Calif.) which has a 6* His (SEQ ID NO:33) tag. The vector and the purified Tla1 cDNAs were double digested with Kpn I and Hind III. Ligation of the 733 bp Tla1 PCR product immediately downstream of the 6* His (SEQ ID NO:33) tag sequence in the pQE80L vector was performed following the protocol given in the New England Biolab (NEB, Beverly, Mass.) technical manual. E. coli strain DH5α cells were transformed. Transformants were isolated by screening colonies on LB+ Amp (100 μg/mL-1) plates. In-frame insertion of Tla1 with the His tag sequence in the recombinant clone was verified by double restriction enzyme digestion analyses with Kpn I and Hind III and DNA sequencing.
Overexpression and Purification of His-tagged Tla1 Protein for the Generation of Polyclonal Specific Antibodies
Selected E. coli clones of Tla1 were grown at 37° C. in 200 mL of LB media on a rotary shaker. The cells were induced for 5 h with 1 mM IPTG when the culture OD600 was between 0.6 and 0.7. Both induced and uninduced E. coli cells were harvested and resuspended in lysis buffer [100 mM NaH 2 PO 4 , 10 mM Tris-Cl (pH 8), 8 M urea] followed by sonication. Equal amounts of protein samples from induced and uninduced cells were subjected to 12.5% SDS-PAGE gel electrophoresis to test for the overexpression of the recombinant protein.
The recombinant fusion protein was purified by a one-step affinity chromatography using Ni-NTA superflow columns. Crude sonicated cell extracts were passed through Ni-NTA superflow columns (1 mL of the nickel-charged resin binds 10-15 mg of the recombinant protein). The column was washed with 6 L of wash buffer [100 mM NaH 2 PO 4 , 10 mM Tris-HCl (pH 6.3), 8 M urea]. At the final step, fusion proteins were eluted from the column by elution buffer [100 mM NaH 2 PO 4 , 10 mM Tris-HCl (pH 4.5), 8 M urea]. Purified recombinant proteins were further concentrated by a passage through Centricon columns (Amicon, Billerica, Mass.). The recombinant proteins were recovered from the membrane of the filter upon elution with phosphate buffered saline (pH 7.4) containing 137 mM NaCl, 2.7 mM KCl, 4.3 mM NaH 2 PO 4 and 1.4 mM KH 2 PO 4 4. Purification of the recombinant protein was tested upon SDS-PAGE using the Benchmark prestained protein ladder (Invitrogen, Carlsbad, Calif. The purified recombinant protein was used for the generation of specific polyclonal antibodies (ProSci Incorporated (Poway, Calif.) following a standard protocol. Approximately 1.6 mg of protein in each of two rabbits was used to generate the Tla1 antibodies.
Cellular Protein Analysis
Chlamydomonas cells were harvested, washed twice with fresh medium and resuspended in TEN buffer (10 mM Tris-HCl, 10 mM EDTA and 150 mM NaCl; pH 8). Following sonication, the crude cell extract was incubated in the presence of solubilization buffer (Smith et al. 1990). Protein concentration was determined and gel lanes were loaded with an equal amount of Chl, in the range of 4 to 6 nmol Chl, as indicated. SDS-PAGE analysis was performed on a 12.5% gel, using either the Benchmark prestained or unstained protein ladder (Invitrogen, Carlsbad, Calif.), at a constant current of 10 mA for 5 h. Gels were stained with 1% Coomassie brilliant Blue R for protein visualization.
Western Blot Analysis
Electrophoretic transfer of the SDS-PAGE resolved proteins onto nitrocellulose was carried out for 2 h at a constant current of 400 mA in the transfer buffer (25 mM Tris, 192 mM glycine and 20% methanol). The titer of the Tla1 immune serum was probed with different amounts of the purified recombinant His tagged Tla1 protein (2 pg-20 ng), as well as with the total protein extract of wild type (CC425), tla1 mutant, and tla1-complements. The Tla1 immune serum was diluted with buffer [Tris-buffered saline, 0.005% Tween 20 and 1% bovine serum albumin (pH 7.4)] to a ratio of 1:3,000 before being used as a primary probe. The secondary antibody used for Western blotting was conjugated to horseradish peroxidase (BioRad, Hercules, Calif.) and diluted to a ratio of 1:30,000 with the antibody buffer. Western blots were developed by using The Supersignal West chemiluminescent substrate kit (Pierce, Rockford, Ill.).
Accession Numbers
GenBank Accession numbers for the exemplary Tla1 sequences in the examples are AF534570 (complete Tla1 genomic DNA sequence with exons and intron) and AF534571 (complete mRNA sequence with 5′ and 3′ untranslated regions).
Example 1
Cloning of the Tla1 Gene
Southern blot analyses of the Chlamydomonas reinhardtii tla1 mutant revealed a single pJD67 plasmid insert in the nuclear genome. Genetic crosses and random progeny analyses revealed that the exogenous ARG7.8 gene co-segregated with the tla1 phenotype (Polle et al. 2003, supra). On the basis of these properties, it was inferred that insertion of the pJD67 plasmid must have interrupted, or deleted, a gene that is involved in the regulation of the light-harvesting Chl antenna size of photosynthesis.
The 5′ end vector sequence information, required for plasmid rescue, had been deleted from the insert site ( FIG. 1A ). Thus, plasmid rescue could not be employed for the cloning of the genomic DNA that is flanking the insert. To identify the gene, two different partial genomic libraries of the tla1 mutant, representing the 5′ and 3′ plasmid insert flanking sequences were constructed and screened with appropriate probes (see Materials and methods). Three positive clones were identified from the 5′ insert flanking DNA library and only one positive clone from the 3′ insert flanking DNA library. All of the above four positive clones were confirmed by restriction enzyme and sequence analysis.
A database search with the 5′-insert flanking sequence did not show significant homology to any existing EST sequences. However, a BLAST search with the 3′-insert flanking sequence matched the Chlamydomonas EST sequence 894001DO4.yl, which was deposited in the GenBank with Accession No. BE024188. The designation ‘y’ in this EST sequence denoted a 5′ end of the respective cDNA.
Isolation of a BAC Clone Containing the Full Length Tla1 Gene
The 3′-insert flanking sequence of tla1 was used to screen a high-density filter containing a Chlamydomonas wild type BAC library. A BAC clone, number 39e16, was identified as containing the complete Tla1 gene sequence. Southern blot analysis of the 39e16 clone DNA with several restriction enzymes (using the 3′-insert flanking sequence as a probe) permitted construction of a Tla1 restriction map.
FIG. 1A shows a map of the pJD67 insertion site in the nuclear genome of the tla1 mutant. It is shown that about 2.3 kb of the 5′ end of the pJD67 was deleted upon plasmid insertion in the C. reinhardtii nuclear genome. It is also shown that about 6 kb of genomic DNA was deleted upon plasmid insertion. Nine bps of the 3′ end of the plasmid sequences were also deleted upon plasmid insertion.
A full-length cDNA was obtained upon RT-PCR, and 5′ and 3′ RACE analyses using cDNA from the WT (cw15) strain. The full-length cDNA showed an open reading frame encoding a protein of 213 amino acids. DNA sequence analyses of the 39e16 BAC clone revealed the structure of the full-length Tla1 genomic DNA. Genomic and cDNA analysis of the Tla1 gene showed the presence of a 104 bp 5′ UTR, a single intron of 116 bases, and 1.26 kb of 3′ UTR. FIG. 1B also compares the DNA structure in the Tla1 upstream region in wild type and tla1 mutant. In the tla1 mutant, the 3′ end of the pJD67 plasmid replaced the promoter and 5′ UTR of the wild type gene.
Transcription of the Tla1 gene in wild type and tla1 mutant was tested by RT-PCR and compared to that of genomic DNA PCR. Given the presence of the pJD67 insert in the 5′ UTR of the Tla1 gene, a question was raised as to whether the tla1 mutant was able to transcribe the remnant of the Tla1 gene. RT-PCR was performed with a forward primer designed from the 5′ UTR sequence of Tla1, (“primer 2”) and a reverse primer (“primer 5”) from the coding-2 sequence of this gene ( FIG. 2 ). This RT-PCR yielded products in the WT but not in the tla1 mutant ( FIG. 3 , lanes 1 and 2). With the set of PCR primers that were designed from within the coding sequence of the Tla1 (“primer 3” and “primer 5”), RT-PCR yielded products in both the WT and tla1 mutant ( FIG. 3 , lanes 4 and 5). PCR products obtained with the same primers from the genomic DNA of the tla1 strain were 116 bp larger than those obtained from the cDNA due to the presence of an intron ( FIG. 3 , lane 6).
5′ Race analysis of the Tla1 cDNAs from the wild type and mutant revealed polymorphism in the 5′ UTR sequences of wild type and tla1 mutant. FIG. 4 (upper) shows the 5′ RACE analysis of the wild type cDNA with a portion of the 5′ UTR, the ATG start codon, and the corresponding downstream coding nucleotide sequence. In the tla1 mutant ( FIG. 4 , middle panel), the ATG start codon is preserved. However, the entire upstream 5′ UTR and promoter regions of the Tla1 gene are deleted and replaced by the 3′ end of the pJD67 plasmid sequence, represented by the lower case and underlined nucleotide sequence. FIG. 4 (lower panel) shows the nucleotide sequence of the complete 3′ end of the pJD67 plasmid DNA. Nucleotides denoted in upper case characters belong to the ARG7.8 gene. Nucleotides denoted in lower case characters belong to the 3′ end of the vector sequence (pBR322). The underlined portion of the pJD67 3′end is also found in the cDNA nucleotide sequence obtained from the 5′ RACE analysis of the tla1 mutant ( FIG. 4 , middle panel, lower case underlined nucleotides). Note that nine bases, i.e., a t t a a a g c t, at the 3′ end of the full-length pJD67 ( FIG. 4 , lower panel) were deleted from the insertion site ( FIG. 4 , lower panel, black background). In sum, 187 bp of the 3′ end of the pJD67 vector sequence have become the 5′ UTR sequence of the Tla1 gene in the tla1 mutant, as they were amplified by the 5′ RACE in the latter.
Complementation of the tla1 Mutant
A 4.7 kb genomic DNA, representing the full length Tla1 gene was cloned in pBluescript ( FIG. 5 ). This plasmid was digested with Hind III and the Ble gene was added at the 5′ end of the Tla1 gene to generate plasmid pSK9.2BleFTla1 (see Materials and methods). This plasmid was used to complement the tla1 mutant. Transformant colonies were selected on agar plates in the presence of 5 μM zeocin and screened for dark green coloration. Three dark green colonies, putative complements of the Tla1 gene were randomly isolated and streaked on to a TAP agar plate along with the wild type and tla1 mutant strains ( FIG. 6 ). These putative complements, tla1-comp1, tla1-comp2 and tla1-comp3, showed wild type phenotype in terms of coloration and in vivo chlorophyll fluorescence induction kinetics. The putative complements were grown autotrophically in TBP medium and tested for the Chl/cell and Chl a/Chl b ratios.
Table 2 shows that wild type C. reinhardtii had a Chl a/Chl b ratio of 2.6, whereas the tla1 mutant had a Chl a/Chl b ratio of 6. The putative tla1-complemeted strains had much lower Chl a/Chl b ratios, ranging between 2.8-3.0. These values are much closer to that of the wild type than to the tla1 parental host strain. A lower Chl a/Chl b ratio suggests assembly of peripheral subunits of the Chl a-b light-harvesting complex, underlying an enlarged photosystem Chl antenna size (Polle, et al., Plant Cell Physiol. 42:482-491, 2001; and Polle et al., 2003, supra). Table 2 also shows the Chl/cell values of the various strains. Chl/cell in the wild type (3.2×10-15 mol/cell) was substantially greater than that in the tla1 mutant (1.1×10 −15 mol/cell). The complemented strains had Chl/cell values (2.2-2.8×10 −15 mol/cell) comparable to that of the wild type, providing evidence of the return of the tla1-complemented strains to wild type levels of Chl content. Moreover, chlorophyll fluorescence induction kinetic measurements, with intact cells in the presence of DCMU, showed that the complemented strains, very much like the wild type, had a sigmoidal fluorescence rise curve, evidence of a statistical pigment bed organization afforded by a large Chl antenna size, as compared with the exponential fluorescence induction kinetics in the tla1 mutant (not shown). The lower Chl a/Chl b ratio, greater Chl/cell ratio (Table 2) and sigmoidal fluorescence induction kinetics in the Tla1-complemented strains are evidence of a direct cause-and-effect relationship between the amount of the Tla1 protein and the amount of chlorophyll in C. reinhardtii . Thus, it is concluded that the Tla1 gene regulates the Chl antenna size of photosynthesis in this model green alga.
TABLE 2
Chl a/Chl b ratio and Chl content per cell in C. reinhardtii
wild type (WT), tla1 mutant and tla1 mutant complemented
with the Tla1 gene (comp1–3). Statistical error
(+/−SD) was <10% of the values shown.
Chl a/Chl b
Chl, × 10 −15
Strain
ratio
mol/cell
WT (cw15)
2.6
3.2
tla1
6.0
1.1
tla1-comp1
2.9
2.8
tla1-comp2
3.0
2.2
tla1-comp3
2.8
2.4
Example 2
Tla1 Gene Expression is Reduced in the tla1 Mutant Strain
In the subsequent more detailed biochemical and molecular analyses, a comparative and quantitative evaluation of wild type, tla1 mutant, tla1-comp1 and tla1-comp2 was undertaken. When PCR was performed on the genomic DNA using “primer 1” and “primer 4” (Tla1 5′UTR/Exon-2, FIGS. 2A and 2C ) wild type, tla1-comp1 and tla1-comp2 yielded a 589 bp product, whereas the tla1 mutant failed to yield a product, consistent with the absence of its 5′UTR region ( FIG. 7A ). When “primer 7” and “primer 4” (pJD67 3′ end/Tla1 Exon-2, FIG. 2B ) were used in the PCR reaction, the tla1 mutant, tla1-comp1 and tla1-comp2 generated a product of 684 bp whereas the wild type did not, consistent with the absence of the pJD67 plasmid in the latter ( FIG. 7B ). When Ble primers, “primer 8” and “primer 9” ( FIG. 2C ) were used for the genomic DNA PCR reaction, tla1-comp1 and tla1-comp2 yielded a product of 436 bp, whereas both wild type and tla1 mutant failed to generate a product ( FIG. 7C ). PCR was also employed to test for the presence of the intact full length Tla1 gene in the two complements using the “primer 1” and “primer 6” (Tla1 5′UTR/Tla1 3′UTR, FIG. 2A ). Wild type, tla1-comp1 and tla1-comp2 gave a product of 939 bp whereas the tla1 mutant did not yield a product ( FIG. 7D ). When the same primers were used to perform RT-PCR, wild type, tla1-comp1 and tla1-comp2 gave a product of 823 bp, whereas the tla1 mutant did not yield a product ( FIG. 7E ). These results are evidence of successful complementation of the tla1 mutant by the ble-Tla1 construct.
Western Blot Analysis with Tla1-Specific Antibodies in Wild Type tla1 Mutant and Tla1 Complemented Strains
E. coli cells harboring the recombinant 6* His-Tla1 construct were induced for 5 h at 37° C. to overexpress the His-tagged Tla1 fusion protein. The overexpressed recombinant Tla1 protein comprised approximately 20% of the total E. coli protein ( FIG. 8A ). The recombinant fusion protein was purified by one-step affinity chromatography using Ni-NTA superflow columns and further concentrated by a passage through Centricon columns. Purification of the 25 kD fusion protein was confirmed by SDS-PAGE and Coomassie staining ( FIG. 8B ).
Tla1 specific polyclonal antibodies positively cross-reacted with the purified 25 kD recombinant Tla1 protein and at levels as low as 2 pg ( FIG. 9A ). Whereas the molecular weight of the native Tla1 protein is 23.2 kD, the recombinant protein was slightly larger (25 kD) because of the extra seventeen amino acids, including the 6 * His (SEQ ID NO:33) tag, at its N-terminal end.
Total cell extract from wild type (CC425) and the tla1 mutant were loaded on a 12.5% SDS-PAGE gel on an equal chlorophyll basis ( FIG. 9B ). Tla1 antibodies detected the 23.2 kD Tla1 protein in the total protein extract from the wild type and tla1 mutant ( FIG. 9C ). The amount of the Tla1 protein was substantially lower in the tla1 mutant compared to that in the wild type ( FIG. 9C ). This provides evidence that a limited translation of the tla1 mRNA did occur in the mutant, however, this is in no way comparable to the levels of translation seen in the wild type. The substantially suppressed translation level of the Tla1 protein in the tla1 mutant is attributed to the absence of the native 5′UTR in this strain. The apparent molecular weight of the Tla1 protein is the same in WT and tla1 mutant ( FIG. 9C ). This observation is consistent with the notion that the wild type Tla1 protein lacks a transit peptide and is apparently a cytoplasmic protein.
Total protein extracts from the wild type, tla1 mutant and two tla1 complements (tla1-comp1 and tla1-comp2) were resolved on a 12.5% SDS-PAGE gel, lanes loaded on an equal chlorophyll basis ( FIG. 10A ). Western blot analysis of the total cell extract from these samples showed that the amount of the Tla1 protein in the two complements ( FIG. 10B , lanes 1 and 2) was comparable to that in the wild type ( FIG. 10B , W), whereas the amount of the Tla1 protein in the tla1 mutant was substantially lower from that of the other three ( FIG. 10B , lane T).
Example 3
Analysis of Tla1 Protein
Hydropathy Analysis of the Tla1 Protein
Analysis of the N-terminus sequence of the predicted Tla1 protein by ChloroP, (http://www.cbs.dtu.dk/services/ChloroP/), TargetP (http://www.cbs.dtu.dk/services/TargetP/) and MitoP (http://ihg.gsf.de/ihg/mitoprot.html) software programs failed to indicate the presence of a transit peptide, suggesting that Tla1 is a cytosolic protein. This indication was strengthened by the results of the Western blot analysis, where the mature protein size matched the predicted translation product size, suggesting absence of a cleavable transit peptide. FIG. 11 shows the hydropathy plot of the deduced amino acid sequence of the Tla1 protein, derived according to the method of Kyte & Doolittle (Kyte and Doolittle, J Mol Biol. 157:105-32982, 1982; http://occawlonline.pearsoned.com/bookbind/pubbooks/bc_mcampbell_genomics — 1/medialib /activities/kd/kyte-doolittle.htm). The Tla1 protein contains 213 mostly hydrophilic amino acids, suggesting that it is a soluble cytosolic protein. There was a single hydrophobic domain comprising 27 amino acids between residues 42 and 69, theoretically long enough to qualify as a transmembrane domain. This hydrophobic domain of 27 amino acids is highly conserved in similar proteins from other diverse organisms, suggesting a role in the catalytic/regulatory activity of the Tla1 protein.
Tla1 Homology with Genes from Other Organisms
A Blastp (protein database using protein sequence) search showed high homology of the Tla1 protein with expressed protein sequences of Arabidopsis thaliana (GenBank Accession No. NP — 568832) Oryza sativa (japonica cultivar-group) (Accession No. CAD39888) Ustilago maydis (Accession No. EAK83164), Drosophila melanogaster (Accession No. NP — 611731), Homo sapiens (Accession No. AAQ83690), Danio rerio (zebrafish) (Accession No. NP — 956420), Rattus norvegicus (Norway rat) (Accession No. XP — 214198), Xenopus tropicalis (Accession No. NP — 989181), Mus musculus (house mouse) (Accession No. NP — 035056). In view of the Chlamydomonas reinhardtii specific codon usage, we also searched nucleotide databases using the Tla1 protein sequence (tblastn-protein query against translated database). EST sequences deposited from several other plant species showed fairly high homology with the Tla1, including sequences from Hordeum vulgare, Solanum tuberosum, Medicago truncatula, Lycopersicon esculentum, Gossypium arboretum, Secale cereale, Triticum aestivum, Pinus taeda, Beta vulgaris, Populus tremula, Sorghum bicolor (results not shown). It is concluded that the Tla1 gene is present in many eukaryotes, including many wild-land and crop plants.
FIG. 12A shows an alignment of the deduced amino acid sequence of the Tla1 protein from C. reinhardtii alongside that of proteins from A. thaliana, O. sativa, H. sapiens and D. melanogaster . The sequence alignment in FIG. 12A shows very high similarity between the Tla1 protein in C. reinhardtii and the related proteins in these diverse organisms. Moreover, examination of identity/similarity patterns in FIG. 12A , based on the ClustalW analysis, revealed the common occurrence of domains where high similarity or identity of amino acids is observed. The highly conserved nature of these domains across diverse species suggest a common functional role for these proteins.
These related protein sequences were also aligned pair-wise and degrees of identity, high and low similarity were calculated on the basis of a ClustalW comparison. Results from such analyses (Table 3) showed that the C. reinhardtii Tla1 protein had a 72.68% homology to the corresponding protein in A. thaliana, 75.99% homology to O. sativa, 70.94% to D. melanogaster and 67.14% to H. sapiens (CGI-112). FIG. 12B shows a phylogenetic tree of the above-mentioned Tla1 homologues, based on the amino acid sequence comparisons http://www.ebi.ac.uk/clustalw/).
TABLE 3 Homology comparison of Tla1-like proteins in Chlamydomonas reinhardtii , Arabidopsis thaliana , Oryza sativa , Drosophila melanogaster and Homo sapiens . The % of amino acid identity, high similarity and low similarity was based on a ClustalW analysis of the deduced amino acid sequence of the respective proteins. % Pair compared Identity High similarity Low similarity % Homology C.r.-A.t. 35.62 23.75 13.31 72.68 C.r.-O.s.. 38.27 23.92 13.8 75.99 C.r.-D.m. 30.54 23.15 17.24 70.94 C.r.-H.s. 28.09 24.76 14.28 67.14
Summary
The ability of the photosynthetic apparatus to regulate the size of the functional Chl antenna was first recognized in pioneering work by Bjorkman and co-workers, more than 30-years ago (Bjorkman et al., Carnegie Institution Yearbook 71:115-135, 1972). In spite of the substantial number of physiological and biochemical studies on this phenomenon (reviewed Anderson, Annu Rev Plant Physiol 37:93-136, 1986; Melis, In, Oxygenic Photosynthesis: The Light Reactions ” (DR Ort, CF Yocum, eds), Kluwer Academic Publishers, Dordrecht, The Netherlands, pp. 523-538, 1996), genes for the regulation of the Chl antenna size of photosynthesis have not been identified. The current invention is based on the discovery that Tla1 plays a role in the regulation of the chlorophyll antenna size of photosynthesis. Not to be bound by theory, Tla1 is likely to regulate the expression of other genes that directly affect the chloroplast and the Chl antenna size and may define the relationship between nucleus and organelle in green algae, thereby regulating the rate of Chl biosynthesis and by extension the Chl antenna size of the photosystems. For example, in the tla1 mutant, total amount of Chl, Lhcb gene expression, abundance of LHC polypeptides, and levels of Chl b were all down regulated (Table 2), presumably as a consequence of down-regulation of translation of the Tla1 mRNA. Sensitive absorbance-difference kinetic spectrophotometry confirmed that the tla1 mutant had a truncated PSII Chl antenna size, down to 50%, and a truncated PSI Chl antenna size, down to 67% of that in the wild type (Polle et al. 2003, supra). Thus, in the tla1 mutant, the Chl antenna size of both photosystems, as well as total chlorophyll per cell were lowered relative to the wild type.
Further evidence for the role of the Tla1 gene in the regulation of the Chl antenna size of photosynthesis was obtained from the study of C. reinhardtii diploid analysis and from Tla1 complementation studies. Diploid analysis showed that the tla1 mutation is recessive (results not shown). About 25 diploids were tested, all of which showed WT phenotype in terms of normal green coloration of the colonies, normal Chl fluorescence and normal Chl a to Chl b ratio (in the range of 2.2-3.0) as opposed to the tla1 mutant phenotype of yellow-green coloration, lower Chl fluorescence and higher Chl a to Chl b ratio. The results of the diploid analysis served as the basis upon which a functional complementation of the tla1 mutant was undertaken. This was successfully implemented ( FIGS. 6 and 7 ) upon transformation of the tla1 strain with a WT copy of the Tla1 gene, containing about a 4.7 kb DNA sequence comprising the promoter region and its 5′ flanking sequence, the 5′ UTR, the coding sequence with a single intron, and the 3′ UTR region of the Tla1 gene.
Sequence analysis of the 3′-insert flanking sequence from the tla1 mutant revealed that the 3′ end of the plasmid was inserted within the C. reinhardtii genomic DNA, just prior to the ATG start codon of the Tla1 gene. In spite of the absence of the promoter and 5′UTR region of the Tla1 gene and the presence of a sizable plasmid insertion just prior to the ‘ATG’ start codon of the Tla1 gene, RT-PCR analysis ( FIG. 3 ) revealed the presence of Tla1 transcripts in the tla1 mutant. One possible explanation of this unusual observation is that, in the tla1 mutant, the Tla1 gene is co-transcribed along with the ARG7 gene under the control of the ARG7 gene promoter. Northern blot analyses, using the coding region of the Tla1 gene as a probe, revealed similar the Tla1-transcript size from both WT and tla1 mutant (results not shown). High molecular weight transcripts of the Tla1 gene could not be detected in the tla1 mutant, as would be expected from the unprocessed ARG7-Tla1 hybrid transcripts.
From the above characteristics (tla1 phenotype, diploid properties, complementation of the tla1 mutant with wild type Tla1 gene, and presence of Tla1 transcripts in the tla1 mutant), it is concluded that transcription of the Tla1 gene occurs in the tla1 mutant but translation of the respective mRNA is either impaired or minimized. Polymorphism in the 5′ UTR of the Tla1 gene has not measurably affected its mRNA stability since levels of these transcripts detected by Northern blot (data not shown) and RT-PCR analysis were the same in both the wild type and mutant. However, it has had a substantial effect on the rate of translation of the respective mRNAs, as evidenced from the Western blot analysis results. In the tla1 mutant, the 5′UTR consists of 187 bp sequences from the 3′end of the plasmid pJD67. Normally, the eukaryotic translation machinery does not recognize prokaryotic sequences. This could explain the much lower translation levels of the Tla1 mRNA in the mutant relative to that in the wild type.
It is apparent from these data that in green unicellular algae the Tla1 gene acts as an early component affecting the molecular regulatory mechanism for the Chl antenna size in of oxygenic photosynthesis. A genetic tendency of the algae to assemble large arrays of light absorbing chlorophyll antenna molecules in their photosystems is a survival strategy and a competitive advantage in the wild, where light is often limiting (Kirk, Light and photosynthesis in aquatic ecosystems, 2nd edn. Cambridge University Press, Cambridge, England, 1994). This property of the algae is detrimental to the yield and productivity in a mass culture under direct sunlight (Melis, Trends in Plant Science 4: 130-135, 1999), however. A truncated Chl antenna size, which would compromise the ability of the strain to compete and survive in the wild, is helpful in a controlled mass culture environment in photoreactors in diminshing the over-absorption and wasteful dissipation of excitation energy by individual cells. The size reduction of the Chl antenna will also diminish photoinhibition of photosynthesis (Powles, Annu Rev Plant Physiol 35: 15-44, 1984; Melis, 1999, supra) at the surface while permitting for greater transmittance of light deeper into the culture (Melis, 2005, supra). Such altered optical properties of the cells result in greater photosynthetic productivity and enhanced solar conversion efficiency by the culture as a whole. In support of this contention, preliminary experiments (Powles, Annu Rev Plant Physiol 35: 15-44, 1984) confirmed that a smaller Chl antenna size would result in a relatively higher light intensity for the saturation of photosynthesis in individual cells, while permitting for an overall greater solar conversion efficiency and productivity by the mass culture (Powles, Annu Rev Plant Physiol 35: 15-44, 1984). Thus, the Tla1 gene can be useful as a target to down-regulation Chl antenna size, e.g., in green microalgae.
The above examples are provided by way of illustration only and not by way of limitation. Those of skill in the art will readily recognize a variety of noncritical parameters that could be changed or modified to yield essentially similar results.
All publications, accession numbers, and patent applications cited in this specification are herein incorporated by reference as if each individual publication or patent application were specifically and individually indicated to be incorporated by reference.
Table of Exemplary Tla1 Nucleic Acid and Polypeptide Sequences
1 ggaacctcga tgtcgtgttg actttgcgtt acaaccgtga agtatattag aactcatttg 61 cctgccacaa cctcagacca agagacgcgc gaaaaactga cacgatgact ttcagctgct 121 ccgctgacca aaccgcgctc ttaaagattc ttgcacacgc ggctaagtat ccatcaaata 181 gcgtgaatgg tgtcctcgtc gggacagcga aggagggcgg ctctgtcgaa atcctggacg 241 cgattccact gtgtcacacg acgctgaccc tggcgccagc actggagata ggtctcgccc 301 aggtggagtc ctacacgcat atcacgggca gcgtggcgat tgtgggctac taccaatcag 361 acgcacgttt cggccccggg gacctacccc cgctaggtcg caaaattgcg gacaaggtgt 421 ctgagcacca ggctcaggcg gtggtgctgg tgctggacaa caagcggctg gagcagttct 481 gcaaggcgca ggcggacaac ccgttcgagc tgttcagcaa ggatggcagc aagggttgga 541 agcgcgcgag cgccgatggc ggagagctgg cgcttaaaaa cgcggactgg aagaagctgc 601 gcgaggagtt cttcgttatg ttcaagcagc tgaagcaccg gacactccac gattttgagg 661 agcacctgga cgacgccggg aaagactggc tcaacaaggg cttcgcctcc tcggtcaaat 721 tcctgttgcc cggcaacgcg ctgtaagggc cgcgtgaggc tagccgggat ggcggttccg 781 cgggatggtc gcagtgccgg ggtgtgtgtt gagaggagga gccggtgggg gggaaagagg 841 ttgaggaggt aggagagagg cgctggcatg gaggccggga ggcgctggag ctggagctgg 901 cgagctggtg ggtggtgctg ggcgagatcc tggaggcaca ggagtggtat gggcggtgca 961 gggacagcga cagcggatcg gcggacggta ttggtggagg gtgcgggggc cctggggtag 1021 tgtgcagggt gtgtgccacg tggcttgccg caaagcgcag cgtaccgata gttgagagaa 1081 agcacctgcg gccctgcgcg gccgcggcgt ggcggcgcgt ggggacacgc gcatcgtgcc 1141 gggtcgccgc aggccggagt gaatttcgtg ctgcacggcg cgttgaccag tccaccgact 1201 gacggccaac ggccatgagg gcttgttttg ggggataggg tcacatgaca ttttcggcgt 1261 tctttgcagt cagaatcagg atacgcttgc tttagtcttg attgtcagac ttgtcaggct 1321 gacgtttcag gcagacgaga gctcatgtgg ttttgactaa ccgggcgttg accatgggca 1381 gtcccaaacg tgccgtgcca cagggcatag cgagtgccat gtgctctcga gggcgaggtc 1441 gtgaggcacg tggaaactgt tgcggcgcct tcaccatggg tgctttctcg cgtgaggcac 1501 gtgaaactgt tgcggcgcct tcaccatggg tgctctctct cgtgaggctc agcggcaagt 1561 accagggagg gcgcaagaca cggatgaagc agtggttgcg catgccgcgg tctgttggcc 1621 gccgggaggt gatcggtgtg acgtggctgg tgcgtgtggt ggtttctccc gtggcctccc 1681 gtgtgtgact ggtgcgtgtt tgacgtggca aggtaggtaa atagtagtaa agcggcccag 1741 atacgttgct gtggcggttg tgcgtgcgca ggtggtgcat aggacagcgt tggttgtgtg 1801 tgcctgtgct gtgctgtgcg gtgccggacc gaagcgcggg gcggacaggc gcagggtggt 1861 agcggcgtgg cgggtaggct gccgcacaca gtacgtgtaa ctgtatgctg cgctgcatgt 1921 tactctgctt acggatgctt cctgactgta cgtgtggtgc ttgggtcgtg tcgccgtgca 1981 acgctgctgg cggcttcaat gggtggctgc ggatcagtgg gtggctgcgt gtatcggcgc 2041 gcccgtgttg aatcgaggac tgcag
SEQ ID NO:2 Tla1 Polypeptide Sequence
MTFSCSADQTALLKILAHAAKYPSNSVNGVLVGTAKEGGSVEILDAIPLC HTTLTLAPALEIGLAQVESYTHITGSVAIVGYYQSDARFGPGDLPPLGRK IADKVSEHQAQAVVLVLDNKRLEQFCKAQADNPFELFSKDGSKGWKRASA DGGELALKNADWKKLREEFFVMFKQLKHRTLHDFEEHLDDAGKDWLNKGF ASSVKFLLPGNAL
Conserved Domains: (SEQ ID NOS:24-28):
Domain A: amino acid positions 9–33 (QTALLKILAHAAKYPSNSVNGVLVG) Domain B: amino acid positions 41–70 (VEILDAIPLCHTTLTLAPALEIGLAQVESY) Domain C: amino acid positions 75–129 (GSVAIVGYYQSDARFGPGDLPPLGRKIADKVSEHQAQAVVLVLDNKRLE QFCKAQ) Domain D: amino acid positions 135–163 (ELFSKDGSKGWKRASADGGELALKNADWK) Domain E: amino acid positions 177–200 (KHRTLHDFEEHLDDAGKDWLNKGF)
SEQ ID NO:3 Tla1 Genomic Sequence
1
ggaacctcga tgtcgtgttg actttgcgtt acaaccgtga
agtatattag aactcatttg
61
cctgccacaa cctcagacca agagacgcgc gaaaaactga
cacgatgact ttcagctgct
121
ccgctgacca aaccgcgctc ttaaagattc ttgcacacgc
ggctaagtat ccatcaaata
181
gcgtgaatgg tgtcctcgtc gggacagcga aggagggcgg
ctctgtcgaa atcctggacg
241
cgattccact gtgtcacacg acgctgaccc tggcgccagc
actggagata ggtctcgccc
301
aggtgcgcat ggccccgaga gcccggggcg tggcttgtgc
tcgtcgatct gcgtgcatta
361
gttaccgcat cgctcccatg ctgcattccg cgctcagcct
caaataccct gattgcaggt
421
ggagtcctac acgcatatca cgggcagcgt ggcgattgtg
ggctactacc aatcagacgc
481
acgtttcggc cccggggacc tacccccgct aggtcgcaaa
attgcggaca aggtgtctga
541
gcaccaggct caggcggtgg tgctggtgct ggacaacaag
cggctggagc agttctgcaa
601
ggcgcaggcg gacaacccgt tcgagctgtt cagcaaggat
ggcagcaagg gttggaagcg
661
cgcgagcgcc gatggcggag agctggcgct taaaaacgcg
gactggaaga agctgcgcga
721
ggagttcttc gttatgttca agcagctgaa gcaccggaca
ctccacgatt ttgaggagca
781
cctggacgac gccgggaaag actggctcaa caagggcttc
gcctcctcgg tcaaattcct
841
gttgcccggc aacgcgctgt aagggccgcg tgaggctagc
cgggatggcg gttccgcggg
901
atggtcgcag tgccggggtg tgtgttgaga ggaggagccg
gtggggggga aagaggttga
961
ggaggtagga gagaggcgct ggcatggagg ccgggaggcg
ctggagctgg agctggcgag
1021
ctggtgggtg gtgctgggcg agatcctgga ggcacaggag
tggtatgggc ggtgcaggga
1081
cagcgacagc ggatcggcgg acggtattgg tggagggtgc
gggggccctg gggtagtgtg
1141
cagggtgtgt gccacgtggc ttgccgcaaa gcgcagcgta
ccgatagttg agagaaagca
1201
cctgcggccc tgcgcggccg cggcgtggcg gcgcgtgggg
acacgcgcat cgtgccgggt
1261
cgccgcaggc cggagtgaat ttcgtgctgc acggcgcgtt
gaccagtcca ccgactgacg
1321
gccaacggcc atgagggctt gttttggggg atagggtcac
atgacatttt cggcgttctt
1381
tgcagtcaga atcaggatac gcttgcttta gtcttgattg
tcagacttgt caggctgacg
1441
tttcaggcag acgagagctc atgtggtttt gactaaccgg
gcgttgacca tgggcagtcc
1501
caaacgtgcc gtgccacagg gcatagcgag tgccatgtgc
tctcgagggc gaggtcgtga
1561
ggcacgtgga aactgttgcg gcgccttcac catgggtgct
ttctcgcgtg aggcacgtga
1621
aactgttgcg gcgccttcac catgggtgct ctctctcgtg
aggctcagcg gcaagtacca
1681
gggagggcgc aagacacgga tgaagcagtg gttgcgcatg
ccgcggtctg ttggccgccg
1741
ggaggtgatc ggtgtgacgt ggctggtgcg tgtggtggtt
tctcccgtgg cctcccgtgt
1801
gtgactggtg cgtgtttgac gtggcaaggt aggtaaatag
tagtaaagcg gcccagatac
1861
gttgctgtgg cggttgtgcg tgcgcaggtg gtgcatagga
cagcgttggt tgtgtgtgcc
1921
tgtgctgtgc tgtgcggtgc cggaccgaag cgcggggcgg
acaggcgcag ggtggtagcg
1981
gcgtggcggg taggctgccg cacacagtac gtgtaactgt
atgctgcgct gcatgttact
2041
ctgcttacgg atgcttcctg actgtacgtg tggtgcttgg
gtcgtgtcgc cgtgcaacgc
2101
tgctggcggc ttcaatgggt ggctgcggat cagtgggtgg
ctgcgtgtat cggcgcgccc
2161
gtgttgaatc gaggactgca g
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The invention provides method and compositions to minimize the chlorophyll antenna size of photosynthesis by decreasing TLA1 gene expression, thereby improving solar conversion efficiencies and photosynthetic productivity in plants, e.g., green microalgae, under bright sunlight conditions.
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BACKGROUND OF THE INVENTION
The present invention relates to incorporation of meat trimmings into meat.
Meat trimmings are obtained from meat during the standard preparation of whole cuts of meat in the meat industry. The trimmings are usually, but not always, of low quality and usually contain some fat and some muscle tissue. It is possible, by using technology introduced onto the market in recent years, to incorporate suspensions made of meat trimmings into whole cuts of like meat to increase the weight using a multi-needle injector. By controlling parameters such as the amount of trimmings injected, the meat/fat ratio and the quality of the meat, this technology enables the production of cooked ham or other marinated meat products without affecting the standard quality with regard to flavour, shelf-life and lack of visibility of the suspension, and in some cases improving it, for instance, with regard to binding and yield. Such a process is described in U.S. Pat. No. 4,960,599. The cost saving of injecting trimmings is considerable when the trimmings are of low value compared to whole cuts of meat.
In order to impart a specificity to the flavour and to improve microbiological stability, it has been proposed to ferment raw marinated meat by using a starter culture in a brine or marinade prior to cooking to produce bacteriocins. However, since the raw marinated meat can under no circumstances be allowed to ferment at a temperature higher than about +8° C., the biggest problem is to find a starter culture that can produce bacteriocins and a specific flavour at low temperature. We have tested some commercially available cultures, but the effect on the final quality of the product regarding flavour and microbiological stability is minimal. In addition, the production time before the cooking step must be prolonged considerably.
SUMMARY OF THE INVENTION
We have found, surprisingly, that by fermenting meat trimmings with a bacteria prior to incorporation into meat, it is possible to adapt fermentation parameters such as temperature, time, humidity and ingredients, etc. to their optimal values.
Accordingly, the present invention provides a process for preparing meat containing meat trimmings therein which comprises incorporating into a meat piece a suspension of meat trimmings in a brine, marinade, or pickle having a temperature which does not exceed 1° C. and characterised in that before freezing, the meat trimmings are fermented with a bacteria.
The present invention also includes the product of the process which is, thereby, a meat piece having incorporated therein bacterially-fermented meat trimmings.
DETAILED DESCRIPTION OF THE INVENTION
In carrying out the process of the present invention, the meat used may be obtained from all types of meat such as pork, beef, lamb, poultry and fish. Raw whole cuts of meat may be chilled, e.g. to a temperature from -2° to 12° C., preferably from 2° to 10° C. and especially from 3° to 8° C., and deboned, and the trimmings may be removed in the usual manner. The meat trimmings used preferably are those removed from the actual piece of meat to be treated, but it is also possible to use trimmings from the same type of meat as the meat to be treated. It is also possible to use trimmings from a type of meat other than the meat to be treated, although this is generally less preferred.
The trimmings may be incorporated into trimmed whole meat cut pieces as such or into smaller portions of meat formed by dividing the whole meat cut pieces into smaller portion pieces having an average diameter of from 0.5 to 10 cm, more conveniently from 1 to 5 cm.
When the fermented meat trimmings are incorporated into whole cuts of meat, this may be carried out conventionally by injection, using, for instance, a multi-needle injector. When the meat trimmings are incorporated into smaller portions of meat, this may be carried out by mixing the meat trimmings with the smaller portions of meat, e.g. with agitation such as stirring or tumbling. For example, a suspension of the meat trimmings may be added directly to the meat pieces in a tumbler.
Before fermentation, the meat trimmings are conveniently ground until the majority of the particles have a size of less than 30 mm diameter and have an average particle size of from 1 mm to 5 mm, preferably from 2 mm to 4 mm diameter.
Before, during or after the addition of a bacteria starter culture, the ground meat trimmings may be mixed with a brine, pickle, or marinate. As is well known, a pickle is used for preserving meat and may contain brine, or other salt, or vinegar or acid liquor, while a marinade is used for flavouring meat and may contain brine, vinegar or wine, oil, spices and herbs, etc. For instance, the ground meat trimmings may be mixed with sugar and a nitrite salt such as sodium nitrite. The pH of the mixture is usually in the range of from about 5.2 to 6.3, preferably from 5.5 to 6.0.
Suitable bacteria providing starter cultures are species Lactobacillus, Streptococcus and Pediococcus and preferable strains are Lactobacillus sake and Pediococcus acidilacti and salami. Starter culture prepared with the bacteria may be mixed in water, as is conventional, before being added to the meat trimmings. The amount of starter culture used may be from 0.1 to 10 ml, preferably from 0.5 to 5 ml and especially from 0.75 to 2.5 ml per kg of ground meat trimmings. The mixture of ground meat trimmings and the starter culture in the brine, pickle, or marinade is advantageously packed in a vessel or bin suitable for fermentation, such as a plastic bag or pouch, within which fermentation is allowed to proceed. The fermentation may take place at a temperature from 0° to 55° C., preferably from 8° to 45° C. and more preferably from 15° to 40° C. over a period of from about 12 hours to about 7 days, preferably from 18 hours to 5 days. During the early stages of the fermentation, e.g. after a period of from about 6 to 30 hours and more usually after a period of from 12 to 24 hours, the pH falls, for instance to a pH of from 5.2 to 5.3 or below.
After the fermentation, the fermented ground meat trimmings are frozen, e.g. to a temperature from -5° to -30° C., preferably from -15° to -25° C. After freezing, the fermented ground meat trimmings are advantageously flaked, e.g. to particles having a maximum volume of about 2 cc, preferably a maximum volume of 1 cc.
After freezing, a frozen brine, pickle, or marinade may be mixed with the fermented meat trimmings to form a suspension. The mixing may be performed by emulsifying one or more times, e.g. up to four times. The frozen brine may be at a temperature of from 0° to -30° C. and preferably from -5° to -12° C. The ratio of brine, pickle, or marinade to the fermented meat trimmings may be from 1:1 to 20:1, preferably from 1.5:1 to 15:1 and more preferably from 2:1 to 9:1. For example, a brine may consist of a mixture of nitrite salt, sugar, ascorbate and water. The nitrite and ascorbate salts are conveniently the sodium salts.
The suspension of meat trimmings in a brine, marinade, or pickle is then warmed to a temperature of not greater than +1° C., for instance from about -2° to -10° C., preferably from -40° to -8° C., and incorporated into the chilled meat. The temperature of the suspension should not exceed +1° C. since, otherwise, proteins would be extracted which would cause the suspension to thicken rapidly, and this may cause subsequent clogging of the needles when the meat trimmings are injected into the meat with needles.
The amount of meat trimmings incorporated into the meat may be up to 15% by weight based upon the weight of the meat and may vary, e.g., conveniently from 1 to 10% and preferably from 2 to 6% by weight. During the incorporation of the suspension of the meat trimmings into the meat, especially by injection, a portion of the suspension of the meat trimmings is squeezed out of the meat and may be returned to the batch containing the mixture of trimmings with brine where it is chilled down again. Any portion of the suspension returned is preferably emulsified at least one, more preferably at least two or three times, with the next batch because it may contain small meat particles which are disrupted from the muscles during injection and which could cause clogging of the needles. When the meat trimmings are incorporated by injection, a part of the suspension of the meat trimmings preferably is added separately so that some may be absorbed during tumbling, since it is not usually possible to incorporate the exact desired percentage of suspension by injection.
After the injection, the meat may be processed conventionally.
The meat product may be a chilled product which is either non-cooked or cooked, or it may be frozen, preferably marinated, or dried. Examples of non-cooked chilled meat products are LARDON product, bacon, cold smoked ham, etc. An example of a cooked and chilled meat product is cooked ham. For a cooked, chilled product such as cooked ham, the meat may undergo tenderisation, tumbling, moulding, cooking, chilling, storage, slicing and packaging by conventional methods such as are well known in the art. The process of the present invention may provide protection against undesirable bacteria such as Listeria in chilled products and provide improved flavour in frozen and dried products.
EXAMPLES
The following Examples further illustrate the present invention. Parts and percentages are by weight.
Example 1
A whole ham was chilled to 5° C. and trimmed by removing fat, sinews, etc., before being separated into different whole meat cuts. The trimmings removed from the whole ham, i.e., the fat, sinews, etc., were ground in a Kilia grinder to an average particle size of 3 mm, mixed in a Hobart mixer with, per gram of trimmings, 2% dextrose, a mixture of 0.5% sodium nitrite and 0.5% sodium chloride, 1% sodium chloride, and 1.0% of a starter culture of L. sake containing 10 6 -10 7 bacteria. The mixture was packed into plastic pouches and fermented at 25° C. for 36 hours. The pH fell rapidly during the first day from an initial value of pH 6 to pH 5.
After fermentation, the fermented mixture was packed into whole bags and frozen to -20° C., flaked in a magurit flaker to particles having dimensions of 0.5×0.5×0.5 cm and warmed to -15° C. A brine at -8° C. composed of 10.08% sodium nitrite, 0.18% sodium ascorbate, 2.28% dextrose and 87.46% water (corresponding to an injection level of 40.5% and a 7% level of trimmings in the final product) was then mixed with the flakes of the fermented mixture in a ratio of 3 parts brine to 1 part flakes. The mixing was carried out by emulsifying three times to form a suspension. The suspension was then injected at -6° C. into one of the whole cuts of ham through a multi-needle injector, and the ham containing the fermented meat trimmings was then subjected to tenderisation, tumbling, moulding, cooking, chilling, storage, slicing and finally packaging, by conventional methods.
The chilled cooked ham had a longer shelf-life and an improved flavour compared with a similar product containing meat trimmings which had not been fermented. Furthermore, a similar product containing meat trimmings which had been fermented within the whole meat cut at 5° C. had a shorter shelf-life and an inferior flavour compared with the chilled cooked ham product as prepared in Example 1.
Example 2
A similar process to that described in Example 1 was followed except that the injection level of the suspension was only 17.3%, instead of the 40.3% level used in Example 1, giving an addition of only 3% trimmings in the final product instead of 7% in Example 1.
The chilled cooked ham had a longer shelf-life and an improved flavour compared with a similar product containing meat trimmings which had not been fermented. Furthermore, a similar product containing meat trimmings which had been fermented within the whole meat cut at 5° C. had a shorter shelf-life and an inferior flavour compared with the chilled cooked ham product as prepared in Example 2.
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Prior to incorporating meat trimmings into a meat piece, the trimmings are inoculated with starter culture and fermented with the bacteria from the culture to obtain fermented meat trim particles and then frozen for incorporation into a meat piece.
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BACKGROUND
[0001] This disclosure relates generally to network communications and more particularly to network communications in a cluster of computer systems.
[0002] In the Internet Protocol (IP) protocol, IP packets are routed from an originator through a network of routers to the destination. All physical adapter devices in such a network, including those for client and server hosts, are identified by an IP address which is unique within the network. One valuable feature of IP is that a failure of an intermediate router node or adapter need not prevent a packet from moving from source to destination, as long as there is an alternate path through the network.
[0003] In Transmission Control Protocol/Internet Protocol (TCP/IP), TCP sets up a connection between two endpoints, each identified by their respective IP address and port number pair. Unlike failures of an adapter in an intermediate node, if one of the endpoint adapters (or the link leading to it) fails, all connections through that adapter generally fail and must be reestablished. If the failure is on a client workstation, only a relatively few client connections are typically disrupted. However, an adapter failure on a server may mean that hundreds or thousands of connections may be disrupted.
[0004] One alternative to alleviate this situation is to configure a Virtual IP Address (VIPA). A VIPA behaves and is typically configured in the same manner as an IP address would be for a physical network adapter device. However the VIPA, being a virtual object, is not associated with a particular physical device. For example, when a TCP/IP stack on a server receives a networking packet that is destined for one of its configured VIPAs, the TCP/IP stack forwards the packet up the various TCP/IP layers to the destination application. Thus, if a particular physical adapter fails, the remaining attached routing network routes the VIPA-destined packets to the TCP/IP stack using an alternate route. While the VIPA is owned by the TCP/IP stack and reachable through any interface, the VIPA is not tied to any particular adapter. This allows network packets and User Datagram Protocol (UDP) datagram transmissions to be unaffected by a failure of a physical adapter owned by the TCP/IP stack as long as at least one other device remains operational for external connectivity to the same network.
[0005] Similarly, a program that access the TCP/IP stack may initiate an outbound connection, acting as a client rather than a server for the purposes of that particular connection. Such a program will typically not bind the socket to any particular local address before initiating the connection and normal TCP rules will use the address of the physical adapter on which the connection request is transmitted. As a result, the connection may be lost if that physical adapter fails while the connection is still active.
[0006] For outbound connections, the SOURCEVIPA function of the IP configuration process allows a VIPA to be associated with a group of physical adapters. This causes TCP/IP to use the VIPA instead of the adapter address when a program initiates an outbound connection without binding the socket to a particular IP address. This approach works well when a program is hosted on only one TCP/IP stack, or when the program receiving the connection request does not care what IP address is used for the source address of the connection request. There are some cases, however, where the traditional SOURCEVIPA approach does not meet the needs of a particular application. For example, some application pairs require both members to function as both client and server, where one partner establishes a connection to the other, which in turn establishes a connection back to the first. These applications often use the source and destination IP addresses to correlate the connections. Dynamic VIPA (DVIPA) addresses outages due to failures in a TCP/IP stack or an underlying operating system (OS) image. A DVIPA is a VIPA which can move from one TCP/IP stack to another, without operator intervention, in response to actions in an application or under the control of the OS or TCP/IP stack. Since DVIPAs may move from stack to stack, they typically cannot be used for SOURCEVIPA, which must generally be predictable to be useful.
[0007] A TCP connection is generally identified by a combination of source and destination IP address, and source and destination port numbers, known as the connection 4-tuple. Programs initiating outbound connections can rely on the TCP/IP stack to select a port that is not in use, referred to as an ephemeral port or sysplexport. With IP load balancing, such as Sysplex Distributor, the same IP address, referred to as dynamically routable VIPA (DRVIPA), can reside on multiple TCP/IP stacks. Unique connection 4-tuples can be configured using the existing SYSPLEXPORTS option of the VIPADISTRIBUTE configuration statement. However, the configuration process can be complex and error prone.
[0008] In current operation, specialized hardware referred to as a Coupling Facility (CF) includes a centralized shared table of sysplexports. Each computer system that participates in the sysplexports DRVIPA distribution registers with the CF for each DRVIPA. The CF then distributes blocks of sysplexports to the participating computer systems. The ports are used once and must be returned to the CF. In this architecture, each computer system maintains a table of it used ports, and when the table is full, the computer system returns the block of ports to the CF. Another block of ports may be requested. Each CF operation to distribute and manage the sysplexports tables uses at least one input/output (I/O) operation that is serialized by multiple locking operations.
[0009] Isolating the management of the sysplexports table to the Sysplex Distributor rather than sharing it among all computer systems in the Sysplex can eliminate the CF requirement, improve performance by reducing I/O operations, and remove serialization issues associated with the CF.
SUMMARY
[0010] According to one embodiment, a method for allocating a port for a connection originated by an application instance on a computer system is provided whereby the application instance utilizes the port and a shared network address to connect to one or more application instances accessing the shared network address. The method includes creating, by a distributing stack, at least one common table of available ports, whereby each common table of available ports is associated with a different unique shared network address. Responsive to receiving a request from a communication protocol stack on a requesting system for a port to assign the shared network address, the distributing stack allocates a set of available ports. Responsive to receiving a termination message, the distributing stack updates the common table of available ports associated with the shared network address. Responsive to identifying a transfer from the distributing stack to a backup distributing stack, transferring ownership of the common table of available ports to the backup distributing stack.
[0011] According to another embodiment, a computer program product for allocating a port for a connection originated by an application instance on a computer system is provided whereby the application instance utilizes the port and a shared network address to connect to one or more application instances accessing the shared network address is provided. The computer program product includes a computer readable storage medium readable by a processing circuit and storing instructions for execution by the processing circuit for performing a method is provided. The method includes creating, by a distributing stack, at least one common table of available ports, whereby each common table of available ports is associated with a different unique shared network address. Responsive to receiving a request from a communication protocol stack on a requesting system for a port to assign the shared network address, the distributing stack allocates a set of available ports. Responsive to receiving a termination message, the distributing stack updates the common table of available ports associated with the shared network address. Responsive to identifying a transfer from the distributing stack to a backup distributing stack, transferring ownership of the common table of available ports to the backup distributing stack.
[0012] According to another embodiment, a computer system for allocating a port for a connection originated by an application instance on a computer system is provided. The computer system includes a memory, a processing unit communicatively coupled to the memory, and a management module communicatively coupled to the memory and processing unit, whereby the management module is configured to perform the steps of a method is provided. The method includes creating, by a distributing stack, at least one common table of available ports, whereby each common table of available ports is associated with a different unique shared network address. Responsive to receiving a request from a communication protocol stack on a requesting system for a port to assign the shared network address, the distributing stack allocates a set of available ports. Responsive to receiving a termination message, the distributing stack updates the common table of available ports associated with the shared network address. Responsive to identifying a transfer from the distributing stack to a backup distributing stack, transferring ownership of the common table of available ports to the backup distributing stack.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0013] For a more complete understanding of this disclosure, reference is now made to the following brief description, taken in conjunction with the accompanying drawings and detailed description, wherein like reference numerals represent like parts.
[0014] FIG. 1 is a block diagram of a cluster of computer systems which incorporate embodiments of the disclosure.
[0015] FIG. 2 is a flowchart illustrating operations for initialization of cluster-wide port assignments, according to various embodiments of the disclosure.
[0016] FIG. 3 is a flowchart illustrating operations for initiating a connection utilizing cluster-wide port assignment for a dynamical routable virtual IP address.
[0017] FIG. 4 is a flowchart illustrating operations for termination of a connection utilizing a cluster-wide port assignment.
[0018] FIG. 5 is a flowchart illustrating operations for recovery from failure of a communication protocol stack utilizing cluster-wide port assignments.
[0019] FIG. 6 is a schematic block diagram of hardware and software of the computer environment according to an embodiment of the processes of FIGS. 2-5 .
DETAILED DESCRIPTION
[0020] Although an illustrative implementation of one or more embodiments is provided below, the disclosed systems and/or methods may be implemented using any number of techniques. This disclosure should in no way be limited to the illustrative implementations, drawings, and techniques illustrated below, including the exemplary designs and implementations illustrated and described herein, but may be modified within the scope of the appended claims along with their full scope of equivalents.
[0021] As will be appreciated by one skilled in the art, aspects of the present disclosure may be embodied as a system, method or computer program product. Accordingly, aspects of the present disclosure may take the form of an entirely hardware embodiment, an entirely software embodiment (including firmware, resident software, micro-code, etc.) or an embodiment combining software and hardware aspects that may all generally be referred to herein as a “circuit”, “module”, or “system”. Furthermore, aspects of the present invention may take the form of a computer program product embodied in one or more computer readable medium(s) having computer readable program code embodied thereon.
[0022] Aspects of the present disclosure are described below with reference to flowchart illustrations and/or block diagrams of methods, apparatus, (systems), and computer program products according to embodiments of the invention. It will be understood that each block of the flowchart illustrations and/or block diagrams, and combinations of blocks in the flowchart illustrations and/or block diagrams, can be implemented by computer program instructions.
[0023] In a clustered or IP load balanced environment, such as Sysplex Distributor, a distributing stack associates a single dynamically routable virtual IP address (DRVIPA) and port with a plurality of communication protocols stacks, and routes communications to the appropriate communication protocol stack. The DRVIPA can exist on several communication protocol stacks, but is advertised outside the cluster by only one of the stacks, called the distributing stack. While the present invention is described as an embodiment of a z/OS Sysplex, as will be appreciated by those skilled in the art of clustered computing, the present invention may be practiced in other systems where clusters of computers utilize virtual addresses by associating an application or application group, rather than a particular communications adapter, with the addresses. Thus, the present invention should not be construed as limited to the particular exemplar embodiments described herein.
[0024] FIG. 1 illustrates an exemplary cluster of computer systems 20 , 24 , 28 , 32 , and 36 interconnected as a cluster of nodes in Sysplex 10 . While the present invention will be described primarily with respect to the z/OS operating system executing in a zSeries environment, the computer systems 20 , 24 , 28 , 32 , and 36 may include other servers or other operating systems capable of supporting DRVIPA. The computer systems 20 , 24 , 28 , 32 , and 36 include communication protocol stacks 22 , 26 , 30 , 34 and 38 , for example TCP/IP stacks. The communication protocol stacks 22 , 26 , 30 , 34 , and 38 are modified to incorporate a VIPA distribution function 23 that can provide DRVIPAs as a single IP address for the multiple communication protocol stacks 22 , 26 , 30 , 34 , and 38 . As illustrated, each of the communication protocol stacks 22 , 26 , 30 , 34 , and 38 incorporate the VIPA distribution function 23 . However, the present invention may be practiced where two or more communication protocol stacks 22 , 26 , 30 , 34 , and 38 in a cluster support DRVIPA. The communication protocol stacks 22 , 26 , 30 , 34 , and 38 may communicate with an external network 44 , for example a Local Area Network (LAN), wide area network (WAN), or through the Internet using an Internet Service Provider. For example, a client 46 may communicate with an application executing on an OS image in the Sysplex 10 through communication protocol stacks 22 and 38 , which may function as routing protocol stacks. As a further example, the computer system 20 includes OS image z/OS- 1 which hosts an instance of application APP A. The client 46 , through the network 44 , accesses APP A on computer system 20 through communication protocol stack 22 . Similarly, the computer system 24 includes OS image z/OS- 2 which hosts an instance of applications APP A and APP B through the communication protocol stack 26 . The computer system 28 includes OS image z/OS- 3 which hosts a second instance of application APP B through the communication protocol stack 30 . The computer system 32 includes OS image z/OS- 4 hosting a third instance of application APP A through the communication protocol stack 34 . Finally, the computer system 36 includes OS image z/OS- 5 which hosts a third instance of application APP B through the communication protocol stack 38 . Each of the communication protocol stacks 22 , 26 , 30 , 34 , and 38 include an IP address selection module or circuit (SIP) 25 and a cluster-wide port assignment module or circuit (CLP) 27 .
[0025] The VIPA distribution function 23 allows sharing of DRVIPAs among communication protocol stacks and allows network communication through a routing protocol stack. In this way, all communication protocol stacks having a server application which is associated with the DRVIPA appears to the network 44 as a single IP address. The DRVIPAs may be distributed by designating a particular communication protocol stack, such a communication protocol stack 22 , as a routing protocol stack, notifying other communication protocol stacks of the routing protocol stack, and having the other communication protocol stacks notify the routing protocol stack when an application which binds to the DRVIPA is started. At least one backup communication protocol stack can be configured in the cluster. When multiple backup communication protocol stacks are configured, each may be assigned a rank, such as a numeric value, to determine the relative order within the backup chain when a recovery take-over occurs.
[0026] More than one DRVIPA may exist in the cluster, based on application definitions. Therefore, the sets of routing protocol stacks, communication protocol stacks, and backup communication protocol stacks may differ or overlap. For example, although computer system 24 hosts an instance of APP A and APP B, the communication protocol stack 26 supports two DRVIPAs: one shared by the first, second, and third instances of APP A; and one shared by the first, second, and third instance of APP B. Although the two DRVIPAs are configured on communication protocol stack 26 , their routing protocol stacks and backup communication protocol stacks may reside in stacks other than the communication protocol stack 26 .
[0027] FIG. 2 illustrates initializing cluster-wide port assignments. In an exemplary embodiment, the Sysplex Distributor assumes the management of the common table of available ports, hereinafter referred to as the SysplexPorts available ports table when the SYSPLEXPORTS option of the VIPADISTRIBUTE configuration statement is specified.
[0028] At 200 , a check is made for whether the CLUSTERPORTS option is specified in the configuration statement of the DVIPA or DRVIPA. If CLUSTERPORTS is not specified, then the operation terminates. If CLUSTERPORTS is specified, at 205 a SysplexPorts available table for the DRVIPA is created on the distributing stack. The SysplexPorts available ports table tracks the blocks of ports by DRVIPA, for example in groups of “64”, which are issued to each requesting TCP/IP stack. The SysplexPorts available ports table may include an identifier indicating to which target stack the port is assigned, and may take the form of a bitmap, with each bit corresponding to a state of a port such that, for example, a “1” indicates the port is available and a “0” indicates that the port is unavailable. At 210 , if a DRVIPA is not being initialized, at 235 the connection table of the TCP/IP stack is scanned for ports of active DRVIPAs, and the SysplexPorts available ports table is updated at 240 . At 210 , if a DRVIPA is being initialized, the distributing stack searches its connection routing table to obtain port information for connections to the TCP/IP stacks (block 215 ). If at 225 the CLUSTERPORTS parameter is added via a VARY OBEY command, the connection table of the TCP/IP stack is scanned for ports of active DRVIPAs (block 235 ). The VARY OBEY command can be used to update TCP/IP profile configuration statements to dynamically make temporary changes to the TCP/IP configuration. If at 225 the CLUSTERPORTS parameter is not added via the VARY OBEY command, at 240 the SysplexPorts available ports table is updated with the port information obtained at block 215 and/or block 235 .
[0029] FIG. 3 illustrates initiating a connection utilizing cluster-wide port assignment. When a new TCP/IP connection is started on a target stack, for example communication protocol stacks 22 , 26 , 30 , 34 and 38 of FIG. 1 , using the DRVIPA as the source IP address and a sysplexport, the target stack selects the sysplexport from its local available port table. If there is no available port, the target stack may use a cross-system message to request a new block of sysplexports for this DRVIPA from the distributing stack, i.e., the Sysplex Distributor. This message may contain a list of unavailable ports, such as well-known ports or other reserved ports. The distributing stack responds with a new block of sysplexports.
[0030] At 300 , if the socket of the connection request is not bound to the DVIPA, at 350 a conventional non-DVIPA connection is opened. If the socket of the connection request is bound to the DVIPA, but CLUSTERPORTS is not specified, at 310 conventional port selection techniques may be used and the connection is open using the target IP address and the selected port (block 345 ). If CLUSTERPORTS is specified for the DVIPA at 305 , it is determined if the socket is bound to a specific port or if an ephemeral port is selected (block 315 ). An ephemeral port is a short-lived endpoint that is assigned when a program requests a port for a network connection. A sysplexport, as used herein, is an ephemeral port. For example, binding the socket to port “0” may indicate that a sysplexport is to be selected when a connection request is made. If at 315 the socket is bound to a specific port other than port “0”, a check is made to determine if the requested port is available on the distributing stack (block 320 ). At 325 , if the requested port is not available, the connection is rejected with an error notification. If at 320 the requested port is available, specified port may be identified locally as unavailable for use in another connection (block 330 ), and at 345 the selected port is used to open the connection. However, if at 315 the socket is not bound to a specific port and a sysplexport is to be used, the next available port is retrieved from the block of available ports issued by the distributing stack (block 318 ) for this DRVPIA. At 335 , the port is identified as in use in the available ports table on the distribution stack, and at 345 the selected port is used to open the connection.
[0031] FIG. 4 illustrates operations terminating a connection utilizing a cluster-wide port assignment. For a connection having a DVIPA as a source address, the disconnecting target stack issues a cross-system message, for example a TERMCONN message, to the distributing stack. This TERMCONN message may include the connection 4-tuple. The distributing stack may use this information to return the sysplexport back to the SysplexPorts available ports table for this DRVIPA. The returned sysplexport is immediately available for distribution to another target stack.
[0032] At 400 , if a DVIPA is not specified as the source address for the connection, conventional termination operations may be used to terminate the connection (block 435 ). For a connection having a DVIPA as its source address, at 405 the connection is terminated and appropriate tables are updated as for a conventional DVIPA. At 407 , a connection termination message is sent to the distributing stack that owns this DVIPA. At 410 , if this is not a cluster-wide port, the termination is complete. For a cluster-wide port, at 420 the distributing stack identifies the selected port as available in the SysplexPorts available ports table.
[0033] FIG. 5 illustrates recovering from a failure of a distributing stack utilizing cluster-wide port assignment. When a distributing stack that owns a DVIPA changes, a designated backup distributing stack assumes ownership. This may be a planned change, for example by an operator command, or an unplanned change as a result of hardware and/or software failure. For a planned change the distributing stack sends the available ports table information to the backup distributing stack, which assumes management of the SysplexPorts available ports table without operator intervention. For an unplanned change, the target systems send their allocated port information to the backup distributing stack, which rebuilds the available ports table using the collected allocated port information. Collecting the allocated port information and rebuilding the SysplexPorts available ports table occurs without operator intervention.
[0034] At 500 the communication protocol stacks are notified of the change, for example by one or more cross-system message. Upon notification of the change in distributing stack, the backup distributing stack rebuilds the available ports table from the collected allocated port information. At 510 , available ports are identified in the rebuilt SysplexPorts available ports table in the backup distributing stack.
[0035] Referring now to FIG. 6 , computing device 600 may include respective sets of internal components 800 and external components 900 that together may provide an environment for a software application. Each of the sets of internal components 800 includes one or more processors 820 ; one or more computer-readable RAMs 822 ; one or more computer-readable ROMs 824 on one or more buses 826 ; one or more operating systems 828 executing the method of FIGS. 2-5 ; and one or more computer-readable tangible storage devices 830 . The one or more operating systems 828 (including the additional data collection facility) are stored on one or more of the respective computer-readable tangible storage devices 830 for execution by one or more of the respective processors 820 via one or more of the respective RAMs 822 (which typically include cache memory). In the embodiment illustrated in FIG. 6 , each of the computer-readable tangible storage devices 830 is a magnetic disk storage device of an internal hard drive. Alternatively, each of the computer-readable tangible storage devices 830 is a semiconductor storage device such as ROM 824 , EPROM, flash memory or any other computer-readable tangible storage device that can store a computer program and digital information.
[0036] Each set of internal components 800 also includes a R/W drive or interface 832 to read from and write to one or more computer-readable tangible storage devices 936 such as a CD-ROM, DVD, SSD, memory stick, magnetic tape, magnetic disk, optical disk or semiconductor storage device.
[0037] Each set of internal components 800 may also include network adapters (or switch port cards) or interfaces 836 such as a TCP/IP adapter cards, wireless WI-FI interface cards, or 3G or 4G wireless interface cards or other wired or wireless communication links. The operating system 828 that is associated with computing device 600 , can be downloaded to computing device 400 from an external computer (e.g., server) via a network (for example, the Internet, a local area network, or other wide area network) and respective network adapters or interfaces 836 . From the network adapters (or switch port adapters) or interfaces 836 and operating system 828 associated with computing device 600 are loaded into the respective hard drive 830 and network adapter 836 . The network may comprise copper wires, optical fibers, wireless transmission, routers, firewalls, switches, gateway computers and/or edge servers.
[0038] Each of the sets of external components 900 can include a computer display monitor 920 , a keyboard 930 , and a computer mouse 934 . External components 900 can also include touch screens, virtual keyboards, touch pads, pointing devices, and other human interface devices. Each of the sets of internal components 800 also includes device drivers 840 to interface to computer display monitor 920 , keyboard 930 and computer mouse 934 . The device drivers 840 , R/W drive or interface 832 and network adapter or interface 836 comprise hardware and software (stored in storage device 830 and/or ROM 824 ).
[0039] Various embodiments of the invention may be implemented in a data processing system suitable for storing and/or executing program code that includes at least one processor coupled directly or indirectly to memory elements through a system bus. The memory elements include, for instance, local memory employed during actual execution of the program code, bulk storage, and cache memory which provide temporary storage of at least some program code in order to reduce the number of times code must be retrieved from bulk storage during execution.
[0040] Input/Output or I/O devices (including, but not limited to, keyboards, displays, pointing devices, DASD, tape, CDs, DVDs, thumb drives and other memory media, etc.) can be coupled to the system either directly or through intervening I/O controllers. Network adapters may also be coupled to the system to enable the data processing system to become coupled to other data processing systems or remote printers or storage devices through intervening private or public networks. Modems, cable modems, and Ethernet cards are just a few of the available types of network adapters.
[0041] The present invention may be a system, a method, and/or a computer program product. The computer program product may include a computer readable storage medium (or media) having computer readable program instructions thereon for causing a processor to carry out aspects of the present invention.
[0042] The computer readable storage medium can be a tangible device that can retain and store instructions for use by an instruction execution device. The computer readable storage medium may be, for example, but is not limited to, an electronic storage device, a magnetic storage device, an optical storage device, an electromagnetic storage device, a semiconductor storage device, or any suitable combination of the foregoing. A non-exhaustive list of more specific examples of the computer readable storage medium includes the following: a portable computer diskette, a hard disk, a random access memory (RAM), a read-only memory (ROM), an erasable programmable read-only memory (EPROM or Flash memory), a static random access memory (SRAM), a portable compact disc read-only memory (CD-ROM), a digital versatile disk (DVD), a memory stick, a floppy disk, a mechanically encoded device such as punch-cards or raised structures in a groove having instructions recorded thereon, and any suitable combination of the foregoing. A computer readable storage medium, as used herein, is not to be construed as being transitory signals per se, such as radio waves or other freely propagating electromagnetic waves, electromagnetic waves propagating through a waveguide or other transmission media (e.g., light pulses passing through a fiber-optic cable), or electrical signals transmitted through a wire.
[0043] Computer readable program instructions described herein can be downloaded to respective computing/processing devices from a computer readable storage medium or to an external computer or external storage device via a network, for example, the Internet, a local area network, a wide area network and/or a wireless network. The network may comprise copper transmission cables, optical transmission fibers, wireless transmission, routers, firewalls, switches, gateway computers and/or edge servers. A network adapter card or network interface in each computing/processing device receives computer readable program instructions from the network and forwards the computer readable program instructions for storage in a computer readable storage medium within the respective computing/processing device.
[0044] Computer readable program instructions for carrying out operations of the present invention may be assembler instructions, instruction-set-architecture (ISA) instructions, machine instructions, machine dependent instructions, microcode, firmware instructions, state-setting data, or either source code or object code written in any combination of one or more programming languages, including an object oriented programming language such as Smalltalk, C++ or the like, and conventional procedural programming languages, such as the “C” programming language or similar programming languages. The computer readable program instructions may execute entirely on the user's computer, partly on the user's computer, as a stand-alone software package, partly on the user's computer and partly on a remote computer or entirely on the remote computer or server. In the latter scenario, the remote computer may be connected to the user's computer through any type of network, including a local area network (LAN) or a wide area network (WAN), or the connection may be made to an external computer (for example, through the Internet using an Internet Service Provider). In some embodiments, electronic circuitry including, for example, programmable logic circuitry, field-programmable gate arrays (FPGA), or programmable logic arrays (PLA) may execute the computer readable program instructions by utilizing state information of the computer readable program instructions to personalize the electronic circuitry, in order to perform aspects of the present invention.
[0045] Aspects of the present invention are described herein with reference to flowchart illustrations and/or block diagrams of methods, apparatus (systems), and computer program products according to embodiments of the invention. It will be understood that each block of the flowchart illustrations and/or block diagrams, and combinations of blocks in the flowchart illustrations and/or block diagrams, can be implemented by computer readable program instructions.
[0046] These computer readable program instructions may be provided to a processor of a general purpose computer, special purpose computer, or other programmable data processing apparatus to produce a machine, such that the instructions, which execute via the processor of the computer or other programmable data processing apparatus, create means for implementing the functions/acts specified in the flowchart and/or block diagram block or blocks. These computer readable program instructions may also be stored in a computer readable storage medium that can direct a computer, a programmable data processing apparatus, and/or other devices to function in a particular manner, such that the computer readable storage medium having instructions stored therein comprises an article of manufacture including instructions which implement aspects of the function/act specified in the flowchart and/or block diagram block or blocks.
[0047] The computer readable program instructions may also be loaded onto a computer, other programmable data processing apparatus, or other device to cause a series of operational steps to be performed on the computer, other programmable apparatus or other device to produce a computer implemented process, such that the instructions which execute on the computer, other programmable apparatus, or other device implement the functions/acts specified in the flowchart and/or block diagram block or blocks.
[0048] The flowchart and block diagrams in the Figures illustrate the architecture, functionality, and operation of possible implementations of systems, methods, and computer program products according to various embodiments of the present invention. In this regard, each block in the flowchart or block diagrams may represent a module, segment, or portion of instructions, which comprises one or more executable instructions for implementing the specified logical function(s). In some alternative implementations, the functions noted in the block may occur out of the order noted in the figures. For example, two blocks shown in succession may, in fact, be executed substantially concurrently, or the blocks may sometimes be executed in the reverse order, depending upon the functionality involved. It will also be noted that each block of the block diagrams and/or flowchart illustration, and combinations of blocks in the block diagrams and/or flowchart illustration, can be implemented by special purpose hardware-based systems that perform the specified functions or acts or carry out combinations of special purpose hardware and computer instructions.
[0049] Although preferred embodiments have been depicted and described in detail herein, it will be apparent to those skilled in the relevant art that various modifications, additions, substitutions and the like can be made without departing from the spirit of the disclosure, and these are, therefore, considered to be within the scope of the disclosure, as defined in the following claims.
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A method, system, and program product for allocating a port for a connection by an application instance on a computer system is provided. The application instances used the port and a shared network address to connect to one or more application instances accessing the shared network address. A distributing stack creates at least one common table of available ports. Each table is associated with a different unique shared network address. When a request is received for a port to assign the shared network address, the distributing stack allocates a set of available ports. When a termination message is received, the distributing stack updates the common table of available ports associated with the shared network address. When a transfer from the distributing stack to a backup distributing stack is made, ownership of the common table of available ports is transferred to the backup distributing stack.
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BACKGROUND INFORMATION
1. Field of the Invention
The field of the invention relates to gutters on residential and commercial buildings. More particularly, the invention relates to a retractable gutter.
2. Discussion of the Prior Art
Gutters are typically attached to the fascia under the eaves of a structure, to collect rainwater that drains from the roof. The fascia is a trim board that is fixed vertically on edge to the rafter ends or wall which conventionally carries the gutter around the eaves of the roof. In many regions that experience cold winters, snow falls on the roof of the structure and eventually melts, either due to heat loss through the roof, rain, or an ambient temperature that is above freezing. The melting snow water runs to the eaves and then into the gutter. The eave, however, is colder than the roof, so, as the water reaches the gutter, it begins to freeze. The gutter then fills up with ice and may eventually cause an ice dam to form under the eave, which may then cause water to run back up under the shingles, resulting in damage to the structure because of water leaking into the interior of the structure.
Tree debris is another source of failure of the conventional gutter system. Leaves and needles from trees often end up in gutters, carried there by wind and rain. This debris can plug up the entry to the downspout, and, as a result, force water to leak back into the facia area of the roof.
FIG. 1 (prior art) illustrates the problem with the conventional gutter system resulting from a plugged gutter.
What is needed therefore is a gutter system that can quickly and easily be moved away from the normal functional position to a protected position, so as to protect the gutter from ice build-up and/or tree debris.
BRIEF SUMMARY OF THE INVENTION
The invention is a retractable gutter system that includes a retractable support means that is mounted under the eaves of a structure and a gutter mounted on the retractable support means. In its gutter functional position, the retractable support means is pulled out, so that rainwater drains from the roof into the gutter. In regions that experience cold winters or in locations in which tree debris is copious at certain times of the year, it is desirable to avoid the build-up of ice and/or tree debris in the gutter. To that end, the retractable support means is constructed to be movable between a stowed position and its functional position, so that the gutter may be pushed in under the eaves in times of freezing temperatures or tree debris. On residential structures, the eaves overhang, i.e., the distance from the drip edge of the eaves to the outer surface of the wall, is typically 12 inches. The bottom face of this overhang is typically covered with a board, referred to as the soffit. The telescoping slides are not fastened to the fascia, but rather, are either mounted on cross brackets that are fastened to the soffit, or are fastened to the soffit directly.
During the spring and summer, the gutter is pulled out, so as to catch rainwater as it runs from the roof. In the fall, when leaves are coming down, and in the months when the temperature is frequently below freezing, the retractable support means may be pushed in to the stowed position, so that the gutter is under the eaves and, thus, protected from debris and ice.
The downspout on a gutter system includes a gutter downspout and a structure downspout. The gutter downspout is attached to the gutter and, in the conventional gutter system, is fitted into the top of the structure downspout from above. In the retractable gutter system according to the invention, the structure downspout has a cut-out at the top, on the wall that faces the structure. This allows the gutter downspout, when the gutter is pulled out to its functional position, to slide into the upper end of the structure downspout, so as to provide an enclosed conduit for the water to drain from the gutter into the spout.
The retractable gutter system according to the invention is adaptable to various types of structures. The gutters may be constructed of vinyl or metal gutter section, or be seamless metal lengths.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention is described with reference to the accompanying drawings. In the drawings, like reference numbers indicate identical or functionally similar elements. The drawings are not drawn to scale.
FIG. 1 illustrates a conventional gutter system (prior art).
FIG. 2 illustrates the retractable gutter system according to the invention.
FIG. 3 illustrates the gutter of FIG. 2 mounted on the retractable slide and pulled out to the drip edge of the fascia.
FIG. 3A illustrates a second means of mounting the gutter to the extension slide.
FIG. 4 illustrates the gutter of FIG. 2 , mounted on the eaves of a structure and retracted.
FIG. 5 shows a structure downspout with a cut-out.
FIG. 6 illustrates how the gutter downspout fits into the structure downspout.
FIG. 7 illustrates the mounting means for an open-style eave.
FIG. 7A shows a wall-mounting bracket.
FIG. 8 illustrates a long-handled tool for manipulating the retractable gutter system.
FIG. 9 illustrates a modified downspout.
DETAILED DESCRIPTION OF THE INVENTION
The present invention will now be described more fully in detail with reference to the accompanying drawings, in which the preferred embodiments of the invention are shown. This invention should not, however, be construed as limited to the embodiments set forth herein; rather, they are provided so that this disclosure will be complete and will fully convey the scope of the invention to those skilled in the art.
FIG. 1 illustrates a conventional gutter system. Snow is lying on the roof and the gutter is clogged with debris and/or ice. As a result, an ice dam has formed at the drip edge, which is forcing water back up under the roof shingles and into the interior of the structure.
Note: The reference designation D shown in the figures shall refer to debris, which term shall encompass leaves, ice, and any other matter that may clog a gutter.
FIG. 2 illustrates a retractable gutter system 100 according to the invention that is in its functional position. The figure is a top plan view of the system attached to a soffit S. For illustration purposes, roof shingles and fascia that are part of a roof system are not shown. The soffit S is the board that forms the underside of the eaves E, as shown in FIGS. 1 and 3 . The retractable gutter system 100 comprises a gutter 10 , at least two retractable slides 20 , mounting means 30 , and a downspout 40 . Any conventional gutter may be used. The retractable slides 20 may be any type of telescoping slide or bracket that is suitable for this purpose. Drawer runner hardware is quite suitable, because the ball bearings in the runners ensure smooth motion. An example of suitable hardware are the Ball Bearing Side-Mount Drawer Slides Do-It-Yourself D806, made by Liberty Hardware Manufacturing Corp. Ideally, the retractable slide 20 is made of a metal or alloy that does not rust readily.
In the embodiment shown in FIG. 3 , the gutter 10 is attached to the extension slide 20 C of the retractable slide 20 by a gutter-fastening means 22 , which, in this embodiment is a bolt that passes through a hole in the retractable slide 20 and through the bottom of the gutter 10 and is secured with a rubber washer and a nut. Other means of attaching the gutter 10 to the slide 20 are within the scope of the invention. For example, FIG. 3A illustrates a second embodiment, in which a brace 24 that is dimensioned to extend approximately the largest cross-sectional dimension transverse to axial direction of the gutter trough is attached to the underside of the extension slide 20 C by means of the gutter fastening means 22 , which is now a shortened bolt that passes through the slide 20 and the brace 24 , but not through the bottom of the gutter 10 . Fastening means 26 fasten the brace 24 to the front and rear walls of the gutter 10 . The fastening means 26 may be screws, wing nuts, pins, or other suitable means. A particularly suitable material for the brace 24 is ultra high molecular weight polyethylene (UHMW PE), because it will not change dimensions to any significant extent as a function of temperature and humidity and is very rugged. Other suitable materials, however, may also be used.
FIGS. 2 , 3 , and 3 A illustrate the mounting means 30 . There are various suitable mounting means 30 and the following descriptions are not intended to be limiting. In the embodiment shown in these figures, the mounting means 30 includes at least two cross brackets 34 that extend the length of the eaves E that is to be fitted with the retractable gutter system 100 . A front cross bracket 34 A is affixed to the soffit S at a position closer to the structure and a rear cross bracket 34 B affixed to the soffit closer to the fascia F. The cross brackets 34 may be provided as wooden or metal straps, but preferably, UHMW PE straps are used. In the embodiment shown, two cross brackets 34 are fastened through the soffit S to the rafters R. A rafter R is shown in dashed lines in FIG. 3A . The retractable slides 20 has a slide retainer 20 A and an extension slide 20 C captured in the slide retainer 20 A, as shown in FIG. 2 . The slide retainer 20 A has a distal end that is mounted to the cross bracket 34 A closer to the structure wall and a proximal end that is mounted to the cross bracket 34 B closer to the fascia F. The retractable gutter system 100 is shown truncated, but it is understood that the gutter 10 extends the entire length of the eaves E and that a plurality of retractable slides 20 may used with the retractable gutter system 100 , sufficient in number and evenly spaced apart to ensure a substantially even sliding motion of the entire length of gutter 10 . An even sliding motion is particularly important if the gutter 10 along a single run is constructed in sections, as any “snaking” along the length of the gutter 10 may cause seams to open. For this reason, seamless gutters are preferred, as a long single gutter can withstand some snaking, without damaging the gutter.
Another example of the mounting means 30 includes the front cross-bracket 34 B mounted to the soffit S closer to the fascia edge F of the eaves E. At each location where the retractable slide 20 is to be mounted, a transverse bracket that extends generally transverse to the axial direction of the front cross bracket 34 B is affixed at a first end to the front cross bracket 34 B and at a second end to the wall W. This mounting means 30 provides support for the retractable slide 20 from front to back and facilitates adjusting the position of the retractable slide 20 so that the gutter 10 is positioned directly under the drip edge of the eaves E. This particular mounting means 30 is not shown, but it is understood that a person of ordinary skill in the art will know how to place and secure the transverse brackets.
FIG. 4 illustrates the retractable gutter system 100 , retracted under the eaves E. FIGS. 4 and 5 illustrate details of the downspout 40 , which includes a gutter downspout 42 and a structure downspout 44 . A rear wall 44 A in the structure downspout 44 has a cut-out 44 B, that is dimensioned to receive the gutter downspout 42 . FIG. 6 is a plan view of the downspout 40 , viewed from the wall of the structure, showing how the gutter downspout 42 fits into the structure downspout 44 when the retractable gutter system 100 is extended out to its functional position.
Gutters are installed with a slope toward the downspout end of the gutter, to ensure proper drainage of water from the gutter. The retractable gutter system 100 according to the invention is mounted to the soffit S, which provides a horizontal plane, so the retractable gutter system requires some means to ensure the slope of the gutter. To maintain the desired slope, spacers or washers are used when mounting the retractable slides 20 to the soffit S. For example, assuming the retractable slides 20 are mounted to the soffit S spaced five feet apart, then a series of spacers with increasing thicknesses may be used to provide the desired slope. At the end opposite the downspout end, at the first retractable slide 20 , no spacer is used, but then, at every mounting point toward the downspout end, a spacer with a slightly greater thickness is used, thereby achieving the desired slope of the gutter 10 . The spacers may be provided with increasing thickness, or multiple spacers may be used to achieve the desired thickness. A suggested increment in thickness is ⅛-inch. Over a 40-foot span, spacers ranging from ⅛-inch to 1-inch may be used to achieve a ¼-inch drop per every ten feet of span. As with the cross brackets 34 , the spacers may be stamped from UHMW PE. Metal washers or spacers made of other materials may also be suitable for this purpose.
FIG. 7 illustrates a suitable mounting means 30 for an eaves that does not have a soffit. A cross bracket 34 is attached close to the leading edge of the eaves and wall-mounting brackets 36 are fastened to the outer wall at spaced intervals. The distal end 20 B of the slide 20 is supported by the wall-mounting bracket 36 and a proximal end 20 A of the retractable slide 20 , shown in FIG. 2 , is then fastened to the cross bracket 34 and. The wall-mounting bracket 36 may be any suitable means to affix the distal end of 20 B of the retractable slide 20 to the wall of the structure. FIG. 7A is an enlarged view of a simple bracket 36 that provides sufficient support to hold the retractable slide 20 firmly in place. The bracket 36 is, for example, stamped or machined from a piece of UHMW PE, having two through-bores 36 A for mounting fasteners and a retainer bore 36 B that is dimensioned to receive the distal end of the retractable slide 20 . The distal end 20 B is inserted into the retainer bore 36 B and the proximal end 20 A of the slide 20 then mounted to the cross bracket 34 . Although the inventor has used UHMW PE for this bracket 36 , because of the ability of the dense material to hold a threaded fastener, it is understood that other materials and other types of brackets may be used for the wall-mounting bracket 36 .
FIG. 8 illustrates a device 200 for manipulating the retractable gutter system 100 . The device 200 has a handle 210 and, at its upper end, a C-shaped bracket 220 for engaging the body of the gutter 10 , when retracting the retractable gutter system and a hook 230 for engaging an upper edge of the gutter 10 when pulling the retractable gutter system to its functional position. The handle 210 may have extensions, to obtain the necessary height to engage the gutter 10 and move it between the protected and the functional positions.
The retractable gutter system 100 according to the invention will typically extend across a long expanse on a face of a structure, 20, 30, 40 feet or more. To ensure that the retractable gutter system 100 operates smoothly and easily, the retractable slides 20 are mounted on the cross brackets 34 at suitable distances apart, for example, every five feet or so. When a seamed gutter system is used, the inventor suggests strengthening the span of the gutter, to prevent cracks and, thus, leaks, from forming at the seams. One way to do this is to provide a reinforcing strip along the gutter 10 , to ensure that the various segments of the gutter remain aligned when the gutter is being deployed or stowed away. For example, a one-inch strip of perforated steel may be affixed to the gutter 10 , extending in the longitudinal direction of the gutter 10 , to provide the desired stiffness. Another method is to reinforce the joints between gutters with fiberglass. This misalignment when extending/retracting the retractable gutter system is not a concern with seamless gutters, because there are no seams that will open up if the length of gutter span “snakes” a bit.
FIG. 9 illustrates a modified downspout 50 . It may be desirable to prevent snow, ice, debris from collecting in the upper part of the structure downspout 44 described above. The modified downspout 50 includes a structure downspout 54 , a gutter downspout 52 , and an extension trough 55 . The structure downspout 54 has shortened upper end 54 A that extends at an angle from the wall of the structure, whereby the end of the upper end 54 A is still under the eaves E. The gutter downspout 52 has a lower end 52 A that is angled toward the wall of the structure. The extension trough 55 is adjustable in length and connects the lower end 52 A of the gutter downspout 52 to the upper end 54 A of the structure downspout 54 , to provide a continuous trough to guide water from the gutter 10 into the structure downspout 54 . The extension trough 55 has a first rough section 55 A that is affixed to the gutter downspout 52 and a second trough section affixed to the structure downspout 54 . The first and second trough sections 55 A and 55 B are dimensioned such, that the free end of the first section is slidably held in the free end of the second section. When the gutter 10 is moved to the stowed position, the first section 55 A slides into the second section 55 B of the extension trough, so that the entire downspout system is now under the eaves E. When the gutter 10 is moved to its functional position, the extension trough 55 slidably accommodates the greater distance between the gutter 10 and the structure downspout 54 . The lengths of the first and second trough sections 55 A, 55 B are variable and are dictated by the specific depth dimension of the eaves E.
As a safety measure, a tether means 12 , shown in FIG. 3A , may be provided to securely connect the gutter to the structure. It is conceivable that a gutter filled with leaves, ice, or snow could become so heavy, that its weight exceeds the weight limit to be supported by the gutter fastening means 22 that connects the gutter 10 to the slides 20 . The risk is such a situation is that the gutter 10 could inadvertently detach from the retractable slides 20 . If that were to happen, the gutter 10 could drop away from the retractable gutter system, which could result in damage to the gutter, to the structure, and/or to something that the gutter drops onto. To reduce this risk, the tether means is constructed to prevent the gutter from dropping away into a free fall. The tether means includes a cable that is attached at one end to the structure and at the other end to the gutter. One or more of such cables may be attached to a length of gutter.
It is understood that the embodiments described herein are merely illustrative of the present invention. Variations in the construction of the retractable gutter system may be contemplated by one skilled in the art without limiting the intended scope of the invention herein disclosed and as defined by the following claims.
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The invention is a retractable gutter system that allows the gutter to be moved under the eaves in climates that are typically below freezing, to prevent an ice dam from forming under the eaves, and at times when leaf debris risks clogging the gutter. Slide retainers are affixed to the soffit and the gutter affixed to the extendible slides held in the slide retainers. The gutter is slidable between a first position in which the gutter is placed at the drip edge and a second position in which the gutter is stowed away under the eaves.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention generally relates to an apparatus and methods for drilling, completion and rework of wells. More particularly, the invention relates to an apparatus and method for activating and releasing downhole tools. More particularly still, the invention provides an internal pressure indicator and locking mechanism for the downhole tool.
2. Description of the Related Art
In the drilling of oil and gas wells, a wellbore is formed using a drill bit that is urged downwardly at a lower end of a tubular string. After drilling to a predetermined depth, the tubular string and bit are removed, and the wellbore is lined with a string of steel pipe called casing. The casing provides support to the wellbore and facilitates the isolation of certain areas of the wellbore adjacent to hydrocarbon bearing formations. The casing typically extends down the wellbore from the surface of the well to a designated depth. An annular area is thus defined between the outside of the casing and the earth formation. During the completion process, this annular area is filled with cement to permanently set the casing in the wellbore and to facilitate the isolation of production zones and fluids at different depths within the wellbore.
Various downhole tools are used throughout the well completion process. One such downhole tool is a conventional under-reamer. Generally, the conventional under-reamer is used to enlarge the diameter of wellbore by cutting away a portion of the inner diameter of the existing wellbore. A conventional under-reamer is typically run downhole on a tubing string to a predetermined location with the under-reamer blades in a closed position. Subsequently, fluid is pumped into the conventional under-reamer and the blades extend outward to contact the surrounding wellbore. Thereafter, the blades are rotated through hydraulic means and the front blades enlarge the diameter of the existing wellbore as the conventional under-reamer is urged further into the wellbore.
The conventional under-reamer may also be used in a back-reaming operation. In the same manner as the under-reaming operation, fluid is pumped into the under-reamer and the blades are extended outward into contact with the surrounding wellbore. Thereafter, the blades are rotated through hydraulic means and the back blades enlarge the diameter of the existing wellbore as the under-reamer is pulled toward the surface of the wellbore. However, if the blades are not securely locked in place, the upward pulling of the under-reamer causes the blades to fluctuate between an inward and outward position, thereby creating an uneven hole.
A blade locking mechanism on a conventional under-reamer includes a mandrel with a taper. The mandrel is moved between a first and a second position by a spring. Typically, the mandrel uses the mechanical advantage of the taper to apply a force on a piston to keep the blades in the fully open position. The amount of taper on the mandrel is critical to reduce the coefficient of friction at the mandrel and blade interface. For example, if the taper on the mandrel is too small, the spring will be unable to pull the mandrel from the second position to the first position, thereby causing the conventional under-reamer to become immobilized downhole. On the other hand, if the taper is too large, the mechanical advantage of the mandrel is diminished, thereby reducing the force on the piston. In either case, due to downhole conditions, the coefficient of friction on moving parts can vary greatly, making this method of locking the blades open very unpredictable.
Typically, fluid pumped through the conventional under-reamer is used to move the mandrel from the first position to the second position. In the second position, the mandrel acts against the cam mechanism to open the blades. As the mandrel slides on a body of the conventional under-reamer toward the second position, a plurality of bypass holes are exposed in the body allowing some fluid to flow out of the conventional under-reamer resulting in a lower pressure in the conventional under-reamer. This lower pressure is used as an indicator to the operator that the blades are open because the mandrel is in the second position. There are several problems associated with the use of bypass holes as an indicator. One problem relates to the less positive indication. In this method, the bypass holes are exposed as the mandrel travels on the body, which may cause time flutter and throttling at low flow rates. Another problem is that this method permits a less accurate indication of the exact position of the blades during actuation of the conventional under-reamer.
There is a need therefore, for an under-reamer that includes a positive lock mechanism to ensure the blades remain open during a back reaming operation. There is a further need therefore, for an under-reamer that includes a locking mechanism that is predictable. There is a further need for an under-reamer that includes an indicator that permits an accurate indication of the exact position of the blades during actuation of the under-reamer.
SUMMARY OF THE INVENTION
The present invention generally relates to downhole tools. More particularly, the invention relates to a locking mechanism for use on a downhole tool. A flow actuated locking mechanism is provided for a downhole tool that includes an annular, two-position sleeve having an unlocked position and a locked position. A pin assembly within the tool is used to retain the sleeve in the locked position. In one aspect of the invention, the locking mechanism is used on a reaming tool with extendable cutters that are extendable from the body of the tool to increase the diameter of the tool and aid in forming a wellbore therearound. The locking mechanism prevents the cutters from collapsing or closing as the reamer is moved axially in the wellbore. In another aspect of the invention, a signal to the surface of the well is producible based upon the position of the locking mechanism. In one embodiment, a central bore of the tool is restricted when the mechanism is in an unlocked position and is less restricted when the mechanism is in the locked position. Utilizing this variable restriction, an operator at the surface of the well can determine, based upon back-pressure, the position of the tool in the wellbore.
BRIEF DESCRIPTION OF THE DRAWINGS
So that the manner in which the above recited features of the present invention can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical embodiments of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.
FIG. 1 is a cross-sectional view illustrating a tool in a run-in position.
FIG. 2A is a cross-sectional view illustrating the tool blades in the open position.
FIG. 2B is a cross-sectional view illustrating locking pins in an open position.
FIG. 3 illustrates the first stage in the unlocking sequence as the unlocking sleeve begins to urge the locking pins radially inward.
FIG. 4 illustrates the second stage of the unlocking sequence as the connection pins contact an end portion of the cam.
FIG. 5 illustrates the third stage of the unlocking sequence as the end portion of the cam contacts the upper portion of the locking pins.
FIG. 6A is a cross-sectional view illustrating the tool unlocked and the blades in the closed position.
FIG. 6B is a cross-sectional view illustrating locking pins in a closed position.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 1 is a cross-sectional view illustrating a tool 100 in a run-in position. As shown, the tool 100 is an under-reamer. Generally, the under-reamer is used to enlarge the diameter of an existing wellbore by cutting away a portion of the inner diameter. It should be noted that the invention is not limited to an under-reamer, but may be employed with other downhole tools that require a positive locking mechanism and a flow indicator.
As illustrated in FIG. 1 , the tool 100 includes a sub 215 at the upper end. The sub 215 is used to connect to a string of tubulars (not shown) at a connection 245 . The sub 215 also includes a sub bore 220 to allow fluid communication through sub 215 . As shown, the sub 215 is connected to a body 105 . The body 105 includes a center bore 110 that is fluidly connected with the sub bore 220 to allow the fluid entering the tool 100 to exit out ports 120 .
A housing 260 is disposed around the body 105 and the sub 215 . The housing 260 is moveable between a first position and a second position by fluid pressure. As depicted, a port 270 in the body 105 is in fluid communication with a cavity 275 formed between the sub 215 and a housing surface 280 . As fluid flows through the tool 100 , a portion of fluid in the center bore 110 is communicated through the port 270 into the cavity 275 . As more fluid enters the cavity 275 , the pressurized fluid acts against the housing surface 280 to urge the housing 260 from the first position to the second position.
As illustrated on FIG. 1 , a piston 185 is disposed around the body 105 and connected to the housing 260 . The piston 185 is movable between a first position and a second position. As shown, a port 195 in the body 105 is in fluid communication with a cavity 285 formed between a ring 305 and a piston surface 190 . As fluid flows through the tool 100 , a portion of fluid from the center bore 110 is communicated through the port 195 into the cavity 285 . As more fluid enters the cavity 285 , the pressurized fluid acts against the piston surface 190 to urge the piston 185 from the first position to the second position. At that time, the force against the piston surface 190 overcomes an opposite force created by biasing member 115 , thereafter the piston 185 moves axially downward toward the second position compressing the biasing member 115 against a stop 180 .
The lower end of the piston 185 is connected to an unlocking sleeve 160 by connection pins 165 . The unlocking sleeve 185 includes a taper 170 at an upper end and a sleeve shoulder 265 at a lower end. The sleeve shoulder 265 is constructed and arranged to mate with a cam shoulder 140 on cam 155 . The cam 155 is arranged to shift blades 145 from the closed position to the open position upon activation of the tool 100 .
As further illustrated in FIG. 1 , a plurality of locking pins 150 are disposed in a plurality of side bores 175 . The locking pins 150 are movable between an open and a closed position. In the closed position, as shown in FIG. 1 , the locking pins 150 restrict the flow of fluid through the center bore 110 resulting in a higher pressure in the tool 100 . Each locking pin 150 includes an O-ring 230 disposed around the lower portion of the locking pin 150 to create a fluid tight seal between the locking pin 150 and the side bore 175 .
FIG. 2A is a cross-sectional view illustrating the blades 145 in the open position. The fluid pumped down a tubular string (not shown) through the sub bore 270 enters the center bore 110 . Thereafter, the fluid in the center bore 110 is communicated to ports 270 , 195 and subsequently into cavities 275 , 285 . The fluid pressure in the cavities 275 , 285 urge the housing 260 , the unlocking sleeve 160 and the piston 185 from the first position to the second position, thereby compressing biasing member 115 against stop 180 . At the same time, the sleeve shoulder 265 acts against the cam shoulder 140 to extend the blades 145 to the open position.
Additionally, the fluid pumped through the center bore 110 urges the locking pins 150 radially outward towards the open position. In the open position, an upper portion 130 of the locking pins 150 project out from the body 105 , thereby exposing a pin shoulder 225 . The pin shoulder 225 interacts with a cam surface 290 to prevent axial movement of the cam 155 . In this respect, the locking pins 150 act as a lock to ensure the cam 155 will not move axially, thereby allowing the blades 145 to remain open throughout the operation of the tool 100 .
FIG. 2B is a cross-sectional view illustrating locking pins 150 in the open position. As shown, the locking pins 150 have moved radially outward away from the center bore 110 . In the open position, the locking pins 150 no longer restrict the flow through the center bore 110 resulting in a lower pressure in the tool 100 . The lower pressure corresponds to a predetermined pressure, which indicates to the operator that the blades 145 are fully extended to the open position. Conversely, the locking pins 150 in the closed position restricts the flow through the central bore 110 creating a higher pressure in the tool 100 to indicate to the operator that the blades are in the closed position. In this respect, the locking pins 150 act as an indicator to inform the operator whether the blades 145 are in the open position or in the closed position.
As clearly shown on FIG. 2B , the locking pins 150 include a shear groove 125 at the upper portion 130 . The shear groove 125 is constructed and arranged to allow the upper portion 130 of the locking pins 150 to shear off at a predetermined force. Generally, if the tool 100 becomes immobilized downhole because the biasing member (not shown) or the unlocking sleeve (not shown) fails to function properly, the tool 100 may be removed by axially pulling up on the tool 100 and shearing the top portion of the locking pins 150 . In this respect, the shear groove 125 acts as a back-up means to remove the locking pins 150 from contact with the cam 155 and allow the tool 100 to be removed if the tool 100 fails to function properly.
FIG. 3 illustrates the first stage in the unlocking sequence as the unlocking sleeve 160 begins to urge the locking pins 150 radially inward. After the downhole operation is complete, flow through the tool 100 is reduced, thereby causing the biasing member 115 to expand. As the biasing member 115 expands, the piston 185 , pins 165 and the unlocking sleeve 160 are urged axially upward toward the sub (not shown). As the piston 185 , pins 165 and the unlocking sleeve 160 move from the second position to the first position, the taper 170 on the unlocking sleeve 160 contacts the upper portion 130 of the locking pins 150 , thereby urging the locking pins 150 radially inward toward the center bore 110 . Additionally, the sleeve shoulder 265 loses contact with the cam shoulder 140 , thereby allowing the cam 155 to begin releasing the blades 145 .
FIG. 4 illustrates the second stage of the unlocking sequence as the connection pins 165 contact an end portion 295 of the cam 155 . As the piston 185 , pins 165 and the unlocking sleeve 160 continue to move axially upward toward the sub (not shown), the connection pins 165 travel up slot 135 formed in the cam 155 until the pins 165 contact the end portion 295 . At that point, the axial upper movement of the piston 185 , pins 165 and unlocking sleeve 160 pulls the cam 155 away from the blades 145 , thereby allowing the blades 145 to move from the open position toward the closed position. As further shown in FIG. 4 , the locking pins 150 are urged further inward toward the central bore 110 as the unlocking sleeve 160 moves across the upper portion 130 of the locking pins 150 . As the locking pins 150 restrict the flow through the center bore 110 , a higher pressure is created in the tool 100 . The higher pressure corresponds to a predetermined pressure, which indicates to the operator that the unlocking sequence is in the second stage.
FIG. 5 illustrates the third stage of the unlocking sequence as the end portion 165 of the cam 155 contacts the upper portion 130 of the locking pins 150 . As shown, the cam 155 has moved axially upward allowing the end portion 165 to contact the upper portion 130 to further urge the locking pins 150 inward toward the center bore 110 . As further shown, the blades 145 have started to retract inward to allow the tool 100 to be removed from the wellbore.
FIG. 6A is a cross-sectional view illustrating the tool 100 unlocked and the blades 145 in the closed position. As shown, the tool 100 is in a deactivated state, the cam 155 has pushed the locking pins 150 to the closed position therefore ending the unlocking sequence. As further shown, biasing member 115 is uncompressed and the piston 185 is in the first position. Also shown, the blades 145 are completely closed allowing the tool 100 to be removed from the wellbore. FIG. 6B is a cross-sectional view illustrating locking pins 150 in a closed position. At this point, the operator may verify that the tool 100 is completely deactivated by pumping fluid through a tubular string (not shown) into the tool 100 . As the fluid encounters the locking pins 150 in the closed position, a higher pressure is created in the tool 100 . The higher pressure corresponds to a predetermined pressure, which indicates to the operator that the blades 145 are closed and the tool 100 is deactivated.
In operation, the tool is lowered on a tubular string to a predetermined location in the wellbore. Thereafter, fluid is pumped down the tubular string through the sub bore and enters the center bore. The fluid in the center bore is communicated to ports in the body and subsequently into cavities. The fluid pressure in the cavities urge the housing, the unlocking sleeve and the piston from the first position to the second position, thereby compressing a biasing member against a stop. At the same time, the sleeve shoulder acts against the cam shoulder to extend the blades to the open position.
The fluid pumped through the center bore also urges the locking pins radially outward towards the open position. In the open position, an upper portion of the locking pins project out from the body, thereby exposing a pin shoulder. The pin shoulder interacts with a cam surface to prevent axial movement of the cam. In this respect, the locking pins act as a lock to ensure the cam will not move axially, thereby allowing the blades to remain open throughout the operation of the tool.
After the downhole operation is complete, flow through the tool is reduced causing the biasing member to expand and begin the first stage of the unlocking sequence. As the biasing member expands, the piston, connection pins and the unlocking sleeve are urged axially upward toward the sub. As the piston, connection pins and the unlocking sleeve move from the second position to the first position, the taper on the unlocking sleeve interacts with the upper portion of the locking pins, thereby urging the locking pins radially inward toward the center bore. Additionally, the sleeve shoulder loses contact with the cam shoulder, thereby allowing the cam to begin the release of the blades.
In the second stage of the unlocking sequence, the connection pins contact an end portion of the cam. As the piston, connection pins and the unlocking sleeve continue to move axially upward toward the sub, the connection pins travel up slot formed in the cam until the connection pins contact the end portion of the slot. At that point, the axial upper movement of the piston, connection pins and unlocking sleeve pulls the cam away from the blades, thereby allowing the blades to move from the open position toward the closed position. Additionally, the locking pins are urged further inward toward the central bore as the unlocking sleeve moves across the upper portion of the locking pins. As the locking pins restrict the flow through the center bore, a higher pressure is created in the tool. The higher pressure corresponds to a predetermined pressure, which indicates to the operator that the unlocking sequence is in the second stage. In the third stage of the unlocking sequence, the end portion of the cam contacts the upper portion of the locking pins to further urge the locking pins inward toward the center bore.
After the unlocking sequence is complete, the blades are closed and the locking pins are in the closed position. At this point, the operator may verify that the tool is completely deactivated by pumping fluid through a tubular string into the tool. As the fluid encounters the locking pins in the closed position, a higher pressure is created in the tool. The higher pressure corresponds to a predetermined pressure, which indicates to the operator that the blades are closed and the tool is deactivated. Thereafter, the tool may be removed from the wellbore.
While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
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The present invention generally relates to downhole tools. More particularly, the invention relates to a locking mechanism for use on a downhole tool. A flow actuated locking mechanism is provided for a downhole tool that includes an annular, two-position sleeve having an unlocked position and a locked position. A pin assembly within the tool is used to retain the sleeve in the locked position. In one aspect of the invention, the locking mechanism is used on a reaming tool with extendable cutters that are extendable from the body of the tool to increase the diameter of the tool and aid in forming a wellbore therearound. The locking mechanism prevents the cutters from collapsing or closing as the reamer is moved axially in the wellbore.
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FIELD OF THE INVENTION
The present invention relates to automotive window regulators. More specifically, the present invention relates to a lift plate for a window regulator that resists backdrive forces.
BACKGROUND OF THE INVENTION
Automotive window regulators are required to resist backdrive in order to prevent a partially opened window from being forced down from the outside of the vehicle, such as in a break-in attempt. Current industry practice is to resist backdrive by using a torsion spring clutch in a manual window regulator, and by the electric motor gear ratio in a power window regulator. The disadvantages of both these systems is that the complete window regulator must be robust enough to withstand the backdrive force since the transmitted load path extends all the way from the window glass to the lift plate to the drive assembly (either a manual crank assembly or a power motor). In addition, the traditional methods of resisting backdrive create inefficiencies when the window regulator is operated normally. In a manual system the clutch torque, which could be as
high as 20% of the total operating torque, must be overcome before motion is transmitted to the lift plate. In a power system, single-start worms are required in the motor gearset to ensure suitable backdrive gear efficiency, but single-start worms also create a very low driving efficiency for normal operation of the window regulator.
It is therefore desired to provide a window regulator that resists backdrive in a manner that mitigates or obviates at least one of the above-described disadvantages.
SUMMARY OF THE INVENTION
The present invention provides a window regulator that resists backdrive forces directly at the lift plate and rail, rather than by the drive assembly. A locking shoe is mounted within the lift plate and selectively frictionally engages the rail while the drive assembly is at rest. Thus, any backdrive forces are transmitted from the window glass to the lift plate, and then directly to the rail, avoiding the drive assembly. A release fork that is coupled to the drive cable automatically disengages the locking shoe when the drive assembly is activated, and engages the locking shoe when the drive assembly disengages.
BRIEF DESCRIPTION OF THE DRAWINGS
Preferred embodiments of the present invention will now be described, by way of example only, with reference to the attached Figures, wherein:
FIG. 1 shows a perspective view of a portion of a window regulator in accordance with an aspect of the invention;
FIG. 2 shows a perspective view of a lift plate located on the window regulator shown in FIG. 1 ;
FIG. 3 shows a perspective view of a locking shoe and a nipple housing located on the window regulator shown in FIG. 1 ;
FIG. 4 shows a perspective view of the nipple housing shown in FIG. 3 with the locking shoe removed;
FIG. 5 shows a perspective view of a the locking shoe shown in FIG. 3 from an alternate angle;
FIG. 6 shows a perspective view of the nipple housing shown in FIG. 4 from an alternate angle; and
FIG. 7 shows a perspective view of the nipple housing shown in FIGS. 4 and 6 from an alternate angle.
DETAILED DESCRIPTION OF THE INVENTION
Referring now to FIG. 1 , a portion of a window regulator 10 is shown. Window regulator 10 includes a rail 12 that slidably mounts a lift plate 14 . Lift plate 14 is operable to traverse rail 12 using a drive cable 16 that is wound around a conventional drive and pulley assembly 18 (not shown). A locking shoe 20 is slidably mounted to rail 12 and retained within a cutout on lift plate 14 . Additionally, a nipple housing 22 floats within the cutout on lift plate 14 .
Rail 12 is preferably formed from a unitary piece of metal or plastic and can be manufactured by conventional molding, stamping or roll forming techniques. Rail 12 is attached to a substructure (not shown) of a vehicle door frame via conventional fasteners. Alternatively, rail 12 can be attached to or otherwise formed as part of the substrate of a door hardware module. Rail 12 provides an opposing first surface 21 and second surface 23 (not shown), and further includes a parallel first edge 24 and a second edge 26 that run longitudinally along rail 12 . An arcuate flange 28 is integrally formed from first edge 24 and curves away from first surface 21 of rail 12 , providing a mounting surface for lift plate 14 (described in greater detail below). Proximate to the second edge 26 is a semicircular groove channel 30 that runs parallel to second edge 26 .
Lift plate 14 is raised or lowed by drive and pulley assembly 18 (not shown). As known to those of skill in the art, drive and pulley assembly 18 typically includes a pulley mounted at each end of rail 12 , and a cable drum mounted to window regulator 10 between the two pulleys, but displaced away from rail 12 . Other arrangements of pulleys and cable drums will occur to those of skill in the art, and are within the scope of the invention. For example, the pulleys or the cable drum could be mounted directly to a door hardware module, instead of rail 12 . Drive cable 16 is threaded around the cable drum and pulleys, and is described in greater detail below, terminates with a nipple 17 at each end inside nipple housing 22 located within lift plate 14 . The cable drum is further coupled to a conventional manual crank system or an electric motor to move the lift plate along rail 12 .
Referring now to FIG. 2 , lift plate 14 is shown in greater detail. Lift plate 14 is preferably formed from a unitary piece of metal or plastic and can be manufactured by conventional casting or molding techniques. Lift plate 14 is adapted to mount a window glass (not shown) on a first surface 29 using conventional fasteners, tabs or the like. As described earlier, lift plate 14 is slidably mounted to rail 12 . An arcuate quadrant slot 32 is provided in an opposing second surface 31 of lift plate 14 and is complementarily fitted over arcuate flange 28 . This mounting configuration provides a degree of axial freedom of rotation of lift plate 14 around rail 12 without affecting the locking or unlocking action of lift plate 14 (described in greater detail below). Axial freedom of rotation provides for correct glass tracking and alignment of the window glass with the glass run channels in the door frame (not shown). As mentioned earlier, lifting plate 14 further includes a cutout 34 between first surface 29 and second surface 31 . In the current embodiment, cutout 34 includes a generally rectangular area 36 in communication with a generally oval area 38 . As can be seen in FIG. 1 and is described in greater detail below, locking shoe 20 is retained against the sidewalls of rectangular area 36 and nipple housing 22 floats more loosely within oval area 38 . Two cable passages 40 coaxial with rail 12 extend from opposing side walls 33 of lifting plate 14 into oval area 38 and provide means to thread drive cable 16 through to nipple housing 22 .
Referring now to FIGS. 3 to 5 , locking shoe 20 is described in greater detail. Locking shoe 20 is generally ‘C shaped’ piece of metal or plastic and is fitted over both surfaces of rail 12 at the second edge 26 . Locking shoe 20 includes a sidewall 44 that abuts second edge 26 of rail 12 , a retaining wall 46 that extends around a portion of first surface 21 that includes groove channel 30 , and a retaining wall 48 extending around a portion of second surface 23 that includes the under-surface of groove channel 30 . A flange 50 with a central cutout 52 depends from retaining wall 46 . Locking shoe 20 is located around the second edge 26 of rail 12 by two resilient balls 54 ( FIG. 4 ) that are retained between groove channel 30 in the rail and two symmetrically oriented grooves 56 formed on the interior surface of retaining wall 46 of locking shoe 20 . Preferably, balls 54 are metal bearing. A lip 58 is formed between the edge of grooves 56 and the inner surface of sidewall 44 . A fin 60 , acting as a fulcrum is integrally formed on the inner surface of sidewall 44 and retaining wall 46 midway between the two grooves 56 . Both flanges 50 and lip 58 slope away from first surface 21 on rail 12 as they extend outwards from a centerline defined by central cutout 52 and fin 60 . An opposing pair of ramps 62 are situated on the inner surface of retaining wall 48 and provide a reaction force against the underside of groove channel 30 on second surface 23 . On each side of fin 60 , ramps 62 are sloped inversely to flange 50 and lip 58 .
Referring now to FIGS. 4 , 6 and 7 , nipple housing 22 is described in greater detail. Nipple housing 22 is located in oval area 38 of cutout 34 . A chamber 64 provided inside nipple housing 22 is adapted to retain the one or two nipples 17 located at the ends of drive cable 16 . A slot 66 is provided in a portion of the sidewalls of nipple housing 22 for drive cable 16 to pass through into chamber 64 . Additionally, a gap 68 is provided in the sidewall of nipple housing 22 to fit nipples 17 into chamber 64 through during assembly of window regulator 10 .
Floating nipple housing 22 further includes an integrally molded release fork 70 . Release fork 70 includes a central finger 72 disposed between two spring fingers 74 . The ends of spring fingers 74 are generally parallel to central finger 72 . Central finger 72 passes through central cutout 52 into locking shoe 20 . A slot 76 on the end of central finger 72 locates nipple housing 22 on fin 60 ( FIG. 5 ) and allows nipple housing 22 to partially pivot there around. The range of pivotal motion of nipple housing 22 is limited by the sidewalls of central cutout 52 in flange 52 . Spring fingers 74 abut against lip 58 and urge release fork 70 into a neutral, “locked” position equidistant between the two grooves 56 and perpendicular to the axis of motion in locking shoe 20 . Additionally, spring fingers 74 preload spherical balls 54 into full contact with grooves 56 and groove channel 30 when lift plate 14 is stationary, locking lift plate 14 . Release fork 70 has two cam faces 78 that are aligned with the longitudinal centerline of groove channel 30 and with the center of balls 54 ( FIG. 4 ). The ratio of the overall length of central finger 72 to the distance from its base against sidewall 46 to the center of cam faces 78 provides a mechanical advantage which reduces the effort required to release spherical balls 54 .
The rotation of release fork 70 , due to the movement of drive cable 16 locks and unlocks lift plate 14 . At rest, lift plate 14 is effectively locked. The relationship between the angle subtended by groove channel 30 on rail 12 and grooves 56 (formed by flange 50 and lip 58 ) on locking shoe 20 , together with the operating coefficient of friction in the locking shoe 20 and rail 12 , are such that locking shoe 20 is locked in place to rail 12 by a wedging action by the leading ball 54 generally perpendicular to first surface 21 on rail 12 . Backdriving of window regulator 10 is resisted directly at lift plate 14 —force is transmitted from the window glass to the lift plate, and subsequently to locking shoe 20 . The backdrive force wedges the leading balls 54 between its groove 56 and groove channel 30 . The opposing ramp 48 provides a reaction force against the underside of groove channel 30 on rail 12 . Force is then transmitted directly to rail 12 , and not down drive cable 16 to the drive assembly. A small clearance is provided between cam faces 78 and balls 54 to ensure release fork 70 does not dislodge the locking ball 54 .
Lift plate 14 is effectively unlocked by engaging drive and pulley assembly 18 . The initial movement of drive cable 16 causes nipple housing 22 to rotate slightly in lift plate 14 around fin 60 , bringing the leading cam face 78 of release fork 70 into contact with the leading ball 54 . This contact pushes the leading ball 54 out of secure engagement between groove channel 30 and groove 56 . At this point, lift plate 14 is still stationary. Continued movement of drive cable 16 then rotates nipple housing 22 further until the leading sidewall of nipple housing 22 comes into contact with the side face of rectangular area 36 on cutout 34 so that nipple housing 22 reacts against lip plate 14 . Then, drive cable 16 , locking shoe 20 , nipple housing, 22 and lift plate 14 then move together as a single unit. Additionally, as nipple housing 22 is rotated around fin 60 , the trailing spring finger 74 is restrained by the slope of lip 58 and flange 50 , placing the trailing spring finger 74 under tension. When the movement of drive cable 16 stops, the release of tension forces in drive cable 16 and the trailing spring fingers 74 combine to return nipple housing 22 and balls 54 to a locked position between groove channel 30 and grooves 56 , as is described above. Only the leading ball 54 needs to be released by release fork 70 as the trailing ball 54 has no influence on the motion of lift plate 14 .
The above-described embodiments of the invention are intended to be examples of the present invention and alterations and modifications may be effected thereto, by those of skill in the art, without departing from the scope of the invention which is defined solely by the claims appended hereto.
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A window regulator that resists backdrive forces directly at the lift plate and rail, rather than by the drive assembly. A locking shoe mounted within the lift plate and selectively frictionally engages the rail while the drive assembly is at rest. Thus, any backdrive forces are transmitted from the window glass to the lift plate, and then directly to the rail, avoiding the drive assembly. A release fork that is coupled to the drive cable automatically disengages the locking shoe when the drive assembly is activated, and engages the locking shoe when the drive assembly disengages.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a portable chamfering machine for chamfering the edge portions of the undersurface of a workpiece efficiently.
2. Description of the Related Art
A conventional portable chamfering machine for chamfering the edge portion of a workpiece by means of the cutting edges formed on the outer periphery of a rotary cutter has a main body provided with a guide which comprises two guide faces intersecting with each other at right angles and are arranged such that the cutting edges of the rotary cutter are slantwise exposed at the intersecting portion thereof. The chamfering is carried out by moving the chamfering machine along the edge of the workpiece to be chamfered with the perpendicularly intersecting guide faces in contact with the both side faces of the edge of the workpiece.
When the edge of the undersurface of a workpiece is chamfered with this conventional machine, the workpiece must be turned upside down or the chamfering machine must be inverted to be applied to the underside edge of the workpiece to be chamfered. A conventional portable chamfering machine is proposed by this applicant in U.K. Patent application Ser. No. 8919027,6.
However, it takes time to turn the workpieces over every time their underside edges are to be chamfered. Particularly, it is not easy to upturn bulky workpieces each time. When the chamfering machine is used in a reverted manner, on the other hand, the operator must take an unnatural position and he cannot operate the machine easily. In either case, the operational efficiency is lowered.
SUMMARY OF THE INVENTION
The object of this invention is to provide a portable chamfering machine which chamfers the edge portions of not only the upper surface but the undersurface of a workpiece efficiently even if the workpiece is bulky.
In order to attain the object, a chamfering machine of this invention comprises a rotary shaft, a guide base provided perpendicularly to the rotary shaft, an adjusting unit for adjusting the relative positional relationship between the rotary shaft and the guide base, a cutter detachably mounted on the rotary shaft for chamfering the edge portion of a workpiece, a guide detachably mounted on the rotary shaft for contacting a lateral face of the workpiece and a fixing member for fixing the guide to the rotary shaft after the vertical positional relationship has been adjusted between the guide and the cutter.
When the edge portion of the upper surface of a workpiece is chamfered with the chamfering apparatus of this invention, the cutter is positioned to direct the cutting edges downward, and the cutter and the guide are fixedly mounted on the rotary shaft so as to locate the guide under the cutter. The rotary shaft is lifted or lowered with respect to the guide base such that the downward directed cutting edges bite into the edge portion of the upper surface of the workpiece by the predetermined amount. As the cutter is rotated, the chamfering machine is moved along the edge of the workpiece to be chamfered with the guide set in contact with the lateral sides of the workpiece.
When the edge portion of the undersurface of a workpiece is chamfered, the cutter is set to direct the cutting edges upward and the guide is positioned over the cutter. The rotary shaft is moved upward or downward with respect to the guide base so that the upward directed cutting edges bite into the edge of the undersurface of the workpiece by the predetermined amount. As the cutter is rotated, the chamfering machine is moved along the edge by contacting the guide with the lateral sides of the workpiece.
Additional objects and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objects and advantages of the invention may be realized and obtained by means of the instrumentalities and combinations particularly pointed out in the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate a presently preferred embodiment of the invention, and together with the general description given above and the detailed description of the preferred embodiment given below, serve to explain the principles of the invention.
FIG. 1 is a partially broken front view of one embodiment of the chamfering machine of this invention which is set to chamfer the edge portion of the upper surface of a workpiece;
FIG. 2 is a partially broken front view of the main part of the chamfering machine in which the positional relationship between the cutter and the guide bearing is reversed and which is set to chamfer the edge portion of the undersurface of a workpiece;
FIG. 3 is a perspective view of a part of the cutter holder having a recessed portion formed in its end portion;
FIG. 4 is a perspective view of a part of the rotary shaft having a projecting portion at its stepped portion; and
FIG. 5 is a perspective view of the lock nut having a projecting portion on its end portion.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
As shown in FIG. 1, an embodiment of the chamfering machine of this invention comprises a casing 3 provided on its upper end with a grip portion 1 and on its lateral side with an auxiliary handle 2, and also provided with a motor, not shown, housed in the casing 3 and driven by a fluid pressure or an electric power. The rotational force of the motor is transmitted directly or through a transmission, not shown, to a rotary shaft 4 downwardly extending from the casing 3.
A guide base 5 to be placed on the surface of a workpiece 6 is extended perpendicularly to the rotary shaft 4. Elevating guide posts 8 (four in number, for example) are perpendicularly mounted on the guide base 5 and arranged equidistantly in the circumferential direction with a through hole 7 formed in the guide base 5 as a center. The upper portions of the elevating guide posts 8 pass through an annular holder 9 fixed to the outer periphery of the casing 3 such that the casing 3 is lifted and lowered with respect to the guide base 5 to adjust the relative positional relationship between the rotary shaft 4 and the guide base 5 in the axial direction of the rotary shaft 4. The portions of the annular holder 9 through which the elevating guide posts 8 pass are thick and threadably engaged by thumbscrews 10 for tightening the elevating guide posts 8 to the annular holder 9. A bellows type cover 11 is disposed between the upper surface of the guide base 5 and the undersurface of the casing 3 so as to surround the rotary shaft 4.
The rotary shaft 4 downwardly extended from the casing 3 has a shoulder. On the front end portion of the rotary shaft 4 is fixedly mounted a cutter 13 for chamfering the edge portion of the workpiece 12 and is fitted a guide bearing or a guide 14 which rotates in contact with the lateral side portion of the workpiece 12. The cutter 13 and the guide bearing 14 can be turned upside down each other and are set in position on the rotary shaft 4 by means of a lock nut 15 in such a manner that they are sandwiched between the shoulder of the rotary shaft 4 and a lock nut 15 mounted on the tip end of the rotary shaft 4. The cutter 13 has square cutting tips 16 having cutting edges formed on their four side edges. The cutter 13 further has a holder 18 formed with fixing grooves 17 arranged in a mirror image relationship and receiving the cutting tips 16 so as to extend one cutting edge of each cutting tip 15 from the respective groove 17 at an inclining angle of 45 degrees with respect to the guide holder 18. The cutting tips 16 are fixed to the holder 18 by means of screws 19.
FIG. 1 shows the arrangement for chamfering the edge portion of the upper surface of the workpiece 12 with the cutter 13. The cutter 13 is set to direct downwards those cutting edges 16A of the cutting tips 16 which are extended from the holder 18, and the guide bearing 14 is disposed under the cutter 13. Thereafter, both the cutter 13 and the guide bearing 14 are tightened together by means of the lock nut 15.
On the contrary to FIG. 1, FIG. 2 shows the arrangement for chamfering the edge portion of the undersurface of the workpiece 12. The cutter 13 is set to direct upwardly those cutting edges 16 of the cutting tips 16 which are extended from the holder 18, and the guide bearing 14 is placed over the cutter 14. Then, the cutter 13 and the guide bearing 14 are fastened to each other by means of the lock nut 15.
A fixing structure of the cutter 13 and the guide bearing 14 to the rotary shaft 4 will now be explained.
In this embodiment, substantially rectangular recessed portions 21 are formed in the central parts of the upper and lower boss portions 20 (see FIG. 3). On the shoulder of the rotary shaft 4 is formed a substantially rectangular projecting portion 22 which can be fitted in the recessed portions 21 (see FIG. 4). On one end of the lock nut 15 is provided a substantially rectangular projecting portion 23 which can be inserted in the recessed portions 21 (see FIG. 5). When the cutter holder 18 is reversed, therefore, it can also be mounted on the rotary shaft 4. Further, the holder 18 and the guide bearing 14 are mounted on the rotary shaft 4 by sandwiching them between the projecting portion 22 on the shoulder of the rotary shaft 4 and the lock nut 15.
The operation of the above-mentioned embodiment will now be explained.
First, the chamfering of the edge portion of the upper surface of the workpiece 12 will be described.
As shown in FIG. 1, the cutter 13 is disposed to direct downwardly the cutting edge 16A of the cutting tips 16 which are held in the holder 18, and the guide bearing 14 is placed under the cutter 13. Then, the cutter 13 and the guide bearing 14 are mounted on the rotary shaft 4 and fixed thereto. Thereafter, the thumbscrews 10 are loosened, and the casing 3 is lifted or lowered until the downwardly directed cutting edges 16A are extended downward by a required chamfering amount from the undersurface of the guide base 5 in the through hole 7. After then, the thumbscrews 10 are tightened again to fix the casing 3 at the required level. In this state, the chamfering machine is held by an operator with his hands at the grip portion 1 and the auxiliary handle 2. By rotating the rotary shaft 4, the chamfering machine is mounted at the guide base 5 on the workpiece 12. As the chamfering machine is moved along the edge portion of the workpiece 12 with the guide bearing 14 in contact with the lateral side of the workpiece 12, the edge portion of the upper surface of the workpiece 12 is camfered by the cutting edges 16A of the cutter 13 rotating together with the rotary shaft 4.
Next, the chamfering of the undersurface of the workpiece 12 will be explained.
In this case, the chamfering machine is not turned upside down. Instead, as shown in FIG. 2, the cutter 13 is disposed to direct upwardly the cutting edges 16A of the cutting tips 16 which is held in the holder 18, and the guide bearing 14 is positioned above the cutter 13 by reversing the positions of the cutter 13 and the guide bearing 14. Then, the cutter 13 and the guide bearing 14 are fixedly mounted on the rotary shaft 4. In this state, the casing 3 is lowered until the upwardly directed cutting edges 16A contact the edge portion of the undersurface of the workpiece 12. After the amount of chamfering has been set to the predetermined one, the rotary shaft 4 is likewise rotated and the chamfering machine is placed at the guide base 5 on the workpiece 12. The edge portion of the undersurface of the workpiece 12 is chamfered by the cutting edges 16A of the cutter 13, as the chamfering machine is moved along the edge portion of the workpiece 12 with the guide bearing 14 in contact with the lateral side of the workpiece 12.
In place of lifting or lowering the casing 3 along the elevating guide posts 8 as in the case of the abovementioned embodiment, the guide base 5 may be fixed to the casing 3 when the rotary shaft 4 is made to be lifted and lowered with respect to the casing 3. The chamfering cutting edges are not limited to the cutting tips but may be the ones directly formed on the bulk shape cutter. Further, the structure for preventing the cutter and the guide bearing from freely rotating may comprise sliding keys formed on the rotary shaft and key grooves formed loosely fitted in the respective sliding keys and formed in the holes of the cutter and the guide bearing in which the rotary shaft is inserted.
This invention is not limited to the above-mentioned embodiments but various modifications are availably within the scope of this invention.
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A chamfering machine comprises a rotary shaft, a guide base provided perpendicularly to the rotary shaft, an adjusting unit for adjusting the relative positional relationship between the rotary shaft and the guide base, a cutter detachably mounted on the rotary shaft for chamfering the edge of a workpiece, a guide detachably mounted on the rotary shaft for contacting a lateral face of the workpiece and a fixing member for fixing the guide to the rotary shaft after the vertical positional relationship has been adjusted between the guide and the cutter.
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BACKGROUND OF THE INVENTION
The present invention relates to the field of well tools located downhole in a borehole. More particularly, the invention relates to an apparatus and method for locating and for retrieving downhole well tools.
Logging tools and other devices are run downhole in boreholes to investigate subterranean structures and to perform different exploratory and production operations. Logging tools are typically lowered into a borehole with a wireline which provides a structural connection to surface equipment and further provides a conductor for transmitting power and electrical signals. Wirelines are subject to failure due to wear and to binding forces exerted by the borehole wall against the tool. When a wireline separates from a logging tool in a vertical or inclined borehole, gravity pulls the tool lower within the borehole. Accordingly, the last known location of the logging tool may not accurately reflect the final resting location of the tool. Such location may be particularly difficult to locate in multilateral wells having multiple borehole branches.
Rig down time caused by a lost logging tool is costly. Wireline failure can strand a logging tool thousands of feet downhole in borehole, and abandonment of a million dollar logging tool is not economic. Loose logging tools impede further rig operations, and drilling rig time on offshore wells can cost over one hundred thousand dollars per day. This cost is increased by the travel time required by well contractors specializing in tool retrieval. When a tool is lost in a well, such well contractors may travel for one or more days to reach the borehole site before the tool retrieval operations can begin. Although certain of these costs can be avoided by effective equipment maintenance, logging tools are also lost due to tool sticking, formation collapse, and other causes unrelated to the wireline.
The process of locating and retrieving a lost tool (known as a "fish") is known as "fishing". Casing collar search tools are sometimes successful in locating lost tools. Alternatively, fishing operations are typically conducted by lowering a drill string into the borehole until the drill string lower end contacts the lost tool. Such contact places weight on the lost tool and reduces the weight on the drill string. If the tool is lodged in the borehole, the drill string weight can further drive the tool into the geologic formations. The reduction in drill string weight is monitored to identify contact with the downhole tool, however the weight reduction is almost imperceptible in deep boreholes requiring a long drill string. Additionally, false weight readings can occur in deviated and horizontal wells as the drill string contacts the borehole wall.
After the lower end of the drill string has located the downhole tool, an "overshot" is attached to the tool for retrieval to the borehole surface. Overshots typically comprise a coiled steel ribbon which is lowered over a tool. The overshot constricts to grip the tool as the drill string and overshot are withdrawn from the borehole. Overshots are effective when the tool is stuck in the borehole and the wireline is still attached to the tool. In such circumstances, the wireline guides the overshot over the tool end so that an effective grip can be achieved. However, overshots are difficult to operate when the tool has parted from the wireline and the tool location is unknown.
Accordingly, a need exists for an improved system for locating and retrieving tools downhole in a borehole. The system should be easy to deploy and to operate, and should be sufficiently flexible to handle different lost tool conditions.
SUMMARY OF THE INVENTION
The present invention provides an apparatus and method for locating a downhole well tool and for retrieving the tool. The apparatus comprises a housing moveable within the borehole, a means for generating a signal indicating the tool location downhole in the borehole, a controller attached to said housing for detecting the signal, and a mechanism for engaging the housing and the tool. In different embodiments of the invention, the controller can initiate a signal to the tool, and the tool can reflect the controller signal or can include a beacon for returning a beacon signal to the controller. The controller can determine the distance between the housing and the tool, and a catch can be attached to the tool for selectively engaging the mechanism.
The method of the invention is practiced by moving the housing within the borehole, by operating the controller to detect a signal emanating from the tool and to identify the distance between the housing and tool, and by operating the mechanism to engage the tool. In different embodiments of the method, the controller can broadcast the signal to the tool, or the tool beacon can broadcast a signal to the controller. The catch can engage the mechanism to permit retrieval of the tool from the borehole.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates a housing lowered into proximity with a logging tool lodged downhole in a borehole.
FIG. 2 illustrates multiple tools within a borehole, wherein each tool responds to a different signal broadcast from a controller.
FIGS. 3 and 4 illustrate the operation of a grappling mechanism for engaging a catch on the tool and for retrieval of the tool from the borehole.
FIG. 5 illustrates a locking catch.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention provides an apparatus and method for locating a downhole well tool and for retrieving the tool from the borehole. FIG. 1 illustrates borehole 10 within subterranean geologic formations 12. A tool such as logging tool 14 is located within borehole 10 and is attached to severed wireline end 16. The other length of the original tool wireline is removed from borehole 10 and is not illustrated. In this position, tool 14 is "lost" within borehole 10 because surface control of tool 14 has ceased. The location of tool 14 may not be accurately known, thereby hampering efforts to dislodge or to retrieve tool 14.
As shown in FIG. 1, housing 18 is lowered into borehole 10 with another wireline such as cable 20. Although cable 20 is illustrated as a multistrand wireline cable, cable 20 can also comprise a tubular member such as drill pipe, coiled tubing, or other component useful in pushing housing 18 into deviated and horizontal boreholes 10. For all embodiments of the invention, housing 18 can be lowered into an open hole borehole 10 or can be lowered through well tubing or casing (not shown) within borehole 10.
Housing 18 includes controller 22 and grappling attachment 24. Controller 22 can detect a signal emanating from tool 14 and can indicate the location of tool 14 relative to housing 18 to facilitate movement of housing 18 toward tool 14. Controller 22 can perform these functions in different ways. In one embodiment of the invention as shown in FIG. 1, beacon 26 is attached to tool 14 and generates a signal detectable by receiver 28 within controller 22. Such beacon signal can comprise an acoustic rescue signal or other signal suitable for transmission within borehole 10 or through geologic formations 12. Beacon 26 can be enclosed within an interior volume of tool 14, can be enclosed within cable head 30 connecting tool 14 and wireline end 16, or can be attached to the exterior of tool 14. Beacon 26 can be powered through the original tool wireline or with battery or capacitor power if wireline end 16 is damaged or severed as illustrated in FIG. 1.
Beacon 26 can operate continuously or can be activated upon the occurrence of different events. Beacon 26 can emit an acoustic rescue signal or other signal detectable by controller 22. For example, beacon 26 can be selectively activated if wireline 16 is separated from tool 14, or if tool 14 is normally moveable and becomes stationary for a selected time period, or if signal communication between tool 14 and the surface of borehole 10 is lost. In another embodiment of the invention, beacon 26 can be activated by the transmission of a controller signal from controller 22 or another exterior signal generating source.
The acoustic rescue signal generated by beacon 26 can comprise a simple "ping" detectable by controller 22. The ping can be transmitted at regular intervals or in a particular sequence. The sequence can be designed to identify the particular tool in a borehole 10 having multiple tools, can be sequenced to identify the power reserves remaining, or can be sequenced to respond to other signals such as a signal generated from the well surface or from a position downhole in borehole 10.
In one embodiment of the invention, controller 22 can broadcast a signal such as an acoustic signal which is reflected by tool 14 and partially returned to controller 22 for detection. The reflected signal can be processed by controller 22 to identify the location of tool 14 relative to housing 18. In another embodiment of the invention previously discussed, controller 22 can broadcast a controller signal which is received by beacon 26, and which instructs beacon 26 to send a beacon signal in response. The returning beacon signal detected by controller 22 can be processed to determine the elapsed transmission time for the controller signal and the returning beacon signal, and the calculated distance between tool 14 and housing 18. The distance between controller 22 and tool 14 comprises the elapsed time between transmission of the controller signal and the receipt of the beacon signal, minus the response time required by beacon 26 after the controller signal is received. The intensity of the signal can be processed, depending on the transmission media through borehole 10 or through geologic formations 12 for a sidetrack or offset measurement, to determine the distance between tool 14 and housing 18.
As controller 22 is lowered into borehole 10, controller 22 can estimate the remaining distance between controller 22 and tool 14. As controller 22 travels closer to tool 14, the round trip travel time of the controller signal and reflected signal or beacon signal will become shorter. Twice the change in controller 22 depth divided by the change in round trip travel time is equal to the average sound speed in borehole 10. The borehole distance between controller 22 and tool 14 can be approximated by multiplying one-half the round trip travel time by the average sound speed in borehole 10 between controller 22 and tool 14. The change in such round trip travel time, when correlated with the measured depth of controller 22 within borehole 10 as controller is lowered, provides sufficient information to estimate the remaining distance between controller 22 and tool 14, and the projected time of contact at various rates of controller 22 descent within borehole 10.
Although controller 22 is shown as a single component, controller 22 can comprise multiple sensors, controller units and signal transmitters which are located together or are positioned at various positions along cable 20. For example, tool 14 could be located in the sidetracked portion of borehole 10. In such a position, multiple controllers 22 could be positioned along cable 20 to detect signals emanating from tool 14. If multiple controllers 22 are located at different positions within borehole 10, triangulation calculation procedures can determine the precise location of tool 14 relative to controllers 22. Cross-correlation between signals can be used to infer direction of the signal.
Data from controller 22 can be transmitted through cable 20 or through conductors (not shown) attached to cable 20 to control equipment 32 located at the surface of borehole 10. Control equipment 32 can generate the controller signals, can receive the signals emanating from tool 14 as a reflected signal or as a beacon signal from beacon 26, and can perform all processing functions necessary to identify and locate tool 14. These functions can be performed by controller 22 downhole within wellbore 10 and a signal transmitted to an operator at the surface. Alternatively, these functions can be performed with control equipment 32 at the surface to protect sensitive electronic equipment from hazardous downhole conditions such as elevated temperatures and corrosive fluid conditions.
FIG. 2 illustrates another embodiment of the invention wherein multiple tools 14 are located within borehole 10. As shown in FIG. 2, such tools can comprise well completion equipment such as sliding sleeves, valves, packers, chemical injection nozzles, or other tools. A separate beacon 26 is attached to each tool 14, and each beacon 26 is capable of generating a distinct beacon signal. When controller 22 is positioned within borehole 10, controller 22 can selectively generate different controller signals correlating with a selected beacon 26 for a selected tool 14. Selective broadcast of a controller signal will operate the beacon signal for a selected beacon 26, thereby permitting the placement of housing 18 toward the selected tool 14. This feature of the invention permits controller 22 to identify and locate one tool 14 within a multiple well tool installation. As previously noted, controller 22 can operate within an open borehole 10 or within a tubing or casing string positioned within borehole 10.
FIG. 1 illustrates one embodiment of grappling attachment 24 which is configured to encircle one end of tool 14. Operation of attachment 24 closes a metal loop around tool 14 to permit retrieval of tool 14 from borehole 10. Another embodiment of grappling attachment 34 is illustrated in FIGS. 3 and 4. In FIG. 3, housing 18 is lowered into proximity with tool 14, and controller 22 releases ring assembly 36 from an enclosure within the interior of housing 18. Ring assembly 36 comprises numerous circular rings which are released to fill the interior cross section of borehole 10. Leaf springs, floats, or other devices can expand such circular rings within the volume defined by borehole 10.
Controller signal from controller 22 activates a mechanism such as catch 38 attached to tool 14. Catch 38 can comprise many different shapes or configurations, and is illustrated as one or more retractable hooks 40 rotated outwardly from tool 14. Catch 38 is initially contained within tool 14 to prevent friction and other contact with the wall of borehole 10, and is operable to expose hooks 40 to grappling attachment such as ring assembly 34. Catch 38 can be activated with a coded signal from controller 22 which comprises a coded sequence or frequency of acoustic pulse. By coding such open signal, premature or accidental opening of catch 38 can be prevented.
FIG. 4 shows catch 38 in an operable condition having extended hooks 40 in engagement with ring assembly 36. Each hook 40 can have a spring loaded gate or clasp 42 as illustrated in FIG. 5 to resist disengagement of hook 40 with ring assembly 36 after the initial engagement is made. To secure the connection between housing 18 and tool 14, cable 20 and housing 18 can be reciprocated within borehole 10 to increase the number of hooks 40 engaged with different loops within ring assembly 36. After the attachment between housing 18 and tool 14 is secured, cable 20 can be reeled in from borehole 10 surface to dislodge or to retrieve tool 14 from wellbore 10. Even if cable 20 is insufficiently strong to dislodge tool 14, cable 20 is positioned to guide the operation of conventional drill string and overshot fishing tools.
The invention is particularly useful in the location and retrieval of moveble tools such as logging tools which have become lodged or lost within a borehole. In multilateral wells having various wellbores connected to a central wellbore, the invention facilitates the entry of tool retrieval mechanisms into the correct wellbore branch. The invention accomplishes this function by providing continuous downhole communication between controller 22 and beacon 26 at tool 14. If the signals transmitted between controller 22 and beacon 26 indicate that the distance between such components is becoming greater (or the signal weaker) as housing 18 is lowered into one borehole branch within the borehole system, controller 22 or an operator at the well surface will perceive that housing 18 has entered an incorrect borehole branch and operating changes can be made.
The invention saves rig time by reducing the complexity and performance of fishing operations. By integrating a beacon 26 or signal reflector within tool 14, a positive location signal source is attached to tool 14. This source signal facilitates identification of the tool 14 location by the onsite rig operator. This onsite capability reduces the need for fishing specialists and equipment located several days travel time from the rig site. The rig operator can lower controller 22 within borehole 10 to identify tool 14, to locate the position of tool 14, and to deploy grappling equipment for engaging and for retrieving tool 14. As previously discussed, this capability is particularly useful where a moveable tool such as a logging tool has become separated from the wireline or otherwise lodged in a borehole.
Although the invention has been described in terms of certain preferred embodiments, it will be apparent to those of ordinary skill in the art that modifications and improvements can be made to the inventive concepts herein without departing from the scope of the invention. The embodiments shown herein are merely illustrative of the inventive concepts and should not be interpreted as limiting the scope of the invention.
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An apparatus as method for identifying, locating, and retrieving a downhole tool from a borehole. A controller is lowered into the borehole and is capable of detecting a signal from the tool. The signal can be broadcast from the tool, can be generated in response to a signal from the controller, or can be reflected from a controller signal. The controller processes the signal to identify the location and heading of the controller from the tool, and to guide the controller toward the tool. When the controller is moved proximate to the tool, a catch mechanism can be activated to connect the tool and controller housing. The tool is then dislodged for further operation, or is retrieved to the borehole surface.
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CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This is a divisional of U.S. patent application Ser. No. 11/707,787, filed Feb. 16, 2007, which is a divisional of U.S. patent application Ser. No. 11/188,297, filed Jul. 22, 2005, which is a divisional of U.S. patent application Ser. No. 10/823,248, filed on Apr. 13, 2004, which is a divisional of U.S. patent application Ser. No. 10/161,780, filed on Jun. 4, 2002, which claims priority under 35 U.S.C. § 119(e) to U.S. Provisional Patent Application No. 60/296,848, filed on Jun. 8, 2001.
BACKGROUND OF THE INVENTION
[0002] This invention relates to a process for processing natural gas or other methane-rich gas streams to produce a liquefied natural gas (LNG) stream that has a high methane purity and a liquid stream containing predominantly hydrocarbons heavier than methane.
[0003] Natural gas is typically recovered from wells drilled into underground reservoirs. It usually has a major proportion of methane, i.e., methane comprises at least 50 mole percent of the gas. Depending on the particular underground reservoir, the natural gas also contains relatively lesser amounts of heavier hydrocarbons such as ethane, propane, butanes, pentanes and the like, as well as water, hydrogen, nitrogen, carbon dioxide, and other gases.
[0004] Most natural gas is handled in gaseous form. The most common means for transporting natural gas from the wellhead to gas processing plants and thence to the natural gas consumers is in high pressure gas transmission pipelines. In a number of circumstances, however, it has been found necessary and/or desirable to liquefy the natural gas either for transport or for use. In remote locations, for instance, there is often no pipeline infrastructure that would allow for convenient transportation of the natural gas to market. In such cases, the much lower specific volume of LNG relative to natural gas in the gaseous state can greatly reduce transportation costs by allowing delivery of the LNG using cargo ships and transport trucks.
[0005] Another circumstance that favors the liquefaction of natural gas is for its use as a motor vehicle fuel. In large metropolitan areas, there are fleets of buses, taxi cabs, and trucks that could be powered by LNG if there were an economic source of LNG available. Such LNG-fueled vehicles produce considerably less air pollution due to the clean-burning nature of natural gas when compared to similar vehicles powered by gasoline and diesel engines which combust higher molecular weight hydrocarbons. In addition, if the LNG is of high purity (i.e., with a methane purity of 95 mole percent or higher), the amount of carbon dioxide (a “greenhouse gas”) produced is considerably less due to the lower carbon:hydrogen ratio for methane compared to all other hydrocarbon fuels.
[0006] The present invention is generally concerned with the liquefaction of natural gas while producing as a co-product a liquid stream consisting primarily of hydrocarbons heavier than methane, such as natural gas liquids (NGL) composed of ethane, propane, butanes, and heavier hydrocarbon components, liquefied petroleum gas (LPG) composed of propane, butanes, and heavier hydrocarbon components, or condensate composed of butanes and heavier hydrocarbon components. Producing the co-product liquid stream has two important benefits: the LNG produced has a high methane purity, and the co-product liquid is a valuable product that may be used for many other purposes. A typical analysis of a natural gas stream to be processed in accordance with this invention would be, in approximate mole percent, 84.2% methane, 7.9% ethane and other C 2 components, 4.9% propane and other C 3 components, 1.0% iso-butane, 1.1% normal butane, 0.8% pentanes plus, with the balance made up of nitrogen and carbon dioxide. Sulfur containing gases are also sometimes present.
[0007] There are a number of methods known for liquefying natural gas. For instance, see Finn, Adrian J., Grant L. Johnson, and Terry R. Tomlinson, “LNG Technology for Offshore and Mid-Scale Plants”, Proceedings of the Seventy-Ninth Annual Convention of the Gas Processors Association, pp. 429-450, Atlanta, Ga., Mar. 13-15, 2000 and Kikkawa, Yoshitsugi, Masaaki Ohishi, and Noriyoshi Nozawa, “Optimize the Power System of Baseload LNG Plant”, Proceedings of the Eightieth Annual Convention of the Gas Processors Association, San Antonio, Tex., Mar. 12-14, 2001 for surveys of a number of such processes. U.S. Pat. Nos. 4,445,917; 4,525,185; 4,545,795; 4,755,200; 5,291,736; 5,363,655; 5,365,740; 5,600,969; 5,615,561; 5,651,269; 5,755,114; 5,893,274; 6,014,869; 6,062,041; 6,119,479; 6,125,653; 6,250,105 B1; 6,269,655 B1; 6,272,882 B1; 6,308,531 B1; 6,324,867 B1; and 6,347,532 B1 also describe relevant processes. These methods generally include steps in which the natural gas is purified (by removing water and troublesome compounds such as carbon dioxide and sulfur compounds), cooled, condensed, and expanded. Cooling and condensation of the natural gas can be accomplished in many different manners. “Cascade refrigeration” employs heat exchange of the natural gas with several refrigerants having successively lower boiling points, such as propane, ethane, and methane. As an alternative, this heat exchange can be accomplished using a single refrigerant by evaporating the refrigerant at several different pressure levels. “Multi-component refrigeration” employs heat exchange of the natural gas with one or more refrigerant fluids composed of several refrigerant components in lieu of multiple single-component refrigerants. Expansion of the natural gas can be accomplished both isenthalpically (using Joule-Thomson expansion, for instance) and isentropically (using a work-expansion turbine, for instance).
[0008] Regardless of the method used to liquefy the natural gas stream, it is common to require removal of a significant fraction of the hydrocarbons heavier than methane before the methane-rich stream is liquefied. The reasons for this hydrocarbon removal step are numerous, including the need to control the heating value of the LNG stream, and the value of these heavier hydrocarbon components as products in their own right. Unfortunately, little attention has been focused heretofore on the efficiency of the hydrocarbon removal step.
[0009] In accordance with the present invention, it has been found that careful integration of the hydrocarbon removal step into the LNG liquefaction process can produce both LNG and a separate heavier hydrocarbon liquid product using significantly less energy than prior art processes. The present invention, although applicable at lower pressures, is particularly advantageous when processing feed gases in the range of 400 to 1500 psia [2,758 to 10,342 kPa(a)] or higher.
[0010] For a better understanding of the present invention, reference is made to the following examples and drawings. Referring to the drawings:
[0011] FIG. 1 is a flow diagram of a natural gas liquefaction plant adapted for co-production of NGL in accordance with the present invention;
[0012] FIG. 2 is a pressure-enthalpy phase diagram for methane used to illustrate the advantages of the present invention over prior art processes;
[0013] FIG. 3 is a flow diagram of an alternative natural gas liquefaction plant adapted for co-production of NGL in accordance with the present invention;
[0014] FIG. 4 is a flow diagram of an alternative natural gas liquefaction plant adapted for co-production of LPG in accordance with the present invention;
[0015] FIG. 5 is a flow diagram of an alternative natural gas liquefaction plant adapted for co-production of condensate in accordance with the present invention;
[0016] FIG. 6 is a flow diagram of an alternative natural gas liquefaction plant adapted for co-production of a liquid stream in accordance with the present invention;
[0017] FIG. 7 is a flow diagram of an alternative natural gas liquefaction plant adapted for co-production of a liquid stream in accordance with the present invention;
[0018] FIG. 8 is a flow diagram of an alternative natural gas liquefaction plant adapted for co-production of a liquid stream in accordance with the present invention;
[0019] FIG. 9 is a flow diagram of an alternative natural gas liquefaction plant adapted for co-production of a liquid stream in accordance with the present invention;
[0020] FIG. 10 is a flow diagram of an alternative natural gas liquefaction plant adapted for co-production of a liquid stream in accordance with the present invention;
[0021] FIG. 11 is a flow diagram of an alternative natural gas liquefaction plant adapted for co-production of a liquid stream in accordance with the present invention;
[0022] FIG. 12 is a flow diagram of an alternative natural gas liquefaction plant adapted for co-production of a liquid stream in accordance with the present invention;
[0023] FIG. 13 is a flow diagram of an alternative natural gas liquefaction plant adapted for co-production of a liquid stream in accordance with the present invention;
[0024] FIG. 14 is a flow diagram of an alternative natural gas liquefaction plant adapted for co-production of a liquid stream in accordance with the present invention;
[0025] FIG. 15 is a flow diagram of an alternative natural gas liquefaction plant adapted for co-production of a liquid stream in accordance with the present invention;
[0026] FIG. 16 is a flow diagram of an alternative natural gas liquefaction plant adapted for co-production of a liquid stream in accordance with the present invention;
[0027] FIG. 17 is a flow diagram of an alternative natural gas liquefaction plant adapted for co-production of a liquid stream in accordance with the present invention;
[0028] FIG. 18 is a flow diagram of an alternative natural gas liquefaction plant adapted for co-production of a liquid stream in accordance with the present invention;
[0029] FIG. 19 is a flow diagram of an alternative natural gas liquefaction plant adapted for co-production of a liquid stream in accordance with the present invention;
[0030] FIG. 20 is a flow diagram of an alternative natural gas liquefaction plant adapted for co-production of a liquid stream in accordance with the present invention; and
[0031] FIG. 21 is a flow diagram of an alternative natural gas liquefaction plant adapted for co-production of a liquid stream in accordance with the present invention.
[0032] In the following explanation of the above figures, tables are provided summarizing flow rates calculated for representative process conditions. In the tables appearing herein, the values for flow rates (in moles per hour) have been rounded to the nearest whole number for convenience. The total stream rates shown in the tables include all non-hydrocarbon components and hence are generally larger than the sum of the stream flow rates for the hydrocarbon components. Temperatures indicated are approximate values rounded to the nearest degree. It should also be noted that the process design calculations performed for the purpose of comparing the processes depicted in the figures are based on the assumption of no heat leak from (or to) the surroundings to (or from) the process. The quality of commercially available insulating materials makes this a very reasonable assumption and one that is typically made by those skilled in the art.
[0033] For convenience, process parameters are reported in both the traditional British units and in the units of the International System of Units (SI). The molar flow rates given in the tables may be interpreted as either pound moles per hour or kilogram moles per hour. The energy consumptions reported as horsepower (HP) and/or thousand British Thermal Units per hour (MBTU/Hr) correspond to the stated molar flow rates in pound moles per hour. The energy consumptions reported as kilowatts (kW) correspond to the stated molar flow rates in kilogram moles per hour. The production rates reported as pounds per hour (Lb/Hr) correspond to the stated molar flow rates in pound moles per hour. The production rates reported as kilograms per hour (kg/Hr) correspond to the stated molar flow rates in kilogram moles per hour.
DESCRIPTION OF THE INVENTION
Example 1
[0034] Referring now to FIG. 1 , we begin with an illustration of a process in accordance with the present invention where it is desired to produce an NGL co-product containing the majority of the ethane and heavier components in the natural gas feed stream. In this simulation of the present invention, inlet gas enters the plant at 90° F. [32° C.] and 1285 psia [8,860 kPa(a)] as stream 31 . If the inlet gas contains a concentration of carbon dioxide and/or sulfur compounds which would prevent the product streams from meeting specifications, these compounds are removed by appropriate pretreatment of the feed gas (not illustrated). In addition, the feed stream is usually dehydrated to prevent hydrate (ice) formation under cryogenic conditions. Solid desiccant has typically been used for this purpose.
[0035] The feed stream 31 is cooled in heat exchanger 10 by heat exchange with refrigerant streams and demethanizer side reboiler liquids at −68° F. [−55° C.] (stream 40 ). Note that in all cases heat exchanger 10 is representative of either a multitude of individual heat exchangers or a single multi-pass heat exchanger, or any combination thereof. (The decision as to whether to use more than one heat exchanger for the indicated cooling services will depend on a number of factors including, but not limited to, inlet gas flow rate, heat exchanger size, stream temperatures, etc.) The cooled stream 31 a enters separator 11 at −30° F. [−34° C.] and 1278 psia [8,812 kPa(a)] where the vapor (stream 32 ) is separated from the condensed liquid (stream 33 ).
[0036] The vapor (stream 32 ) from separator 11 is divided into two streams, 34 and 36 . Stream 34 , containing about 20% of the total vapor, is combined with the condensed liquid, stream 33 , to form stream 35 . Combined stream 35 passes through heat exchanger 13 in heat exchange relation with refrigerant stream 71 e , resulting in cooling and substantial condensation of stream 35 a . The substantially condensed stream 35 a at −120° F. [−85° C.] is then flash expanded through an appropriate expansion device, such as expansion valve 14 , to the operating pressure (approximately 465 psia [3,206 kPa(a)]) of fractionation tower 19 . During expansion a portion of the stream is vaporized, resulting in cooling of the total stream. In the process illustrated in FIG. 1 , the expanded stream 35 b leaving expansion valve 14 reaches a temperature of −122° F. [−86° C.], and is supplied at a mid-point feed position in demethanizing section 19 b of fractionation tower 19 .
[0037] The remaining 80% of the vapor from separator 11 (stream 36 ) enters a work expansion machine 15 in which mechanical energy is extracted from this portion of the high pressure feed. The machine 15 expands the vapor substantially isentropically from a pressure of about 1278 psia [8,812 kPa(a)] to the tower operating pressure, with the work expansion cooling the expanded stream 36 a to a temperature of approximately −103° F. [−75° C.]. The typical commercially available expanders are capable of recovering on the order of 80-85% of the work theoretically available in an ideal isentropic expansion. The work recovered is often used to drive a centrifugal compressor (such as item 16 ) that can be used to re-compress the tower overhead gas (stream 38 ), for example. The expanded and partially condensed stream 36 a is supplied as feed to distillation column 19 at a lower mid-column feed point.
[0038] The demethanizer in fractionation tower 19 is a conventional distillation column containing a plurality of vertically spaced trays, one or more packed beds, or some combination of trays and packing. As is often the case in natural gas processing plants, the fractionation tower may consist of two sections. The upper section 19 a is a separator wherein the top feed is divided into its respective vapor and liquid portions, and wherein the vapor rising from the lower distillation or demethanizing section 19 b is combined with the vapor portion (if any) of the top feed to form the cold demethanizer overhead vapor (stream 37 ) which exits the top of the tower at −135° F. [−93° C.]. The lower, demethanizing section 19 b contains the trays and/or packing and provides the necessary contact between the liquids falling downward and the vapors rising upward. The demethanizing section also includes one or more reboilers (such as reboiler 20 ) which heat and vaporize a portion of the liquids flowing down the column to provide the stripping vapors which flow up the column. The liquid product stream 41 exits the bottom of the tower at 115° F. [46° C.], based on a typical specification of a methane to ethane ratio of 0.020:1 on a molar basis in the bottom product.
[0039] The demethanizer overhead vapor (stream 37 ) is warmed to 90° F. [32° C.] in heat exchanger 24 , and a portion of the warmed demethanizer overhead vapor is withdrawn to serve as fuel gas (stream 48 ) for the plant. (The amount of fuel gas that must be withdrawn is largely determined by the fuel required for the engines and/or turbines driving the gas compressors in the plant, such as refrigerant compressors 64 , 66 , and 68 in this example.) The remainder of the warmed demethanizer overhead vapor (stream 38 ) is compressed by compressor 16 driven by expansion machines 15 , 61 , and 63 . After cooling to 100° F. [38° C.] in discharge cooler 25 , stream 38 b is further cooled to −123° F. [−86° C.] in heat exchanger 24 by cross exchange with the cold demethanizer overhead vapor, stream 37 .
[0040] Stream 38 c then enters heat exchanger 60 and is further cooled by refrigerant stream 71 d . After cooling to an intermediate temperature, stream 38 c is divided into two portions. The first portion, stream 49 , is further cooled in heat exchanger 60 to −257° F. [− 160 C] to condense and subcool it, whereupon it enters a work expansion machine 61 in which mechanical energy is extracted from the stream. The machine 61 expands liquid stream 49 substantially isentropically from a pressure of about 562 psia [3,878 kPa(a)] to the LNG storage pressure (15.5 psia [107 kPa(a)]), slightly above atmospheric pressure. The work expansion cools the expanded stream 49 a to a temperature of approximately −258° F. [−161° C.], whereupon it is then directed to the LNG storage tank 62 which holds the LNG product (stream 50 ).
[0041] Stream 39 , the other portion of stream 38 c , is withdrawn from heat exchanger 60 at −160° F. [−107° C.] and flash expanded through an appropriate expansion device, such as expansion valve 17 , to the operating pressure of fractionation tower 19 . In the process illustrated in FIG. 1 , there is no vaporization in expanded stream 39 a , so its temperature drops only slightly to −161° F. [−107° C.] leaving expansion valve 17 . The expanded stream 39 a is then supplied to separator section 19 a in the upper region of fractionation tower 19 . The liquids separated therein become the top feed to demethanizing section 19 b.
[0042] All of the cooling for streams 35 and 38 c is provided by a closed cycle refrigeration loop. The working fluid for this cycle is a mixture of hydrocarbons and nitrogen, with the composition of the mixture adjusted as needed to provide the required refrigerant temperature while condensing at a reasonable pressure using the available cooling medium. In this case, condensing with cooling water has been assumed, so a refrigerant mixture composed of nitrogen, methane, ethane, propane, and heavier hydrocarbons is used in the simulation of the FIG. 1 process. The composition of the stream, in approximate mole percent, is 7.5% nitrogen, 41.0% methane, 41.5% ethane, and 10.0% propane, with the balance made up of heavier hydrocarbons.
[0043] The refrigerant stream 71 leaves discharge cooler 69 at 1001° F. [38° C.] and 607 psia [4,185 kPa(a)]. It enters heat exchanger 10 and is cooled to −31° F. [−35° C.] and partially condensed by the partially warmed expanded refrigerant stream 71 f and by other refrigerant streams. For the FIG. 1 simulation, it has been assumed that these other refrigerant streams are commercial-quality propane refrigerant at three different temperature and pressure levels. The partially condensed refrigerant stream 71 a then enters heat exchanger 13 for further cooling to −114° F. [−81° C.] by partially warmed expanded refrigerant stream 71 e , condensing and partially subcooling the refrigerant (stream 71 b ). The refrigerant is further subcooled to −257° F. [−160° C.] in heat exchanger 60 by expanded refrigerant stream 71 d . The subcooled liquid stream 71 c enters a work expansion machine 63 in which mechanical energy is extracted from the stream as it is expanded substantially isentropically from a pressure of about 586 psia [4,040 kPa(a)] to about 34 psia [234 kPa(a)]. During expansion a portion of the stream is vaporized, resulting in cooling of the total stream to −263° F. [−164° C.] (stream 71 d ). The expanded stream 71 d then reenters heat exchangers 60 , 13 , and 10 where it provides cooling to stream 38 c , stream 35 , and the refrigerant (streams 71 , 71 a , and 71 b ) as it is vaporized and superheated.
[0044] The superheated refrigerant vapor (stream 71 g ) leaves heat exchanger 10 at 93° F. [34° C.] and is compressed in three stages to 617 psia [4,254 kPa(a)]. Each of the three compression stages (refrigerant compressors 64 , 66 , and 68 ) is driven by a supplemental power source and is followed by a cooler (discharge coolers 65 , 67 , and 69 ) to remove the heat of compression. The compressed stream 71 from discharge cooler 69 returns to heat exchanger 10 to complete the cycle.
[0045] A summary of stream flow rates and energy consumption for the process illustrated in FIG. 1 is set forth in the following table:
[0000]
TABLE I
(FIG. 1)
Stream Flow Summary - Lb. Moles/Hr [kg moles/Hr]
Stream
Methane
Ethane
Propane
Butanes+
Total
31
40,977
3,861
2,408
1,404
48,656
32
32,360
2,675
1,469
701
37,209
33
8,617
1,186
939
703
11,447
34
6,472
535
294
140
7,442
36
25,888
2,140
1,175
561
29,767
37
47,771
223
0
0
48,000
39
6,867
32
0
0
6,900
41
73
3,670
2,408
1,404
7,556
48
3,168
15
0
0
3,184
50
37,736
176
0
0
37,916
Recoveries in NGL*
Ethane
95.06%
Propane
100.00%
Butanes+
100.00%
Production Rate
308,147
Lb/Hr
[308,147
kg/Hr]
LNG Product
Production Rate
610,813
Lb/Hr
[610,813
kg/Hr]
Purity*
99.52%
Lower Heating Value
912.3
BTU/SCF
[33.99
MJ/m 3 ]
Power
Refrigerant Compression
103,957
HP
[170,904
kW]
Propane Compression
33,815
HP
[55,591
kW]
Total Compression
137,772
HP
[226,495
kW]
Utility Heat
Demethanizer Reboiler
29,364
MBTU/Hr
[18,969
kW]
*(Based on un-rounded flow rates)
[0046] The efficiency of LNG production processes is typically compared using the “specific power consumption” required, which is the ratio of the total refrigeration compression power to the total liquid production rate. Published information on the specific power consumption for prior art processes for producing LNG indicates a range of 0.168 HP-Hr/Lb [0.276 kW-Hr/kg] to 0.182 HP-Hr/Lb [0.300 kW-Hr/kg], which is believed to be based on an on-stream factor of 340 days per year for the LNG production plant. On this same basis, the specific power consumption for the FIG. 1 embodiment of the present invention is 0.161 HP-Hr/Lb [0.265 kW-Hr/kg], which gives an efficiency improvement of 4-13% over the prior art processes. Further, it should be noted that the specific power consumption for the prior art processes is based on co-producing only an LPG (C 3 and heavier hydrocarbons) or condensate (C 4 and heavier hydrocarbons) liquid stream at relatively low recovery levels, not an NGL (C 2 and heavier hydrocarbons) liquid stream as shown for this example of the present invention. The prior art processes require considerably more refrigeration power to co-produce an NGL stream instead of an LPG stream or a condensate stream.
[0047] There are two primary factors that account for the improved efficiency of the present invention. The first factor can be understood by examining the thermodynamics of the liquefaction process when applied to a high pressure gas stream such as that considered in this example. Since the primary constituent of this stream is methane, the thermodynamic properties of methane can be used for the purposes of comparing the liquefaction cycle employed in the prior art processes versus the cycle used in the present invention. FIG. 2 contains a pressure-enthalpy phase diagram for methane. In most of the prior art liquefaction cycles, all cooling of the gas stream is accomplished while the stream is at high pressure (path A-B), whereupon the stream is then expanded (path B-C) to the pressure of the LNG storage vessel (slightly above atmospheric pressure). This expansion step may employ a work expansion machine, which is typically capable of recovering on the order of 75-80% of the work theoretically available in an ideal isentropic expansion. In the interest of simplicity, fully isentropic expansion is displayed in FIG. 2 for path B-C. Even so, the enthalpy reduction provided by this work expansion is quite small, because the lines of constant entropy are nearly vertical in the liquid region of the phase diagram.
[0048] Contrast this now with the liquefaction cycle of the present invention. After partial cooling at high pressure (path A-A′), the gas stream is work expanded (path A′-A″) to an intermediate pressure. (Again, fully isentropic expansion is displayed in the interest of simplicity.) The remainder of the cooling is accomplished at the intermediate pressure (path A″-B′), and the stream is then expanded (path B′-C) to the pressure of the LNG storage vessel. Since the lines of constant entropy slope less steeply in the vapor region of the phase diagram, a significantly larger enthalpy reduction is provided by the first work expansion step (path A′-A″) of the present invention. Thus, the total amount of cooling required for the present invention (the sum of paths A-A′ and A″-B′) is less than the cooling required for the prior art processes (path A-B), reducing the refrigeration (and hence the refrigeration compression) required to liquefy the gas stream.
[0049] The second factor accounting for the improved efficiency of the present invention is the superior performance of hydrocarbon distillation systems at lower operating pressures. The hydrocarbon removal step in most of the prior art processes is performed at high pressure, typically using a scrub column that employs a cold hydrocarbon liquid as the absorbent stream to remove the heavier hydrocarbons from the incoming gas stream. Operating the scrub column at high pressure is not very efficient, as it results in the co-absorption of a significant fraction of the methane and ethane from the gas stream, which must subsequently be stripped from the absorbent liquid and cooled to become part of the LNG product. In the present invention, the hydrocarbon removal step is conducted at the intermediate pressure where the vapor-liquid equilibrium is much more favorable, resulting in very efficient recovery of the desired heavier hydrocarbons in the co-product liquid stream.
Example 2
[0050] If the specifications for the LNG product will allow more of the ethane contained in the feed gas to be recovered in the LNG product, a simpler embodiment of the present invention may be employed. FIG. 3 illustrates such an alternative embodiment. The inlet gas composition and conditions considered in the process presented in FIG. 3 are the same as those in FIG. 1 . Accordingly, the FIG. 3 process can be compared to the embodiment displayed in FIG. 1 .
[0051] In the simulation of the FIG. 3 process, the inlet gas cooling, separation, and expansion scheme for the NGL recovery section is essentially the same as that used in FIG. 1 . Inlet gas enters the plant at 90° F. [32° C.] and 1285 psia [8,860 kPa(a)] as stream 31 and is cooled in heat exchanger 10 by heat exchange with refrigerant streams and demethanizer side reboiler liquids at −35° F. [−37° C.] (stream 40 ). The cooled stream 31 a enters separator 11 at −30° F. [−34° C.] and 1278 psia [8,812 kPa(a)] where the vapor (stream 32 ) is separated from the condensed liquid (stream 33 ).
[0052] The vapor (stream 32 ) from separator 11 is divided into two streams, 34 and 36 . Stream 34 , containing about 20% of the total vapor, is combined with the condensed liquid, stream 33 , to form stream 35 . Combined stream 35 passes through heat exchanger 13 in heat exchange relation with refrigerant stream 71 e , resulting in cooling and substantial condensation of stream 35 a . The substantially condensed stream 35 a at −120° F. [−85° C.] is then flash expanded through an appropriate expansion device, such as expansion valve 14 , to the operating pressure (approximately 465 psia [3,206 kPa(a)]) of fractionation tower 19 . During expansion a portion of the stream is vaporized, resulting in cooling of the total stream. In the process illustrated in FIG. 3 , the expanded stream 35 b leaving expansion valve 14 reaches a temperature of −122° F. [−86° C.], and is supplied to the separator section in the upper region of fractionation tower 19 . The liquids separated therein become the top feed to the demethanizing section in the lower region of fractionation tower 19 .
[0053] The remaining 80% of the vapor from separator 11 (stream 36 ) enters a work expansion machine 15 in which mechanical energy is extracted from this portion of the high pressure feed. The machine 15 expands the vapor substantially isentropically from a pressure of about 1278 psia [8,812 kPa(a)] to the tower operating pressure, with the work expansion cooling the expanded stream 36 a to a temperature of approximately −103° F. [−75° C.]. The expanded and partially condensed stream 36 a is supplied as feed to distillation column 19 at a mid-column feed point.
[0054] The cold demethanizer overhead vapor (stream 37 ) exits the top of fractionation tower 19 at −123° F. [−86° C.]. The liquid product stream 41 exits the bottom of the tower at 118° F. [48° C.], based on a typical specification of a methane to ethane ratio of 0.020:1 on a molar basis in the bottom product.
[0055] The demethanizer overhead vapor (stream 37 ) is warmed to 90° F. [32° C.] in heat exchanger 24 , and a portion (stream 48 ) is then withdrawn to serve as fuel gas for the plant. The remainder of the warmed demethanizer overhead vapor (stream 49 ) is compressed by compressor 16 . After cooling to 100° F. [38° C.] in discharge cooler 25 , stream 49 b is further cooled to −12° F. [−80° C.] in heat exchanger 24 by cross exchange with the cold demethanizer overhead vapor, stream 37 .
[0056] Stream 49 c then enters heat exchanger 60 and is further cooled by refrigerant stream 71 d to −257° F. [−160° C.] to condense and subcool it, whereupon it enters a work expansion machine 61 in which mechanical energy is extracted from the stream. The machine 61 expands liquid stream 49 d substantially isentropically from a pressure of about 583 psia [4,021 kPa(a)] to the LNG storage pressure (15.5 psia [107 kPa(a)]), slightly above atmospheric pressure. The work expansion cools the expanded stream 49 e to a temperature of approximately −258° F. [−161° C.], whereupon it is then directed to the LNG storage tank 62 which holds the LNG product (stream 50 ).
[0057] Similar to the FIG. 1 process, all of the cooling for streams 35 and 49 c is provided by a closed cycle refrigeration loop. The composition of the stream used as the working fluid in the cycle for the FIG. 3 process, in approximate mole percent, is 7.5% nitrogen, 40.0% methane, 42.5% ethane, and 10.0% propane, with the balance made up of heavier hydrocarbons. The refrigerant stream 71 leaves discharge cooler 69 at 100° F. [38° C.] and 607 psia [4,185 kPa(a)]. It enters heat exchanger 10 and is cooled to −31° F. [−35° C.] and partially condensed by the partially warmed expanded refrigerant stream 71 f and by other refrigerant streams. For the FIG. 3 simulation, it has been assumed that these other refrigerant streams are commercial-quality propane refrigerant at three different temperature and pressure levels. The partially condensed refrigerant stream 71 a then enters heat exchanger 13 for further cooling to −121° F. [−85° C.] by partially warmed expanded refrigerant stream 71 e , condensing and partially subcooling the refrigerant (stream 71 b ). The refrigerant is further subcooled to −257° F. [−160° C.] in heat exchanger 60 by expanded refrigerant stream 71 d . The subcooled liquid stream 71 c enters a work expansion machine 63 in which mechanical energy is extracted from the stream as it is expanded substantially isentropically from a pressure of about 586 psia [4,040 kPa(a)] to about 34 psia [234 kPa(a)]. During expansion a portion of the stream is vaporized, resulting in cooling of the total stream to −263° F. [−164° C.] (stream 71 d ). The expanded stream 71 d then reenters heat exchangers 60 , 13 , and 10 where it provides cooling to stream 49 c , stream 35 , and the refrigerant (streams 71 , 71 a , and 71 b ) as it is vaporized and superheated.
[0058] The superheated refrigerant vapor (stream 71 g ) leaves heat exchanger 10 at 93° F. [34° C.] and is compressed in three stages to 617 psia [4,254 kPa(a)]. Each of the three compression stages (refrigerant compressors 64 , 66 , and 68 ) is driven by a supplemental power source and is followed by a cooler (discharge coolers 65 , 67 , and 69 ) to remove the heat of compression. The compressed stream 71 from discharge cooler 69 returns to heat exchanger 10 to complete the cycle.
[0059] A summary of stream flow rates and energy consumption for the process illustrated in FIG. 3 is set forth in the following table:
[0000]
TABLE II
(FIG. 3)
Stream Flow Summary - Lb. Moles/Hr [kg moles/Hr]
Stream
Methane
Ethane
Propane
Butanes+
Total
31
40,977
3,861
2,408
1,404
48,656
32
32,360
2,675
1,469
701
37,209
33
8,617
1,186
939
703
11,447
34
6,472
535
294
140
7,442
36
25,888
2,140
1,175
561
29,767
37
40,910
480
62
7
41,465
41
67
3,381
2,346
1,397
7,191
48
2,969
35
4
0
3,009
50
37,941
445
58
7
38,456
Recoveries in NGL*
Ethane
87.57%
Propane
97.41%
Butanes+
99.47%
Production Rate
296,175
Lb/Hr
[296,175
kg/Hr]
LNG Product
Production Rate
625,152
Lb/Hr
[625,152
kg/Hr]
Purity*
98.66%
Lower Heating Value
919.7
BTU/SCF
[34.27
MJ/m 3 ]
Power
Refrigerant Compression
96,560
HP
[158,743
kW]
Propane Compression
34,724
HP
[57,086
kW]
Total Compression
131,284
HP
[215,829
kW]
Utility Heat
Demethanizer Reboiler
22,177
MBTU/Hr
[14,326
kW]
*(Based on un-rounded flow rates)
[0060] Assuming an on-stream factor of 340 days per year for the LNG production plant, the specific power consumption for the FIG. 3 embodiment of the present invention is 0.153 HP-Hr/Lb [0.251 kW-Hr/kg]. Compared to the prior art processes, the efficiency improvement is 10-20% for the FIG. 3 embodiment. As noted earlier for the FIG. 1 embodiment, this efficiency improvement is possible with the present invention even though an NGL co-product is produced rather than the LPG or condensate co-product produced by the prior art processes.
[0061] Compared to the FIG. 1 embodiment, the FIG. 3 embodiment of the present invention requires about 5% less power per unit of liquid produced. Thus, for a given amount of available compression power, the FIG. 3 embodiment could liquefy about 5% more natural gas than the FIG. 1 embodiment by virtue of recovering less of the C 2 and heavier hydrocarbons in the NGL co-product. The choice between the FIG. 1 and the FIG. 3 embodiments of the present invention for a particular application will generally be dictated either by the monetary value of the heavier hydrocarbons in the NGL product versus their corresponding value in the LNG product, or by the heating value specification for the LNG product (since the heating value of the LNG produced by the FIG. 1 embodiment is lower than that produced by the FIG. 3 embodiment).
Example 3
[0062] If the specifications for the LNG product will allow all of the ethane contained in the feed gas to be recovered in the LNG product, or if there is no market for a liquid co-product containing ethane, an alternative embodiment of the present invention such as that shown in FIG. 4 may be employed to produce an LPG co-product stream. The inlet gas composition and conditions considered in the process presented in FIG. 4 are the same as those in FIGS. 1 and 3 . Accordingly, the FIG. 4 process can be compared to the embodiments displayed in FIGS. 1 and 3 .
[0063] In the simulation of the FIG. 4 process, inlet gas enters the plant at 90° F. [32° C.] and 1285 psia [8,860 kPa(a)] as stream 31 and is cooled in heat exchanger 10 by heat exchange with refrigerant streams and flashed separator liquids at −46° F. [−43° C.] (stream 33 a ). The cooled stream 31 a enters separator 11 at −1° F. [−18° C.] and 1278 psia [8,812 kPa(a)] where the vapor (stream 32 ) is separated from the condensed liquid (stream 33 ).
[0064] The vapor (stream 32 ) from separator 11 enters work expansion machine 15 in which mechanical energy is extracted from this portion of the high pressure feed. The machine 15 expands the vapor substantially isentropically from a pressure of about 1278 psia [8,812 kPa(a)] to a pressure of about 440 psia [3,034 kPa(a)] (the operating pressure of separator/absorber tower 18 ), with the work expansion cooling the expanded stream 32 a to a temperature of approximately −81° F. [−63° C.]. The expanded and partially condensed stream 32 a is supplied to absorbing section 18 b in a lower region of separator/absorber tower 18 . The liquid portion of the expanded stream commingles with liquids falling downward from the absorbing section and the combined liquid stream 40 exits the bottom of separator/absorber tower 18 at −86° F. [−66° C.]. The vapor portion of the expanded stream rises upward through the absorbing section and is contacted with cold liquid falling downward to condense and absorb the C 3 components and heavier components.
[0065] The separator/absorber tower 18 is a conventional distillation column containing a plurality of vertically spaced trays, one or more packed beds, or some combination of trays and packing. As is often the case in natural gas processing plants, the separator/absorber tower may consist of two sections. The upper section 18 a is a separator wherein any vapor contained in the top feed is separated from its corresponding liquid portion, and wherein the vapor rising from the lower distillation or absorbing section 18 b is combined with the vapor portion (if any) of the top feed to form the cold distillation stream 37 which exits the top of the tower. The lower, absorbing section 18 b contains the trays and/or packing and provides the necessary contact between the liquids falling downward and the vapors rising upward to condense and absorb the C 3 components and heavier components.
[0066] The combined liquid stream 40 from the bottom of separator/absorber tower 18 is routed to heat exchanger 13 by pump 26 where it (stream 40 a ) is heated as it provides cooling of deethanizer overhead (stream 42 ) and refrigerant (stream 71 a ). The combined liquid stream is heated to −24° F. [−31 31C], partially vaporizing stream 40 b before it is supplied as a mid-column feed to deethanizer 19 . The separator liquid (stream 33 ) is flash expanded to slightly above the operating pressure of deethanizer 19 by expansion valve 12 , cooling stream 33 to −46° F. [−43° C.] (stream 33 a ) before it provides cooling to the incoming feed gas as described earlier. Stream 33 b , now at 85° F. [29° C.], then enters deethanizer 19 at a lower mid-column feed point. In the deethanizer, streams 40 b and 33 b are stripped of their methane and C 2 components. The deethanizer in tower 19 , operating at about 453 psia [3,123 kPa(a)], is also a conventional distillation column containing a plurality of vertically spaced trays, one or more packed beds, or some combination of trays and packing. The deethanizer tower may also consist of two sections: an upper separator section 19 a wherein any vapor contained in the top feed is separated from its corresponding liquid portion, and wherein the vapor rising from the lower distillation or deethanizing section 19 b is combined with the vapor portion (if any) of the top feed to form distillation stream 42 which exits the top of the tower; and a lower, deethanizing section 19 b that contains the trays and/or packing to provide the necessary contact between the liquids falling downward and the vapors rising upward. The deethanizing section 19 b also includes one or more reboilers (such as reboiler 20 ) which heat and vaporize a portion of the liquid at the bottom of the column to provide the stripping vapors which flow up the column to strip the liquid product, stream 41 , of methane and C 2 components. A typical specification for the bottom liquid product is to have an ethane to propane ratio of 0.020:1 on a molar basis. The liquid product stream 41 exits the bottom of the deethanizer at 214° F. [101 C].
[0067] The operating pressure in deethanizer 19 is maintained slightly above the operating pressure of separator/absorber tower 18 . This allows the deethanizer overhead vapor (stream 42 ) to pressure flow through heat exchanger 13 and thence into the upper section of separator/absorber tower 18 . In heat exchanger 13 , the deethanizer overhead at −19° F. [−28° C.] is directed in heat exchange relation with the combined liquid stream (stream 40 a ) from the bottom of separator/absorber tower 18 and flashed refrigerant stream 71 e , cooling the stream to −89° F. [−67° C.] (stream 42 a ) and partially condensing it. The partially condensed stream enters reflux drum 22 where the condensed liquid (stream 44 ) is separated from the uncondensed vapor (stream 43 ). Stream 43 combines with the distillation vapor stream (stream 37 ) leaving the upper region of separator/absorber tower 18 to form cold residue gas stream 47 . The condensed liquid (stream 44 ) is pumped to higher pressure by pump 23 , whereupon stream 44 a is divided into two portions. One portion, stream 45 , is routed to the upper separator section of separator/absorber tower 18 to serve as the cold liquid that contacts the vapors rising upward through the absorbing section. The other portion is supplied to deethanizer 19 as reflux stream 46 , flowing to a top feed point on deethanizer 19 at −89° F. [−67° C.].
[0068] The cold residue gas (stream 47 ) is warmed from −94° F. [−70° C.] to 94° F. [34° C.] in heat exchanger 24 , and a portion (stream 48 ) is then withdrawn to serve as fuel gas for the plant. The remainder of the warmed residue gas (stream 49 ) is compressed by compressor 16 . After cooling to 100° F. [38° C.] in discharge cooler 25 , stream 49 b is further cooled to −78° F. [−61° C.] in heat exchanger 24 by cross exchange with the cold residue gas, stream 47 .
[0069] Stream 49 c then enters heat exchanger 60 and is further cooled by refrigerant stream 71 d to −255° F. [−160° C.] to condense and subcool it, whereupon it enters a work expansion machine 61 in which mechanical energy is extracted from the stream. The machine 61 expands liquid stream 49 d substantially isentropically from a pressure of about 648 psia [4,465 kPa(a)] to the LNG storage pressure (15.5 psia [107 kPa(a)]), slightly above atmospheric pressure. The work expansion cools the expanded stream 49 e to a temperature of approximately −256° F. [−160° C.], whereupon it is then directed to the LNG storage tank 62 which holds the LNG product (stream 50 ).
[0070] Similar to the FIG. 1 and FIG. 3 processes, much of the cooling for stream 42 and all of the cooling for stream 49 c is provided by a closed cycle refrigeration loop. The composition of the stream used as the working fluid in the cycle for the FIG. 4 process, in approximate mole percent, is 8.7% nitrogen, 30.0% methane, 45.8% ethane, and 11.0% propane, with the balance made up of heavier hydrocarbons. The refrigerant stream 71 leaves discharge cooler 69 at 100° F. [38° C.] and 607 psia [4,185 kPa(a)]. It enters heat exchanger 10 and is cooled to −17° F. [−27° C.] and partially condensed by the partially warmed expanded refrigerant stream 71 f and by other refrigerant streams. For the FIG. 4 simulation, it has been assumed that these other refrigerant streams are commercial-quality propane refrigerant at three different temperature and pressure levels. The partially condensed refrigerant stream 71 a then enters heat exchanger 13 for further cooling to −89° F. [−67° C.] by partially warmed expanded refrigerant stream 71 e , further condensing the refrigerant (stream 71 b ). The refrigerant is totally condensed and then subcooled to −255° F. [−160° C.] in heat exchanger 60 by expanded refrigerant stream 71 d . The subcooled liquid stream 71 c enters a work expansion machine 63 in which mechanical energy is extracted from the stream as it is expanded substantially isentropically from a pressure of about 586 psia [4,040 kPa(a)] to about 34 psia [234 kPa(a)]. During expansion a portion of the stream is vaporized, resulting in cooling of the total stream to −264° F. [−164° C.] (stream 71 d ). The expanded stream 71 d then reenters heat exchangers 60 , 13 , and 10 where it provides cooling to stream 49 c , stream 42 , and the refrigerant (streams 71 , 71 a , and 71 b ) as it is vaporized and superheated.
[0071] The superheated refrigerant vapor (stream 71 g ) leaves heat exchanger 10 at 90° F. [32° C.] and is compressed in three stages to 617 psia [4,254 kPa(a)]. Each of the three compression stages (refrigerant compressors 64 , 66 , and 68 ) is driven by a supplemental power source and is followed by a cooler (discharge coolers 65 , 67 , and 69 ) to remove the heat of compression. The compressed stream 71 from discharge cooler 69 returns to heat exchanger 10 to complete the cycle.
[0072] A summary of stream flow rates and energy consumption for the process illustrated in FIG. 4 is set forth in the following table:
[0000]
TABLE III
(FIG. 4)
Stream Flow Summary - Lb. Moles/Hr [kg moles/Hr]
Stream
Methane
Ethane
Propane
Butanes+
Total
31
40,977
3,861
2,408
1,404
48,656
32
38,431
3,317
1,832
820
44,405
33
2,546
544
576
584
4,251
37
36,692
3,350
19
0
40,066
40
5,324
3,386
1,910
820
11,440
41
0
48
2,386
1,404
3,837
42
10,361
6,258
168
0
16,789
43
4,285
463
3
0
4,753
44
6,076
5,795
165
0
12,036
45
3,585
3,419
97
0
7,101
46
2,491
2,376
68
0
4,935
47
40,977
3,813
22
0
44,819
48
2,453
228
1
0
2,684
50
38,524
3,585
21
0
42,135
Recoveries in LPG*
Propane
99.08%
Butanes+
100.00%
Production Rate
197,051
Lb/Hr
[197,051
kg/Hr]
LNG Product
Production Rate
726,918
Lb/Hr
[726,918
kg/Hr]
Purity*
91.43%
Lower Heating Value
969.9
BTU/SCF
[36.14
MJ/m 3 ]
Power
Refrigerant Compression
95,424
HP
[156,876
kW]
Propane Compression
28,060
HP
[46,130
kW]
Total Compression
123,484
HP
[203,006
kW]
Utility Heat
Demethanizer Reboiler
55,070
MBTU/Hr
[35,575
kW]
*(Based on un-rounded flow rates)
[0073] Assuming an on-stream factor of 340 days per year for the LNG production plant, the specific power consumption for the FIG. 4 embodiment of the present invention is 0.143 HP-Hr/Lb [0.236 kW-Hr/kg]. Compared to the prior art processes, the efficiency improvement is 17-27% for the FIG. 4 embodiment.
[0074] Compared to the FIG. 1 and FIG. 3 embodiments, the FIG. 4 embodiment of the present invention requires 6% to 11% less power per unit of liquid produced. Thus, for a given amount of available compression power, the FIG. 4 embodiment could liquefy about 6% more natural gas than the FIG. 1 embodiment or about 11% more natural gas than the FIG. 3 embodiment by virtue of recovering only the C 3 and heavier hydrocarbons as an LPG co-product. The choice between the FIG. 4 embodiment versus either the FIG. 1 or FIG. 3 embodiments of the present invention for a particular application will generally be dictated either by the monetary value of ethane as part of an NGL product versus its corresponding value in the LNG product, or by the heating value specification for the LNG product (since the heating value of the LNG produced by the FIG. 1 and FIG. 3 embodiments is lower than that produced by the FIG. 4 embodiment).
Example 4
[0075] If the specifications for the LNG product will allow all of the ethane and propane contained in the feed gas to be recovered in the LNG product, or if there is no market for a liquid co-product containing ethane and propane, an alternative embodiment of the present invention such as that shown in FIG. 5 may be employed to produce a condensate co-product stream. The inlet gas composition and conditions considered in the process presented in FIG. 5 are the same as those in FIGS. 1 , 3 , and 4 . Accordingly, the FIG. 5 process can be compared to the embodiments displayed in FIGS. 1 , 3 , and 4 .
[0076] In the simulation of the FIG. 5 process, inlet gas enters the plant at 90° F. [32° C.] and 1285 psia [8,860 kPa(a)] as stream 31 and is cooled in heat exchanger 10 by heat exchange with refrigerant streams, flashed high pressure separator liquids at −37° F. [−38° C.] (stream 33 b ), and flashed intermediate pressure separator liquids at −37° F. [−38° C.] (stream 39 b ). The cooled stream 31 a enters high pressure separator 11 at −30° F. [−34° C.] and 1278 psia [8,812 kPa(a)] where the vapor (stream 32 ) is separated from the condensed liquid (stream 33 ).
[0077] The vapor (stream 32 ) from high pressure separator 11 enters work expansion machine 15 in which mechanical energy is extracted from this portion of the high pressure feed. The machine 15 expands the vapor substantially isentropically from a pressure of about 1278 psia [8,812 kPa(a)] to a pressure of about 635 psia [4,378 kPa(a)], with the work expansion cooling the expanded stream 32 a to a temperature of approximately −83° F. [−64° C.]. The expanded and partially condensed stream 32 a enters intermediate pressure separator 18 where the vapor (stream 42 ) is separated from the condensed liquid (stream 39 ). The intermediate pressure separator liquid (stream 39 ) is flash expanded to slightly above the operating pressure of depropanizer 19 by expansion valve 17 , cooling stream 39 to −108° F. [−78° C.] (stream 39 a ) before it enters heat exchanger 13 and is heated as it provides cooling to residue gas stream 49 and refrigerant stream 71 a , and thence to heat exchanger 10 to provide cooling to the incoming feed gas as described earlier. Stream 39 c , now at −15° F. [−26° C.], then enters depropanizer 19 at an upper mid-column feed point.
[0078] The condensed liquid, stream 33 , from high pressure separator 11 is flash expanded to slightly above the operating pressure of depropanizer 19 by expansion valve 12 , cooling stream 33 to −93° F. [−70° C.] (stream 33 a ) before it enters heat exchanger 13 and is heated as it provides cooling to residue gas stream 49 and refrigerant stream 71 a , and thence to heat exchanger 10 to provide cooling to the incoming feed gas as described earlier. Stream 33 c , now at 50° F. [10° C.], then enters depropanizer 19 at a lower mid-column feed point. In the depropanizer, streams 39 c and 33 c are stripped of their methane, C 2 components, and C 3 components. The depropanizer in tower 19 , operating at about 385 psia [2,654 kPa(a)], is a conventional distillation column containing a plurality of vertically spaced trays, one or more packed beds, or some combination of trays and packing. The depropanizer tower may consist of two sections: an upper separator section 19 a wherein any vapor contained in the top feed is separated from its corresponding liquid portion, and wherein the vapor rising from the lower distillation or depropanizing section 19 b is combined with the vapor portion (if any) of the top feed to form distillation stream 37 which exits the top of the tower; and a lower, depropanizing section 19 b that contains the trays and/or packing to provide the necessary contact between the liquids falling downward and the vapors rising upward. The depropanizing section 19 b also includes one or more reboilers (such as reboiler 20 ) which heat and vaporize a portion of the liquid at the bottom of the column to provide the stripping vapors which flow up the column to strip the liquid product, stream 41 , of methane, C 2 components, and C 3 components. A typical specification for the bottom liquid product is to have a propane to butanes ratio of 0.020:1 on a volume basis. The liquid product stream 41 exits the bottom of the deethanizer at 286° F. [141° C.].
[0079] The overhead distillation stream 37 leaves depropanizer 19 at 36° F. [2° C.] and is cooled and partially condensed by commercial-quality propane refrigerant in reflux condenser 21 . The partially condensed stream 37 a enters reflux drum 22 at 2° F. [−17° C.] where the condensed liquid (stream 44 ) is separated from the uncondensed vapor (stream 43 ). The condensed liquid (stream 44 ) is pumped by pump 23 to a top feed point on depropanizer 19 as reflux stream 44 a.
[0080] The uncondensed vapor (stream 43 ) from reflux drum 22 is warmed to 94° F. [34° C.] in heat exchanger 24 , and a portion (stream 48 ) is then withdrawn to serve as fuel gas for the plant. The remainder of the warmed vapor (stream 38 ) is compressed by compressor 16 . After cooling to 100° F. [38° C.] in discharge cooler 25 , stream 38 b is further cooled to 15° F. [−9° C.] in heat exchanger 24 by cross exchange with the cool vapor, stream 43 .
[0081] Stream 38 c then combines with the intermediate pressure separator vapor (stream 42 ) to form cool residue gas stream 49 . Stream 49 enters heat exchanger 13 and is cooled from −38° F. [−39° C.] to −102° F. [−74° C.] by separator liquids (streams 39 a and 33 a ) as described earlier and by refrigerant stream 71 e . Partially condensed stream 49 a then enters heat exchanger 60 and is further cooled by refrigerant stream 71 d to −254° F. [−159° C.] to condense and subcool it, whereupon it enters a work expansion machine 61 in which mechanical energy is extracted from the stream. The machine 61 expands liquid stream 49 b substantially isentropically from a pressure of about 621 psia [4,282 kPa(a)] to the LNG storage pressure (15.5 psia [107 kPa(a)]), slightly above atmospheric pressure. The work expansion cools the expanded stream 49 c to a temperature of approximately −255° F. [−159° C.], whereupon it is then directed to the LNG storage tank 62 which holds the LNG product (stream 50 ).
[0082] Similar to the FIG. 1 , FIG. 3 , and FIG. 4 processes, much of the cooling for stream 49 and all of the cooling for stream 49 a is provided by a closed cycle refrigeration loop. The composition of the stream used as the working fluid in the cycle for the FIG. 5 process, in approximate mole percent, is 8.9% nitrogen, 34.3% methane, 41.3% ethane, and 11.0% propane, with the balance made up of heavier hydrocarbons. The refrigerant stream 71 leaves discharge cooler 69 at 100° F. [38° C.] and 607 psia [4,185 kPa(a)]. It enters heat exchanger 10 and is cooled to −30° F. [−34° C.] and partially condensed by the partially warmed expanded refrigerant stream 71 f and by other refrigerant streams. For the FIG. 5 simulation, it has been assumed that these other refrigerant streams are commercial-quality propane refrigerant at three different temperature and pressure levels. The partially condensed refrigerant stream 71 a then enters heat exchanger 13 for further cooling to −102° F. [−74° C.] by partially warmed expanded refrigerant stream 71 e , further condensing the refrigerant (stream 71 b ). The refrigerant is totally condensed and then subcooled to −254° F. [−159° C.] in heat exchanger 60 by expanded refrigerant stream 71 d . The subcooled liquid stream 71 c enters a work expansion machine 63 in which mechanical energy is extracted from the stream as it is expanded substantially isentropically from a pressure of about 586 psia [4,040 kPa(a)] to about 34 psia [234 kPa(a)]. During expansion a portion of the stream is vaporized, resulting in cooling of the total stream to −264° F. [−164° C.] (stream 71 d ). The expanded stream 71 d then reenters heat exchangers 60 , 13 , and 10 where it provides cooling to stream 49 a , stream 49 , and the refrigerant (streams 71 , 71 a , and 71 b ) as it is vaporized and superheated.
[0083] The superheated refrigerant vapor (stream 71 g ) leaves heat exchanger 10 at 93° F. [34° C.] and is compressed in three stages to 617 psia [4,254 kPa(a)]. Each of the three compression stages (refrigerant compressors 64 , 66 , and 68 ) is driven by a supplemental power source and is followed by a cooler (discharge coolers 65 , 67 , and 69 ) to remove the heat of compression. The compressed stream 71 from discharge cooler 69 returns to heat exchanger 10 to complete the cycle.
[0084] A summary of stream flow rates and energy consumption for the process illustrated in FIG. 5 is set forth in the following table:
[0000]
TABLE IV
(FIG. 5)
Stream Flow Summary - Lb. Moles/Hr [kg moles/Hr]
Stream
Methane
Ethane
Propane
Butanes+
Total
31
40,977
3,861
2,408
1,404
48,656
32
32,360
2,675
1,469
701
37,209
33
8,617
1,186
939
703
11,447
38
13,133
2,513
1,941
22
17,610
39
6,194
1,648
1,272
674
9,788
41
0
0
22
1,352
1,375
42
26,166
1,027
197
27
27,421
43
14,811
2,834
2,189
25
19,860
48
1,678
321
248
3
2,250
50
39,299
3,540
2,138
49
45,031
Recoveries in Condensate*
Butanes
95.04%
Pentanes+
99.57%
Production Rate
88,390
Lb/Hr
[88,390
kg/Hr]
LNG Product
Production Rate
834,183
Lb/Hr
[834,183
kg/Hr]
Purity*
87.27%
Lower Heating Value
1033.8
BTU/SCF
[38.52
MJ/m 3 ]
Power
Refrigerant Compression
84,974
HP
[139,696
kW]
Propane Compression
39,439
HP
[64,837
kW]
Total Compression
124,413
HP
[204,533
kW]
Utility Heat
Demethanizer Reboiler
52,913
MBTU/Hr
[34,182
kW]
*(Based on un-rounded flow rates)
[0085] Assuming an on-stream factor of 340 days per year for the LNG production plant, the specific power consumption for the FIG. 5 embodiment of the present invention is 0.145 HP-Hr/Lb [0.238 kW-Hr/kg]. Compared to the prior art processes, the efficiency improvement is 16-26% for the FIG. 5 embodiment.
[0086] Compared to the FIG. 1 and FIG. 3 embodiments, the FIG. 5 embodiment of the present invention requires 5% to 10% less power per unit of liquid produced. Compared to the FIG. 4 embodiment, the FIG. 5 embodiment of the present invention requires essentially the same power per unit of liquid produced. Thus, for a given amount of available compression power, the FIG. 5 embodiment could liquefy about 5% more natural gas than the FIG. 1 embodiment, about 10% more natural gas than the FIG. 3 embodiment, or about the same amount of natural gas as the FIG. 4 embodiment, by virtue of recovering only the C 4 and heavier hydrocarbons as a condensate co-product. The choice between the FIG. 5 embodiment versus either the FIG. 1 , FIG. 3 , or FIG. 4 embodiments of the present invention for a particular application will generally be dictated either by the monetary values of ethane and propane as part of an NGL or LPG product versus their corresponding values in the LNG product, or by the heating value specification for the LNG product (since the heating value of the LNG produced by the FIG. 1 , FIG. 3 , and FIG. 4 embodiments is lower than that produced by the FIG. 5 embodiment).
Other Embodiments
[0087] One skilled in the art will recognize that the present invention can be adapted for use with all types of LNG liquefaction plants to allow co-production of an NGL stream, an LPG stream, or a condensate stream, as best suits the needs at a given plant location. Further, it will be recognized that a variety of process configurations may be employed for recovering the liquid co-product stream. For instance, the FIGS. 1 and 3 embodiments can be adapted to recover an LPG stream or a condensate stream as the liquid co-product stream rather than an NGL stream as described earlier in Examples 1 and 2. The FIG. 4 embodiment can be adapted to recover an NGL stream containing a significant fraction of the C 2 components present in the feed gas, or to recover a condensate stream containing only the C 4 and heavier components present in the feed gas, rather than producing an LPG co-product as described earlier for Example 3. The FIG. 5 embodiment can be adapted to recover an NGL stream containing a significant fraction of the C 2 components present in the feed gas, or to recover an LPG stream containing a significant fraction of the C 3 components present in the feed gas, rather than producing a condensate co-product as described earlier for Example 4.
[0088] FIGS. 1 , 3 , 4 , and 5 represent the preferred embodiments of the present invention for the processing conditions indicated. FIGS. 6 through 21 depict alternative embodiments of the present invention that may be considered for a particular application. As shown in FIGS. 6 and 7 , all or a portion of the condensed liquid (stream 33 ) from separator 11 can be supplied to fractionation tower 19 at a separate lower mid-column feed position rather than combining with the portion of the separator vapor (stream 34 ) flowing to heat exchanger 13 . FIG. 8 depicts an alternative embodiment of the present invention that requires less equipment than the FIG. 1 and FIG. 6 embodiments, although its specific power consumption is somewhat higher. Similarly, FIG. 9 depicts an alternative embodiment of the present invention that requires less equipment than the FIG. 3 and FIG. 7 embodiments, again at the expense of a higher specific power consumption. FIGS. 10 through 14 depict alternative embodiments of the present invention that may require less equipment than the FIG. 4 embodiment, although their specific power consumptions may be higher. (Note that as shown in FIGS. 10 through 14 , distillation columns or systems such as deethanizer 19 include both reboiled absorber tower designs and refluxed, reboiled tower designs.) FIGS. 15 and 16 depict alternative embodiments of the present invention that combine the functions of separator/absorber tower 18 and deethanizer 19 in the FIGS. 4 and 10 through 14 embodiments into a single fractionation column 19 . Depending on the quantity of heavier hydrocarbons in the feed gas and the feed gas pressure, the cooled feed stream 31 a leaving heat exchanger 10 may not contain any liquid (because it is above its dewpoint, or because it is above its cricondenbar), so that separator 11 shown in FIGS. 1 and 3 through 16 is not required, and the cooled feed stream can flow directly to an appropriate expansion device, such as work expansion machine 15 .
[0089] The disposition of the gas stream remaining after recovery of the liquid co-product stream (stream 37 in FIGS. 1 , 3 , 6 through 11 , 13 , and 14 , stream 47 in FIGS. 4 , 12 , 15 , and 16 , and stream 43 in FIG. 5 ) before it is supplied to heat exchanger 60 for condensing and subcooling may be accomplished in many ways. In the processes of FIGS. 1 and 3 through 16 , the stream is heated, compressed to higher pressure using energy derived from one or more work expansion machines, partially cooled in a discharge cooler, then further cooled by cross exchange with the original stream. As shown in FIG. 17 , some applications may favor compressing the stream to higher pressure, using supplemental compressor 59 driven by an external power source for example. As shown by the dashed equipment (heat exchanger 24 and discharge cooler 25 ) in FIGS. 1 and 3 through 16 , some circumstances may favor reducing the capital cost of the facility by reducing or eliminating the pre-cooling of the compressed stream before it enters heat exchanger 60 (at the expense of increasing the cooling load on heat exchanger 60 and increasing the power consumption of refrigerant compressors 64 , 66 , and 68 ). In such cases, stream 49 a leaving the compressor may flow directly to heat exchanger 24 as shown in FIG. 18 , or flow directly to heat exchanger 60 as shown in FIG. 19 . If work expansion machines are not used for expansion of any portions of the high pressure feed gas, a compressor driven by an external power source, such as compressor 59 shown in FIG. 20 , may be used in lieu of compressor 16 . Other circumstances may not justify any compression of the stream at all, so that the stream flows directly to heat exchanger 60 as shown in FIG. 21 and by the dashed equipment (heat exchanger 24 , compressor 16 , and discharge cooler 25 ) in FIGS. 1 and 3 through 16 . If heat exchanger 24 is not included to heat the stream before the plant fuel gas (stream 48 ) is withdrawn, a supplemental heater 58 may be needed to warm the fuel gas before it is consumed, using a utility stream or another process stream to supply the necessary heat, as shown in FIGS. 19 through 21 . Choices such as these must generally be evaluated for each application, as factors such as gas composition, plant size, desired co-product stream recovery level, and available equipment must all be considered.
[0090] In accordance with the present invention, the cooling of the inlet gas stream and the feed stream to the LNG production section may be accomplished in many ways. In the processes of FIGS. 1 , 3 , and 6 through 9 , inlet gas stream 31 is cooled and condensed by external refrigerant streams and tower liquids from fractionation tower 19 . In FIGS. 4 , 5 , and 10 through 14 flashed separator liquids are used for this purpose along with the external refrigerant streams. In FIGS. 15 and 16 tower liquids and flashed separator liquids are used for this purpose along with the external refrigerant streams. And in FIGS. 17 through 21 , only external refrigerant streams are used to cool inlet gas stream 31 . However, the cold process streams could also be used to supply some of the cooling to the high pressure refrigerant (stream 71 a ), such as shown in FIGS. 4 , 5 , 10 , and 11 . Further, any stream at a temperature colder than the stream(s) being cooled may be utilized. For instance, a side draw of vapor from separator/absorber tower 18 or fractionation tower 19 could be withdrawn and used for cooling. The use and distribution of tower liquids and/or vapors for process heat exchange, and the particular arrangement of heat exchangers for inlet gas and feed gas cooling, must be evaluated for each particular application, as well as the choice of process streams for specific heat exchange services. The selection of a source of cooling will depend on a number of factors including, but not limited to, feed gas composition and conditions, plant size, heat exchanger size, potential cooling source temperature, etc. One skilled in the art will also recognize that any combination of the above cooling sources or methods of cooling may be employed in combination to achieve the desired feed stream temperature(s).
[0091] Further, the supplemental external refrigeration that is supplied to the inlet gas stream and the feed stream to the LNG production section may also be accomplished in many different ways. In FIGS. 1 and 3 through 21 , boiling single-component refrigerant has been assumed for the high level external refrigeration and vaporizing multi-component refrigerant has been assumed for the low level external refrigeration, with the single-component refrigerant used to pre-cool the multi-component refrigerant stream. Alternatively, both the high level cooling and the low level cooling could be accomplished using single-component refrigerants with successively lower boiling points (i.e., “cascade refrigeration”), or one single-component refrigerant at successively lower evaporation pressures. As another alternative, both the high level cooling and the low level cooling could be accomplished using multi-component refrigerant streams with their respective compositions adjusted to provide the necessary cooling temperatures. The selection of the method for providing external refrigeration will depend on a number of factors including, but not limited to, feed gas composition and conditions, plant size, compressor driver size, heat exchanger size, ambient heat sink temperature, etc. One skilled in the art will also recognize that any combination of the methods for providing external refrigeration described above may be employed in combination to achieve the desired feed stream temperature(s).
[0092] Subcooling of the condensed liquid stream leaving heat exchanger 60 (stream 49 in FIGS. 1 , 6 , and 8 , stream 49 d in FIGS. 3 , 4 , 7 , and 9 through 16 , stream 49 b in FIGS. 5 , 19 , and 20 , stream 49 e in FIG. 17 , stream 49 c in FIG. 18 , and stream 49 a in FIG. 21 ) reduces or eliminates the quantity of flash vapor that may be generated during expansion of the stream to the operating pressure of LNG storage tank 62 . This generally reduces the specific power consumption for producing the LNG by eliminating the need for flash gas compression. However, some circumstances may favor reducing the capital cost of the facility by reducing the size of heat exchanger 60 and using flash gas compression or other means to dispose of any flash gas that may be generated.
[0093] Although individual stream expansion is depicted in particular expansion devices, alternative expansion means may be employed where appropriate. For example, conditions may warrant work expansion of the substantially condensed feed stream (stream 35 a in FIGS. 1 , 3 , 6 , and 7 ) or the intermediate pressure reflux stream (stream 39 in FIGS. 1 , 6 , and 8 ). Further, isenthalpic flash expansion may be used in lieu of work expansion for the subcooled liquid stream leaving heat exchanger 60 (stream 49 in FIGS. 1 , 6 , and 8 , stream 49 d in FIGS. 3 , 4 , 7 , and 9 through 16 , stream 49 b in FIGS. 5 , 19 , and 20 , stream 49 e in FIG. 17 , stream 49 c in FIG. 18 , and stream 49 a in FIG. 21 ), but will necessitate either more subcooling in heat exchanger 60 to avoid forming flash vapor in the expansion, or else adding flash vapor compression or other means for disposing of the flash vapor that results. Similarly, isenthalpic flash expansion may be used in lieu of work expansion for the subcooled high pressure refrigerant stream leaving heat exchanger 60 (stream 71 c in FIGS. 1 and 3 through 21 ), with the resultant increase in the power consumption for compression of the refrigerant.
[0094] While there have been described what are believed to be preferred embodiments of the invention, those skilled in the art will recognize that other and further modifications may be made thereto, e.g. to adapt the invention to various conditions, types of feed, or other requirements without departing from the spirit of the present invention as defined by the following claims.
|
A process for liquefying natural gas in conjunction with producing a liquid stream containing predominantly hydrocarbons heavier than methane is disclosed. In the process, the natural gas stream to be liquefied is partially cooled, expanded to an intermediate pressure, and supplied to a distillation column. The bottom product from this distillation column preferentially contains the majority of any hydrocarbons heavier than methane that would otherwise reduce the purity of the liquefied natural gas. The residual gas stream from the distillation column is compressed to a higher intermediate pressure, cooled under pressure to condense it, and then expanded to low pressure to form the liquefied natural gas stream.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a child seat apparatus, and more particularly, it relates to a child seat apparatus that has side guards defining side walls on both sides of the upper half of a child sitting thereon for protecting the child, and armrest portions defining armrests on both sides of the waist of the child for protecting the child's lower half.
2. Description of the Background Art
An exemplary child seat apparatus is a child chair. The child chair is typically used indoors. Such a child chair comprises a seat portion and a backrest portion uprightly extending from the rear part of the seat portion. Some child chairs may further comprise first and second side guards defining a pair of side walls frontwardly extending from both side edges of the backrest portion respectively, and first and second armrest portions defining a pair of armrests upwardly extending from both side edges of the seat portion respectively, in order to improve safety for the child sitting thereon. Further, the backrest portion may be rendered inclinable or reclinable so that a child who falls asleep can recline thereon or the chair also serves as a bed for the child.
The aforementioned structure is applied not only to the child chair but also to other child seat apparatuses such as a baby carriage, a child safety seat for an automobile and the like, for example.
In the aforementioned child seat apparatus having an inclinable backrest portion and comprising a pair of side guards defining a pair of side walls frontwardly extending from both side edges of the backrest portion respectively, and first and second armrest portions defining a pair of armrests upwardly extending from both side edges of the seat portion respectively, the spaces or distances between the pair of side walls and the pair of armrests are generally set on the basis of the posture of the child who sits on the seat apparatus when the backrest portion is in an upright state. In other words, the pair of side walls and the pair of armrests are positioned at relatively narrow spaces or distances apart from one another to be capable of supporting the upper and lower halves of the child from both sides, in consideration of safety for the child who sits up on the seat portion.
When the backrest portion is so inclined that the seat is in the form of a bed for laying the child thereon, however, the child, particularly an infant, sometimes raises its hands, and tends to bend its knees. Therefore, the spaces between the pair of side walls and the pair of armrest portions which are set in the aforementioned manner may be too narrow for the child. It is desirable that the spaces between the pair of side walls and the pair of armrests are sufficient particularly around the shoulders and the waist of the child.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a child chair or other child seat apparatus, which can provide relatively narrow spaces between a pair of side walls and a pair of armrests when a backrest portion is in a generally upright position in consideration of safety for a child who sits on this apparatus, while providing relatively wide spaces when the backrest portion is inclined, i.e. reclined.
According to its first aspect, the present invention is directed to a child chair apparatus comprising a seat portion and a backrest portion uprightly extending from the rear part of the seat portion so as to be inclinable relative thereto, and further comprising first and second side guards defining a pair of side walls frontwardly extending from both side edges of the backrest portion. In order to solve the aforementioned technical problem, the inventive child seat apparatus comprises a holding mechanism for holding the first and second side guards so that the space between the pair of side walls is changeable, and an interlocking mechanism for changing the space in association with inclination of the backrest portion so that the space is widened as the backrest portion is inclined.
According to its second aspect, the present invention is directed to a child chair apparatus comprising a seat portion and a backrest portion uprightly extending from the rear part of the seat portion so as to be inclinable relative thereto, and further comprising first and second armrest portions defining a pair of armrests upwardly extending from both side edges of the seat portion. In order to solve the aforementioned technical problem, the inventive child seat apparatus comprises a holding mechanism for holding the first and second armrest portions so that the space between the pair of armrests is changeable, and an interlocking mechanism for changing the space in association with inclination of the backrest portion so that the space is widened as the backrest portion is inclined.
According to the first aspect of the present invention, the space between the pair of side walls is changed in association with the inclination of the backrest portion so that this space is widened as the backrest portion is inclined.
According to the second aspect of the present invention, the space between the pair of armrests is changed in association with the inclination of the backrest portion so that this space is widened as the backrest portion is inclined.
According to the first aspect of the present invention, therefore, the space between the pair of side walls is made narrower when the backrest portion is moved into an upright position to straighten up the upper half of the child thereby ensuring safety for the child, while this space is widened when the backrest portion is inclined for the child to recline thereon, thereby preventing the child from feeling cramped.
The space between the pair of side walls is changed automatically so to speak, in association with the inclination of the backrest portion, whereby no specific operation is required for changing this space and the overall operation for this child seat apparatus is simplified.
The space between the pair of side walls is narrowed when the backrest portion is moved into an upright position, whereby this child seat apparatus is less bulky as compared with a conventional child seat apparatus having a pair of side walls which are regularly arranged with a wide space therebetween.
Preferably, the first and second side guards comprise first and second major surface walls extending along the backrest portion for positioning the side walls on outer side edges thereof respectively, and the holding mechanism comprises a mechanism for movably supporting the first and second major surface walls with respect to the backrest portion. Thus, the holding mechanism for making the space between the pair of side walls changeable can be implemented in a relatively simple structure.
More preferably, a shaft inclinably supports the backrest portion, and a bridging bar having a lower end rotatably mounted at a position different from that of the shaft and an upper end selectively fixed to any one of a plurality of positions vertically distributed on the rear surface of the backrest portion is employed, in order to adjust the inclined state of the backrest portion.
In this case, the aforementioned holding mechanism comprises pivot pins for rotatably supporting lower ends of the first and second major surface walls with respect to the backrest portion, while the interlocking mechanism for changing the space between the pair of side walls in association with the inclination of the backrest portion comprises a pair of driving pins mounted on the upper end of the bridging bar, a pair of guide slots that extend in parallel with each other are provided in the backrest portion for vertically movably receiving the pair of driving pins respectively, and a pair of driven slots are provided in the major surface walls of the pair of side guards respectively for receiving the pair of driving pins to be movable along longitudinal directions thereof.
The pair of driven slots are directed or oriented so as to approach each other toward the upper ends thereof. Due to this structure, it is possible to rotate the pair of side guards respectively through movement of the upper end of the bridging bar whose position is changed in response to the inclination of the backrest portion, thereby changing the space between the pair of side walls by a simple mechanism.
More preferably, the inventive child seat apparatus further comprises a head guard which is vertically rotatably mounted on the upper end of the backrest portion, and a mechanism for transmitting the operation of the upper end of the bridging bar to the head guard so that the head guard is moved into a position extending substantially flush and parallel with the backrest portion when it is most upright, and is moved into a position extending substantially upright or perpendicularly from the backrest portion when the backrest portion is most inclined. According to this structure, the head guard extends substantially flush with the backrest portion when the backrest portion is uprighted, and alternatively extends substantially upright from the backrest portion when the backrest portion is most inclined, whereby the safety of the child who lies on the child seat apparatus can be further improved. Further, the head guard is tilted upright in association with the inclination of the backrest portion, whereby no specific operation is required for moving the head guard and the overall operation of this child seat apparatus can be simplified.
According to the second aspect of the present invention, on the other hand, the space between the pair of armrests is narrowed when, i.e. made narrower, when the backrest portion is uprighted to straighten up the upper half of the child thereby ensuring safety for the child, while this space is widened when the backrest portion is inclined for the child to recline thereon, thereby preventing the child from feeling cramped.
The space between the pair of armrests is changed automatically, so to speak, in association with the inclination of the backrest portion, whereby no specific operation is required for changing this space and the operation for this child seat apparatus is simplified.
The space between the pair of armrests is narrowed when the backrest portion is moved into an upright position, whereby this child seat apparatus is less bulky as compared with a conventional child seat apparatus having a pair of armrests which are regularly arranged with a wide space therebetween.
Preferably, the first and second armrest portions comprise first and second major surface walls extending along the seat portion for positioning the armrests on outer side edges thereof respectively, and the holding mechanism comprises a mechanism for slidably supporting the first and second major surface walls with respect to the seat portion. Thus, the holding mechanism for making the space between the pair of armrests changeable can be implemented in a relatively simple structure.
More preferably, the backrest portion comprises a working plate which is fixed to a portion close to the lower end on the rear surface of the backrest portion, and the holding mechanism comprises first and third crosswisely extending guide slots provided in the vicinity of front and rear portions of the first major surface wall on the rear surface of the seat portion respectively, second and fourth crosswisely extending guide slots provided in the vicinity of front and rear portions of the second major surface wall on the rear surface of the seat portion, first and third driving pins provided in the vicinity of front and rear portions of the first major surface wall to be received in the first and third guide slots respectively so that the first major surface wall is movable along the first and third guide slots, and second and fourth driving pins provided in the vicinity of front and rear portions of the second major surface wall to be received in the second and fourth guide slots respectively so that the second major surface wall is movable along the second and fourth guide slots. Further preferably, the aforementioned interlocking mechanism comprises a working pin having a rear end rotatably mounted on the working plate, a sliding plate pivotally supporting a front end of the working pin, which is lengthwisely slidable at a substantially central portion on the rear surface of the backrest portion, first and second connecting pins provided on front and rear ends of the sliding plate respectively, first and third connecting plates connecting the first and second connecting pins with the first and third driving pins respectively to horizontally slide the first armrest portion following or linked to the lengthwise movement of the sliding plate, and second and fourth connecting plates for connecting the first and second connecting pins with the second and fourth driving pins to horizontally slide the second armrest portion following or linked to the lengthwise movement of the sliding plate.
According to this structure, the first to fourth connecting plates operate in response to the lengthwise movement of the sliding plate through movement of the working plate which is rotated in response to the inclination of the backrest portion, for horizontally sliding the first and second armrest portions. Thus, the space between the pair of armrest portions can be reliably changed by a simple mechanism.
Further preferably, an extension plate is provided on the front portion of the sliding plate to project from the front portion of the seat portion as the backrest portion is inclined. Thus, the child reliably sits up on the seat portion when the backrest portion is uprighted, while the extension plate extends substantially flush with the seat portion under the feet of the child when the backrest portion is most inclined, whereby the safety of the child who lies on this apparatus can be further improved. Due to the association or linking of the extending operation of the extension plate with the inclination of the backrest portion, the operation for the child seat apparatus can be further simplified.
Further preferably, the holding mechanism comprises first and third horizontally extending guide slots provided in the vicinity of upper and lower ends of the first major surface wall on the rear surface of the backrest portion respectively, second and fourth horizontally extending guide slots provided in the vicinity of upper and lower ends of the second major surface wall on the rear surface of the backrest portion respectively, first and third driving pins provided in the vicinity of upper and lower ends of the first major surface wall to be received in the first and third guide slots respectively so that the first major surface wall is movable along the first and third guide slots, and second and fourth driving pins provided in the vicinity of upper and lower ends of the second major surface wall to be received in the second and fourth guide slots so that the second major surface wall is movable along the second and fourth guide slots. Also, the interlocking mechanism preferably comprises a sliding plate, pivotally supporting the upper end of the bridging bar, which is vertically slidable at a substantially central portion on the rear surface of the backrest portion, first and second connecting pins provided on upper and lower ends of the sliding plate respectively, first and third connecting plates connecting the first and second connecting pins with the first and third driving pins to horizontally slide the first side guard following or linked to the vertical movement of the sliding plate, and second and fourth connecting plates connecting the first and second connecting pins with the second and fourth driving pins respectively to horizontally slide the second side guard following or linked to the vertical movement of the sliding plate.
According to this structure, the first to fourth connecting plates operate in response to the vertical movement of the sliding plate through movement of the upper end of the bridging bar whose position is changed in response to the inclination of the backrest portion, for horizontally sliding the first and second side guards. Thus, the space between the pair of side walls can be reliably changed by a simple mechanism.
The foregoing and other objects, features, aspects and advantages of the present invention will become more apparent from the following detailed description of the present invention when taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side elevational view showing the appearance of a child chair 1 according to a first embodiment of the present invention, with a backrest portion 5 in a most uprighted state;
FIG. 2 is a side elevational view showing the appearance of the child chair 1 shown in FIG. 1, with the backrest portion 5 in a most inclined state;
FIG. 3 is a front elevational view of the backrest portion 5 in the upright state shown in FIG. 1;
FIG. 4 is a front elevational view of the backrest portion 5 in the inclined state shown in FIG. 2;
FIG. 5 is a rear elevational view of the backrest portion 5 in the upright state shown in FIG. 1;
FIG. 6 is a rear elevational view of the backrest portion 5 in the inclined state shown in FIG. 2;
FIG. 7 is an enlarged sectional view taken along the line VII--VII in FIG. 6;
FIG. 8 is an enlarged sectional view taken along the line VIII--VIII in FIG. 6;
FIG. 9 is a sectional view taken along the line IX--IX in FIG. 5, while omitting the side guards 7A and 7B etc. for the sake of clarity;
FIG. 10 is a sectional view taken along the line VII--VII in FIG. 6 and generally corresponds to FIG. 7 on a different scale;
FIG. 11 is a sectional view taken along the line XI--XI in FIG. 5, while omitting an operating member 30 etc. for the sake of clarity;
FIG. 12 is a sectional view taken along the line XII--XII in FIG. 6;
FIG. 13 is a perspective view independently showing a slider 19 shown in FIG. 11;
FIG. 14 is a first diagram showing the structure of a backrest portion in a second embodiment according to the present invention;
FIG. 15 is a second diagram showing the structure of the backrest portion in the second embodiment according to the present invention;
FIG. 16 is a sectional view taken along the line XVI--XVI in FIG. 14;
FIG. 17 is a sectional view taken along the line XVII--XVII in FIG. 15;
FIG. 18 is a sectional view taken along the line XVIII--XVIII in FIG. 14;
FIG. 19 is a sectional view taken along the line XIX--XIX in FIG. 14;
FIG. 20 is a sectional view taken along the line XX--XX in FIG. 15;
FIG. 21 is a first sectional view showing an interlocking state between the backrest portion and an inclination mechanism in the second embodiment;
FIG. 22 is a second sectional view showing the interlocking state between the backrest portion and the inclination mechanism in the second embodiment;
FIG. 23 illustrates the structure of a seat portion in a third embodiment of the present invention;
FIG. 24 is a first sectional view showing an interlocking state between the backrest portion and an inclination mechanism in the third embodiment;
FIG. 25 is a second sectional view showing the interlocking state between the backrest portion and the inclination mechanism in the third embodiment;
FIG. 26 illustrates the structure of a seat portion in a fourth embodiment of the present invention;
FIG. 27 is a first sectional view showing an interlocking state between the backrest portion and an inclination mechanism in the fourth embodiment; and
FIG. 28 is a second sectional view showing the interlocking state between the backrest portion and the inclination mechanism in the fourth embodiment.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
(First Embodiment)
The drawings illustrate a child seat apparatus according to a first embodiment of the present invention. The first embodiment is applied to a child chair 1, for example.
FIGS. 1 and 2 are side elevational views showing the appearance of the overall child chair 1. The child chair 1 generally comprises a base part 2 and a seat part 3. The seat part 3 comprises a seat portion 4 (see FIG. 9 etc.) and a backrest portion 5 uprightly extending from the rear part of the seat portion 4. Further, a pair of armrest portions 86 are provided to define a pair of armrests 85 upwardly extending from both side edges of the seat portion 4 respectively. The backrest portion 5 is inclinable, as understood from FIGS. 1 and 2. In addition, first and second side guards 7A and 7B are provided in relation to or on the backrest portion 5, to define a pair of side walls 6A and 6B frontwardly extending from both side edges of the backrest portion 5 respectively. Further, a head guard 8 is lengthwisely rotatably mounted on an upper end of the backrest portion 5. The head guard 8 extends substantially flush with the backrest portion 5 when the backrest portion is in an ordinary upright state as shown in FIG. 1, while the head guard 8 is uprighted or angled to extend substantially perpendicularly from the backrest portion 5 as shown in FIG. 2, when the backrest portion 5 is in a most inclined state.
On the other hand, the base part 2 comprises front and rear legs 9 and 10. These front and rear legs 9 and 10 intersect with each other, and are coupled with each other by pivot portions 11 at the intersections. Front and rear wheels 12 and 13 are rotatably mounted on lower ends of the front and rear legs 9 and 10 respectively. The front and rear wheels 12 and 13 can roll on a floor face 14, thereby moving the overall chair 1.
The seat part 3 is held by a seat holder 15, which in turn is supported by the front and rear legs 9 and 10. The front and rear legs 9 and 10 are rotatably mounted on the seat holder 15 through pivot portions 16 and 17 respectively. The pivot portions 17 are positioned on movable parts 18 which are provided on the seat holder 15. The movable parts 18 can be adjusted to change the positions thereof along the lengthwise direction of the chair 1, thereby changing the angles of the front and rear legs 9 and 10. Thus, the height of the seat part 3 can be adjusted. The mechanism for changing the positions of the movable parts 18 is not related to the subject matter of the present invention, and hence a detailed description thereof is omitted.
The feature of this embodiment is related to the backrest portion 5. FIGS. 3 to 13 show structures which are related to the backrest portion 5 respectively. FIGS. 3 and 4 are front elevational views illustrating the backrest portion 5 in states corresponding to those shown in FIGS. 1 and 2 respectively. FIGS. 5 and 6 are rear elevational views illustrating the backrest portion 5 in the states corresponding to those shown in FIGS. 1 and 2 respectively. FIGS. 7 and 8 are sectional views taken along lines VII--VII and VIII--VIII in FIG. 6 respectively. FIGS. 9 and 10, which illustrate an inclination mechanism for the backrest portion 5, are sectional views taken along the lines IX--IX and VII--VII in FIGS. 5 and 6 respectively. FIGS. 11 and 12, illustrating a mechanism for driving the side guard 7A, are sectional views taken along the lines XI--XI and XII--XII in FIGS. 5 and 6 respectively. FIG. 13 is a perspective view independently illustrating a slider 19 shown in FIGS. 11 and 12.
Mainly with reference to FIGS. 9 and 10, the inclination mechanism for the backrest portion 5 is now described.
The backrest portion 5 is rotatably supported with respect to the seat holder 15 through a shaft 20, so as to be inclinable. An inverted U-shaped bridging bar 21 is provided in order to fix the backrest portion 5 in an adjusted inclined state. A lower end 22 of the bridging bar 21 is rotatably mounted on the seat holder 15 in a position or location different from that of the shaft 20. On the other hand, an upper end 23 of the bridging bar 21 is selectively fixed to any one of a plurality of positions which are vertically distributed on the rear surface of the backrest portion 5. For example, in order to fix the upper end 23, an engaging member 29 having a plurality of engaging cavities 24, 25, 26, 27 and 28 for selectively engaging with the upper end 23 is provided on the rear surface of the backrest portion 5. In the state shown in FIG. 9, the upper end 23 engages with the lowermost engaging cavity 24, thereby most uprighting the backrest portion 5. In the state shown in FIG. 10, on the other hand, the upper end 23 engages with the uppermost engaging cavity 28, thereby most inclining the backrest portion 5.
An operation member 30 is provided in order to stably maintain the upper end 23 in a state engaging with any one of the engaging cavities 24 to 28 as described above and to bring the upper end 23 into a disengaged state, i.e. engaging with none of the engaging cavities 24 to 28. The operation member 30 has a slot 31 receiving the upper end 23 of the bridging bar 21, so that the upper end 23 is movable in the slot 31 along its longitudinal direction.
The operation member 30 is regularly urged by a compression spring 32 toward the backrest portion 5. An end of the compression spring 32 engages with an end of a thrust pin 33, while the other end thereof is in contact with the operation member 30. Another end of the thrust pin 33 passes through the operation member 30 and extends toward the front surface of the backrest portion 5, to engage with the backrest portion 5. The thrust pin 33 is movable in a slot 34, which is provided in the backrest portion 5, along its longitudinal direction. Therefore, the operation member 30 is also displaceable with respect to the backrest portion 5 along the longitudinal direction of the slot 34 within the range of its extension. The operation member 30 can be separated or pulled slightly away from the backrest portion 5 against the elasticity of the compression spring 32.
The aforementioned head guard 8 is lengthwisely rotatably mounted on the upper end of the backrest portion 5 through a shaft 35. The head guard 8 and the operation member 30 are rotatably coupled with each other through a shaft 36. Due to this structure, the operation of the upper end 23 of the bridging bar 21 is transmitted to the head guard 8 through the operation member 30 via the slot 31 when the backrest portion 5 is most inclined, so that the head guard 8 is uprighted from the backrest portion 5 as shown in FIG. 10.
On the basis of the aforementioned structure, inclination of the backrest portion 5 is now described.
In the state shown in FIG. 9, the backrest portion 5 is most uprighted and this state is supported by the upper end 23 of the bridging bar 21 engaging with the lowermost engaging cavity 24 of the engaging member 29. The state of such engagement of the upper end 23 and the engaging cavity 24 is maintained by the operation member 30 which is urged by the compression spring 32 toward the backrest portion 5. As understood from the position of the thrust pin 33 in the slot 34, the operation member 30 is in a relatively lower position with respect to the backrest portion 5, whereby the head guard 8 extends substantially flush with the backrest portion 5.
In order to incline the backrest portion 5 from the aforementioned state, the operation member 30 is first separated or tiltingly pulled away from the backrest portion 5. This operation is achieved by manually pulling with one's finger engaging an operation rib 37 which is provided on a lower end of the operation member 30 to project inwardly. Due to this operation, the operation member 30 is rotated about the shaft 36 against the elasticity of the compression spring 32. Therefore, the upper end 23 of the bridging bar 21 disengages from the engaging cavity 24 due to the tilting motion of the operation member 30 imparted to the upper end 23 via the slot 31. Thus, the backrest portion 5 can be inclined.
After the backrest portion 5 is inclined to an arbitrary angle as desired, the pulling or rotating force that had been applied to the operation member 30 is removed. Thus, the operation member 30 is urged by the compression spring 32 and rotated toward the backrest portion 5 so that the upper end 23 of the bridging bar 21 engages with any desired one of the engaging cavities 25 to 28.
When the operation member 30 is in the position shown in FIG. 9, engagement of the upper end 23 of the bridging bar 21 and any one of the engaging cavities 24 to 27 can be attained in the range of extension of the slot 31. Also when the upper end 23 having previously been engaged with the engaging cavity 24 now engages with any one of the engaging cavities 25 to 27, therefore, the position of the operation member 30 with respect to the backrest portion 5 remains unchanged, whereby the positional relation between the head guard 8 and the backrest portion 5 is also retained. When the upper end 23 engages with the uppermost engaging cavity 28, on the other hand, it exceeds the range of the slot 31 of the operation member 30 in the position shown in FIG. 9. Therefore, the upper end 23 which is positioned at an end of the slot 31 upwardly displaces the operation member 30 with respect to the backrest portion 5. FIG. 10 shows such a state that the upper end 23 engages with the uppermost engaging cavity 28 while upwardly displacing the operation member 30, as understood from the position of the thrust pin 33 in the slot 34.
In the state shown in FIG. 10, the backrest portion 5 is most inclined and the head guard 8 is uprighted from the backrest portion 5.
In order to upright the backrest portion 5 from the state shown in FIG. 10 to that shown in FIG. 9 or to an intermediate state, an operation substantially similar to the above is carried out. As understood from the range of extension of the slot 31, the head guard 8 extends substantially flush with the backrest portion 5 when the upper end 23 engages with the engaging cavity 24 as shown in FIG. 9, while the same is maintained in the position uprighted from the backrest portion 5 before reaching this state, as shown in FIG. 10. In order to make the head guard 8 extend substantially flush with the backrest portion 5 as shown in FIG. 9 in such an intermediate state, therefore, force is directly applied to the head guard 8 to forcibly rotate the same. Alternatively, the same effect can be achieved without directly manipulating the head guard 8 by temporarily moving the backrest portion 5 to the state shown in FIG. 9 and thereafter again inclining the backrest portion 5 to the desired inclination angle.
The space between the aforementioned pair of side walls 6A and 6B is changed in association with such inclination of the backrest portion 5. More specifically, the aforementioned space is widened as the backrest portion 5 is inclined. This structure is now described with reference to FIGS. 3 to 8 and 11 to 13. The pair of first and second side guards 7A and 7B comprise first and second major surface walls 38A and 38B extending along the front surface of the backrest portion 5 for positioning the side walls 6A and 6B on outer ends respectively. In order to hold the first and second side guards 7A and 7B so that the space between the pair of side walls 6A and 6B is changeable, lower ends of the first and second major surface walls 38A and 38B are rotatably supported with respect to the backrest portion 5 through pivot pins 39A and 39B respectively. The operation of the upper end 23 of the bridging bar 21 is transmitted to the first and second side guards 7A and 7B, so that the space between the pair of side walls 6A and 6B is changed in association with inclination of the backrest portion 5. The structure therefor is now described. As clearly shown in FIGS. 5, 6, 7 and 8, the aforementioned operation member 30 is in the form of a box, with a slider 19 positioned inside the same. The slider 19 is provided with a guide post 40, which is received in a longitudinal guide hole 41 provided in the backrest portion 5 to extend in the vertical direction. Therefore, the slider 19 is slidable with respect to the backrest portion 5 by the range of the guide post 40 which is movable in the guide hole 41. The slider 19 is further provided with a through hole 42 receiving the upper end 23 of the bridging bar 21. The longitudinal direction of the through hole 42 is perpendicular to the plane of extension of the backrest portion 5, to allow the aforementioned engagement and disengagement of the upper end 23 with and from the engaging cavities 24 to 28. Thus, the upper end 23 is so received in the through hole 42 that the slider 19 is vertically displaced along the rear surface of the backrest portion 5 following the motion of the upper end 23.
A pair of brackets 43 are provided to extend from both sides of the slider 19, and a pair of driving pins 44 are provided on these brackets 43. The backrest portion 5 is provided with a pair of guide slots 45 extending in parallel with each other, which receive the pair of driving pins 44 to be vertically movable respectively therein. The pair of driving pins 44 pass through the pair of guide slots 45, to reach the first and second major surface walls 38A and 38B of the first and second side guards 7A and 7B respectively. The first and second major surface walls 38A and 38B of the first and second side guards 7A and 7B are provided with a pair of driven slots 46 for receiving the pair of driving pins 44 to be longitudinally movable respectively therein. As clearly shown in FIGS. 3 and 4, the pair of driven slots 46 are so directed or inclined relative to each other so as to approach toward each other toward upper ends thereof.
As hereinabove described, the upper end 23 of the bridging bar 21 vertically moves along the rear surface of the backrest portion 5 in response to the change of its inclination, and the slider 19 is vertically slid along the rear surface of the backrest portion 5 following such movement of the upper end 23. In response to such sliding of the slider 19, the driving pins 44 vertically move in the guide slots 45 provided in the backrest portion 5. During the movement in the guide slots 45, the driving pins 44 engage with the driven slots 46 provided in the first and second side guards 7A and 7B and thereby rotate the side guards about the pivot pins 39A and 39B.
The backrest portion 5 is most uprighted in the state shown in FIGS. 3 and 5, so that the driving pins 44 are positioned on the lower ends of the guide slots 45 as well as on the lower ends of the driven slots 46. Thus, the first and second side guards 7A and 7B are rotated most closely toward each other, thereby minimizing the space between the side walls 6A and 6B.
On the other hand, the backrest portion 5 is most inclined in the state shown in FIGS. 4 and 6, so that the driving pins 44 are positioned on the upper ends of the guide slots 45 as well as the upper ends of the driven slots 46. Thus, the first and second side guards 7A and 7B most separate from each other, thereby maximizing the space between the side walls 6A and 6B.
When the driving pins 44 are positioned in longitudinal centers of the guide slots 45 and the driven slots 46, the first and second side guards 7A and 7B are rotated to be in intermediate positions between those in the states shown in FIGS. 3 and 5 and FIGS. 4 and 6, so that the space between the pair of side walls 6A and 6B is also in an intermediate state.
Thus, the space between the pair of side walls 6A and 6B can be changed to be widened as the backrest portion 5 is inclined, in association with the inclination of the backrest portion 5.
In the first embodiment shown in FIGS. 1 to 13, the head guard 8 is so provided that its angle is controlled by the operation of the upper end 23 of the bridging bar 21, while this structure is not required for the present invention. The head guard 8 may alternatively be so arranged that its angle can be changed by a direct manual operation or is unchangeable. Further, the inventive child seat apparatus may be provided with no head guard.
(Second Embodiment)
A child seat apparatus according to a second embodiment of the present invention is now described. Comparing the child seat apparatus according to the second embodiment with that according to the first embodiment, first and second side guards 52 and 53 are supported to be translated with respect to a backrest portion 51 according to the structure of the second embodiment, although the first and second side guards are rotatably supported with respect to the backrest portion in the structure of the first embodiment. Therefore, the translated structures of the first and second side guards 52 and 53 are now described in detail with reference to FIGS. 14 to 22.
FIGS. 14 and 15 are rear elevational views of the backrest portion 51, showing the first and second side guards 52 and 53 in relative positions that are most narrowed and most widened respectively. FIGS. 16, 17, 18, 19 and 20 are sectional views taken along the lines XVI--XVI in FIG. 14, XVII--XVII in FIG. 15, XVIII--XVIII in FIG. 14, XIX--XIX in FIG. 14 and XX--XX in FIG. 15 respectively.
With reference to FIGS. 14, 16, 18 and 19, the structure of the backrest portion 51 in this embodiment is now described.
The first and second side guards 52 and 53 are provided with first and second major surface walls 52A and 53A extending along the backrest portion 51 for positioning first and second side walls 52B and 53B on outer side edges respectively.
First and third horizontally extending guide slots 64 and 66 are provided in the vicinity of upper and lower ends of the first major surface wall 52A on the rear surface of the backrest portion 51 respectively. Further, second and fourth horizontally extending guide slots 65 and 67 are provided in the vicinity of upper and lower ends of the second major surface wall 53A on the rear surface of the backrest portion 51 respectively.
First, third, second and fourth driving pins 60, 62, 61 and 63 are provided in positions of the first and second major surface walls 52A and 53A corresponding to positions of the first to fourth guide slots 64 to 67 and are received in the first, third, second and fourth guide slots 64, 66, 65 and 67 respectively so that the first and second major surface walls 52A and 53A are horizontally movable along the first to fourth guide slots 64 to 67.
In an interlocking mechanism for association with an inclination mechanism, a vertically extending guide groove 83 is provided on the rear surface of the backrest portion 51, and a slider 68 is provided to be vertically movably guided by this guide groove 83. This slider 68 is provided with a stopper pin 68a for positioning a sliding plate 68d and the slider 68, and a spring 68b for applying an urging force to the stopper pin 68a.
A projection 68c which is provided on the forward end of the stopper pin 68a is inserted in a selected one of plural positioning holes 72 provided in the backrest portion 51, thereby positioning the slider 68. The slider 68 rotatably supports an upper end 70a of a bridging bar 70 at a bridging bar fixing portion 84.
First and second connecting pins 58 and 59 are provided on upper and lower ends of the sliding plate 68d respectively. First and second connecting plates 54 and 55 which are connected with the first and second driving pins 60 and 61 respectively are mounted on the first connecting pin 58. On the other hand, third and fourth connecting plates 56 and 57 which are connected with the third and fourth driving pins 62 and 63 respectively are mounted on the second connecting pin 59.
In the backrest portion 50 having the aforementioned structure, the slider 68 upwardly moves along the guide groove 83, and the first and second connecting pins 58 and 59 also upwardly move to push up the first to fourth connecting plates 54 to 57. However, second ends of the first to fourth connecting plates 54 to 57 are connected to the first to fourth driving pins 60 to 63 moving along the first to fourth guide slots 64 to 67 respectively, whereby the force pushing up the first to fourth connecting plates 54 to 57 outwardly slides the first to fourth driving pins 60 to 63 along the first to fourth guide slots 64 to 67 respectively. Thus, it is possible to crosswisely widen the side guards 52 and 53 in parallel with each other by raising up the slider 68, as shown in FIGS. 15, 17 and 20.
With reference to FIGS. 21 and 22, the inclination of the backrest portion 50 will be described on the basis of the aforementioned structure. In the state shown in FIG. 21, the backrest portion 50 is most uprighted so that the upper end 70a of the bridging bar 70 is connected to the fixing portion 84, with the projection 68c of the stopper pin 68a in the lowermost one of the positioning holes 72 which are provided in the guide groove 83.
In order to incline the backrest portion 50 from this state, the stopper pin 68a is first raised up against the urging force of the spring 68b, to next allow gradually upwardly sliding the slider 68. At this time, the lower end 70b of the bridging bar 70 is pivotally rotatably supported by a support part 77, whereby the backrest portion 50 is rotated about a shaft 76. When the slider 68 is slid to the uppermost position, for example, the backrest portion 50 is most inclined as shown in FIG. 22. The backrest portion 50 can be readily uprighted again from the state shown in FIG. 22 by an operation opposite to the above.
As hereinabove described, the space between the first and second side guards 52 and 53 can be changed in association with the inclination of the backrest portion 51, so that this space can be horizontally widened as the backrest portion 50 is inclined.
(Third Embodiment)
A third embodiment of the present invention is now described with reference to FIGS. 23 to 25. While the space between the first and second side guards is changed in association with the inclination of the backrest portion in each of the aforementioned first and second embodiments, the space between first and second armrest portions is changed in association with the inclination of a backrest portion in the third embodiment.
FIG. 23 is a bottom plan view of a seat part 73 which is in such a state that the space between first and second armrest portions 78 and 79 is most narrowed.
The first and second armrest portions 78 and 79 are provided with first and second major surface walls 78A and 79A extending along a seat portion 74 for positioning first and second armrests 78B and 79B on outer side edges respectively. Other structures of this embodiment are identical to those of the second embodiment shown in FIG. 14 except that a slider 68 is not provided with a stopper pin 68a and a working pin 81 is rotatably fixed to a working pin fixing portion 84 in the slider 68.
Due to the aforementioned structure which is similar to that of the second embodiment, the space between the first and second armrest portions 78 and 79 is most narrowed when the slider 68 is at the rightmost position as shown in FIGS. 23 and 24, while the space is most widened when the slider 68 is at the leftmost position as shown in FIG. 25.
With reference to FIGS. 24 and 25, the structures for providing an interlocking between the inclination of a backrest portion 50 and the change of the space between the first and second armrest portions 78 and 79.
FIG. 24 shows the backrest portion 50 which is most uprighted. In this case, the space between the first and second armrest portions 78 and 79 is most narrowed.
A working plate 80 is mounted on a lower part of the backrest portion 50, to extend downwardly therefrom. A lower end 81b of the working pin 81 is rotatably mounted on a second or free end of the working plate 80.
From this state, if the backrest portion 50 is gradually inclined, then the working plate 80 is rotated with the backrest portion 50 about a shaft 76. Thus, the working pin 81 which is mounted on the second end of the working plate 80 moves in the direction of the arrow in FIG. 25, to leftwardly slide the slider 68. Thus, the space between the first and second armrest portions 78 and 79 is gradually widened as the backrest portion 50 is inclined.
When the backrest portion 50 is inclined, the horizontal spaces or widths of the seat portion 74 and the backrest portion 50 are widened due to the combination of the mechanisms in the second embodiment as shown in FIGS. 24 and 25, whereby a comfortable space for a child can be ensured.
(Fourth Embodiment)
A fourth embodiment of the present invention is now described with reference to FIGS. 26 to 28. In the fourth embodiment, an extension plate 69A is made to extend from a front part of a seat portion 74 in association with inclination of a backrest portion 50.
FIG. 26 is a bottom plan view showing the seat portion 74. Dissimilarly to the structure of the third embodiment, the extension plate 69A is mounted on a front end of a slider 68. In relation to the aforementioned structure, FIG. 27 shows the backrest portion 50 which is in a most uprighted state, with the slider 68 at the rightmost position and the extension plate 69A retracted within and below the contour of the front edge of the seat portion 74.
When the backrest portion 50 is gradually inclined as shown in FIG. 28, the slider 68 moves leftwardly similarly to the third embodiment, whereby the extension plate 69A projects from the front part of the seat portion 74.
Thus, the extension plate 69A is provided to project from the front part of the seat portion 74 in association with inclination of the backrest portion 50. In combination with the aforementioned second or third embodiment, for example, the horizontal spaces of the seat portion 74 and the backrest portion 50 as well as the front space of the seat portion 74 can be widened or extended in an inclined state of the backrest portion 50, whereby a further comfortable space can be ensured for the child.
While the present invention has been described with reference to the first to fourth embodiments shown in the drawings, various modifications are available within the scope of the present invention.
Further, the mechanisms for changing the spaces between the first and second side walls and between the first and second armrests in association with the inclination of the backrest portions are not restricted to those employed in the embodiments, but can be replaced by various well-known interlocking mechanisms. In addition, the mechanism for adjusting the inclination of the backrest portion can also be replaced by another well-known mechanism.
While the drawings show only the members serving as bases for forming the seat portion 4, the backrest portion 5, the first and second side guards 7A and 7B and the head guard 8 respectively, a surface material which is filled or padded with a cushion material, for example, is arranged on these members serving as bases in the child chair 1 in practice. Such a surface material is arranged not to hinder the operations of the first and second side guards 7A and 7B, for example, as a matter of course.
While the above embodiments have been described with reference to child chairs 1, the present invention is also applicable to another type of child seat apparatus such as a baby carriage or a child safety seat for an automobile, for example.
Although the present invention has been described and illustrated in detail, it is clearly understood that the same is by way of illustration and example only and is not to be taken by way of limitation, the spirit and scope of the present invention being limited only by the terms of the appended claims.
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A child seat apparatus includes a seat, a reclinable backrest, and at least either a pair of side guards rotatably mounted on the backrest or a pair of armrests mounted on the seat, wherein the lateral spacing between the side guards or the armrests is changeable. An interlocking mechanism links the backrest with the side guards or the armrests so that the space between the side guards or the armrests is changed in association with the inclination of the backrest. Specifically, this space is widened as the backrest is reclined. Such an interlocking mechanism, for example, includes driving pins that are driven with an upper end of a bridging bar for supporting the backrest in a reclined state while a pair of driven slots are provided in the side guards for receiving the driving pins respectively. The driven slots are directed at an angle relative to each other so as to be closer to each other at upper ends thereof. Due to this structure, a dimensional allowance is provided around the shoulders of a child when the backrest is reclined into the form of a bed.
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CROSS REFERENCE TO RELATED APPLICATION
[0001] The present application is a continuation of U.S. Ser. No. 11/298,774 filed on Dec. 12, 2005, which is a continuation of U.S. Ser. No. 10/728,834 filed on Dec. 8, 2003, now issued as U.S. Pat. No. 6,991,322, which is a continuation-in-part of U.S. application Ser. No. 10/302,274 filed on Nov. 23, 2002, now issued as U.S. Pat. No. 6,755,509, the entire contents of which are herein incorporated by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to a thermal ink jet printhead, to a printer system incorporating such a printhead, and to a method of ejecting a liquid drop (such as an ink drop) using such a printhead.
BACKGROUND TO THE INVENTION
[0003] The present invention involves the ejection of ink drops by way of forming gas or vapor bubbles in a bubble forming liquid. This principle is generally described in U.S. Pat. No. 3,747,120 (Stemme).
[0004] There are various known types of thermal ink jet (bubblejet) printhead devices. Two typical devices of this type, one made by Hewlett Packard and the other by Canon, have ink ejection nozzles and chambers for storing ink adjacent the nozzles. Each chamber is covered by a so-called nozzle plate, which is a separately fabricated item and which is mechanically secured to the walls of the chamber. In certain prior art devices, the top plate is made of Kapton™ which is a Dupont trade name for a polyimide film, which has been laser-drilled to form the nozzles. These devices also include heater elements in thermal contact with ink that is disposed adjacent the nozzles, for heating the ink thereby forming gas bubbles in the ink. The gas bubbles generate pressures in the ink causing ink drops to be ejected through the nozzles.
[0005] It is an object of the present invention to provide a useful alternative to the known printheads, printer systems, or methods of ejecting drops of ink and other related liquids, which have advantages as described herein.
SUMMARY OF THE INVENTION
[0006] According to a first aspect, the present invention provides an ink jet printhead comprising:
[0007] a plurality of nozzles; and,
[0008] at least one heater element corresponding to each of the nozzles respectively, the heater element configured for thermal contact with a bubble forming liquid; such that, heating the heater element to a temperature above the boiling point of the bubble forming liquid forms a gas bubble that causes the ejection of a drop of an ejectable liquid through the nozzle corresponding to that heater element; wherein,
[0009] the gas bubble displaces less than 4 nanograms of the ejectable liquid to cause the ejection of the drop.
[0010] The invention configures the components of the printhead such that the bubble formed on the heater element need only move a very small mass of liquid in order to eject an ink drop. The displacement of a relatively small mass requires less input energy to the heater element, thereby improving efficiency.
[0011] According to a second aspect, the present invention provides a printer system which incorporates a printhead, the printhead comprising:
[0012] a plurality of nozzles; and,
[0013] at least one heater element corresponding to each of the nozzles respectively, the heater element configured for thermal contact with a bubble forming liquid; such that, heating the heater element to a temperature above the boiling point of the bubble forming liquid forms a gas bubble that causes the ejection of a drop of an ejectable liquid through the nozzle corresponding to that heater element; wherein, the gas bubble displaces less than 4 nanograms of the ejectable liquid to cause the ejection of the drop.
[0014] According to a third aspect, the present invention provides a method of ejecting drops of an ejectable liquid from a printhead, the printhead comprising a plurality of nozzles; and, at least one heater element corresponding to each of the nozzles respectively;
[0015] the method comprising the steps of:
[0016] placing bubble forming liquid into thermal contact with the heater element;
[0017] heating the heater element to a temperature above the boiling point of the bubble forming liquid to form a gas bubble such that a drop of an ejectable liquid is ejected through the nozzle corresponding to that heater element; wherein, the gas bubble displaces less than 4 nanograms of the ejectable liquid to cause the ejection of the drop.
[0018] Preferably, the gas bubble displaces less than 3 nanograms of the ejectable liquid to cause the ejection of the drop. In a further preferred form, the gas bubble displaces less than 2 nanograms of the ejectable liquid to cause the ejection of the drop. In a particularly desirable embodiment, the gas bubble displaces less than 1.5 nanograms of the ejectable liquid to cause the ejection of the drop.
[0019] As will be understood by those skilled in the art, the ejection of a drop of the ejectable liquid as described herein, is caused by the generation of a vapor bubble in a bubble forming liquid, which, in embodiments, is the same body of liquid as the ejectable liquid. The generated bubble causes an increase in pressure in ejectable liquid, which forces the drop through the relevant nozzle. The bubble is generated by Joule heating of a heater element which is in thermal contact with the ink. The electrical pulse applied to the heater is of brief duration, typically less than 2 microseconds. Due to stored heat in the liquid, the bubble expands for a few microseconds after the heater pulse is turned off. As the vapor cools, it recondenses, resulting in bubble collapse. The bubble collapses to a point determined by the dynamic interplay of inertia and surface tension of the ink. In this specification, such a point is referred to as the “point of collapse” of the bubble.
[0020] The printhead according to the invention comprises a plurality of nozzles, as well as a chamber and one or more heater elements corresponding to each nozzle. Each portion of the printhead pertaining to a single nozzle, its chamber and its one or more elements, is referred to herein as a “unit cell”.
[0021] In this specification, where reference is made to parts being in thermal contact with each other, this means that they are positioned relative to each other such that, when one of the parts is heated, it is capable of heating the other part, even though the parts, themselves, might not be in physical contact with each other.
[0022] Also, the term “ink” is used to signify any ejectable liquid, and is not limited to conventional inks containing colored dyes. Examples of non-colored inks include fixatives, infra-red absorber inks, functionalized chemicals, adhesives, biological fluids, water and other solvents, and so on. The ink or ejectable liquid also need not necessarily be a strictly a liquid, and may contain a suspension of solid particles or be solid at room temperature and liquid at the ejection temperature.
[0023] In this specification, the term “periodic element” refers to an element of a type reflected in the periodic table of elements.
DETAILED DESCRIPTION OF THE DRAWINGS
[0024] Preferred embodiments of the invention will now be described, by way of example only, with reference to the accompanying representations. The drawings are described as follows.
[0025] FIG. 1 is a schematic cross-sectional view through an ink chamber of a unit cell of a printhead according to an embodiment of the invention, at a particular stage of operation.
[0026] FIG. 2 is a schematic cross-sectional view through the ink chamber FIG. 1 , at another stage of operation.
[0027] FIG. 3 is a schematic cross-sectional view through the ink chamber FIG. 1 , at yet another stage of operation.
[0028] FIG. 4 is a schematic cross-sectional view through the ink chamber FIG. 1 , at yet a further stage of operation.
[0029] FIG. 5 is a diagrammatic cross-sectional view through a unit cell of a printhead in accordance with the an embodiment of the invention showing the collapse of a vapor bubble.
[0030] FIGS. 6 , 8 , 10 , 11 , 13 , 14 , 16 , 18 , 19 , 21 , 23 , 24 , 26 , 28 and 30 are schematic perspective views ( FIG. 30 being partly cut away) of a unit cell of a printhead in accordance with an embodiment of the invention, at various successive stages in the production process of the printhead.
[0031] FIGS. 7 , 9 , 12 , 15 , 17 , 20 , 22 , 25 , 27 , 29 and 31 are each schematic plan views of a mask suitable for use in performing the production stage for the printhead, as represented in the respective immediately preceding figures.
[0032] FIG. 32 is a further schematic perspective view of the unit cell of FIG. 30 shown with the nozzle plate omitted.
[0033] FIG. 33 is a schematic perspective view, partly cut away, of a unit cell of a printhead according to the invention having another particular embodiment of heater element.
[0034] FIG. 34 is a schematic plan view of a mask suitable for use in performing the production stage for the printhead of FIG. 33 for forming the heater element thereof.
[0035] FIG. 35 is a schematic perspective view, partly cut away, of a unit cell of a printhead according to the invention having a further particular embodiment of heater element.
[0036] FIG. 36 is a schematic plan view of a mask suitable for use in performing the production stage for the printhead of FIG. 35 for forming the heater element thereof.
[0037] FIG. 37 is a further schematic perspective view of the unit cell of FIG. 35 shown with the nozzle plate omitted.
[0038] FIG. 38 is a schematic perspective view, partly cut away, of a unit cell of a printhead according to the invention having a further particular embodiment of heater element.
[0039] FIG. 39 is a schematic plan view of a mask suitable for use in performing the production stage for the printhead of FIG. 38 for forming the heater element thereof.
[0040] FIG. 40 is a further schematic perspective view of the unit cell of FIG. 38 shown with the nozzle plate omitted.
[0041] FIG. 41 is a schematic section through a nozzle chamber of a printhead according to an embodiment of the invention showing a suspended beam heater element immersed in a bubble forming liquid.
[0042] FIG. 42 is schematic section through a nozzle chamber of a printhead according to an embodiment of the invention showing a suspended beam heater element suspended at the top of a body of a bubble forming liquid.
[0043] FIG. 43 is a diagrammatic plan view of a unit cell of a printhead according to an embodiment of the invention showing a nozzle.
[0044] FIG. 44 is a diagrammatic plan view of a plurality of unit cells of a printhead according to an embodiment of the invention showing a plurality of nozzles.
[0045] FIG. 45 is a diagrammatic section through a nozzle chamber not in accordance with the invention showing a heater element embedded in a substrate.
[0046] FIG. 46 is a diagrammatic section through a nozzle chamber in accordance with an embodiment of the invention showing a heater element in the form of a suspended beam.
[0047] FIG. 47 is a diagrammatic section through a nozzle chamber of a prior art printhead showing a heater element embedded in a substrate.
[0048] FIG. 48 is a diagrammatic section through a nozzle chamber in accordance with an embodiment of the invention showing a heater element defining a gap between parts of the element.
[0049] FIG. 49 is a diagrammatic section through a nozzle chamber not in accordance with the invention, showing a thick nozzle plate.
[0050] FIG. 50 is a diagrammatic section through a nozzle chamber in accordance with an embodiment of the invention showing a thin nozzle plate.
[0051] FIG. 51 is a diagrammatic section through a nozzle chamber in accordance with an embodiment of the invention showing two heater elements.
[0052] FIG. 52 is a diagrammatic section through a nozzle chamber of a prior art printhead showing two heater elements.
[0053] FIG. 53 is a diagrammatic section through a pair of adjacent unit cells of a printhead according to an embodiment of the invention, showing two different nozzles after drops having different volumes have been ejected therethrough.
[0054] FIGS. 54 and 55 are diagrammatic sections through a heater element of a prior art printhead.
[0055] FIG. 56 is a diagrammatic section through a conformally coated heater element according to an embodiment of the invention.
[0056] FIG. 57 is a diagrammatic elevational view of a heater element, connected to electrodes, of a printhead according to an embodiment of the invention.
[0057] FIG. 58 is a schematic exploded perspective view of a printhead module of a printhead according to an embodiment of the invention.
[0058] FIG. 59 is a schematic perspective view the printhead module of FIG. 58 shown unexploded.
[0059] FIG. 60 is a schematic side view, shown partly in section, of the printhead module of FIG. 58 .
[0060] FIG. 61 is a schematic plan view of the printhead module of FIG. 58 .
[0061] FIG. 62 is a schematic exploded perspective view of a printhead according to an embodiment of the invention.
[0062] FIG. 63 is a schematic further perspective view of the printhead of FIG. 62 shown unexploded.
[0063] FIG. 64 is a schematic front view of the printhead of FIG. 62 .
[0064] FIG. 65 is a schematic rear view of the printhead of FIG. 62 .
[0065] FIG. 66 is a schematic bottom view of the printhead of FIG. 62 .
[0066] FIG. 67 is a schematic plan view of the printhead of FIG. 62 .
[0067] FIG. 68 is a schematic perspective view of the printhead as shown in FIG. 62 , but shown unexploded.
[0068] FIG. 69 is a schematic longitudinal section through the printhead of FIG. 62 .
[0069] FIG. 70 is a block diagram of a printer system according to an embodiment of the invention.
[0070] FIG. 71 is a schematic, partially cut away, perspective view of a further embodiment of a unit cell of a printhead.
[0071] FIG. 72 is a schematic, partially cut away, exploded perspective view of the unit cell of FIG. 71 .
[0072] FIG. 73 is a schematic, partially cut away, perspective view of a further embodiment of a unit cell of a printhead.
[0073] FIG. 74 is a schematic, partially cut away, exploded perspective view of the unit cell of FIG. 73 .
[0074] FIG. 75 is a schematic, partially cut away, perspective view of a further embodiment of a unit cell of a printhead.
[0075] FIG. 76 is a schematic, partially cut away, exploded perspective view of the unit cell of FIG. 75 .
[0076] FIG. 77 is a schematic, partially cut away, perspective view of a further embodiment of a unit cell of a printhead.
[0077] FIG. 78 is a schematic, partially cut away, perspective view of a further embodiment of a unit cell of a printhead.
[0078] FIG. 79 is a schematic, partially cut away, exploded perspective view of the unit cell of FIG. 78 .
[0079] FIGS. 80 to 90 are schematic perspective views of the unit cell shown in FIGS. 78 and 79 , at various successive stages in the production process of the printhead.
[0080] FIGS. 91 and 92 show schematic, partially cut away, schematic perspective views of two variations of the unit cell of FIGS. 78 to 90 .
[0081] FIG. 93 is a schematic, partially cut away, perspective view of a further embodiment of a unit cell of a printhead.
[0082] FIG. 94 is a schematic, partially cut away, perspective view of a further embodiment of a unit cell of a printhead.
DETAILED DESCRIPTION
[0083] In the description than follows, corresponding reference numerals, or corresponding prefixes of reference numerals (i.e. the parts of the reference numerals appearing before a point mark) which are used in different figures relate to corresponding parts. Where there are corresponding prefixes and differing suffixes to the reference numerals, these indicate different specific embodiments of corresponding parts.
Overview of the Invention and General Discussion of Operation
[0084] With reference to FIGS. 1 to 4 , the unit cell 1 of a printhead according to an embodiment of the invention comprises a nozzle plate 2 with nozzles 3 therein, the nozzles having nozzle rims 4 , and apertures 5 extending through the nozzle plate. The nozzle plate 2 is plasma etched from a silicon nitride structure which is deposited, by way of chemical vapor deposition (CVD), over a sacrificial material which is subsequently etched.
[0085] The printhead also includes, with respect to each nozzle 3 , side walls 6 on which the nozzle plate is supported, a chamber 7 defined by the walls and the nozzle plate 2 , a multi-layer substrate 8 and an inlet passage 9 extending through the multi-layer substrate to the far side (not shown) of the substrate. A looped, elongate heater element 10 is suspended within the chamber 7 , so that the element is in the form of a suspended beam. The printhead as shown is a microelectromechanical system (MEMS) structure, which is formed by a lithographic process which is described in more detail below.
[0086] When the printhead is in use, ink 11 from a reservoir (not shown) enters the chamber 7 via the inlet passage 9 , so that the chamber fills to the level as shown in FIG. 1 . Thereafter, the heater element 10 is heated for somewhat less than 1 micro second, so that the heating is in the form of a thermal pulse. It will be appreciated that the heater element 10 is in thermal contact with the ink 11 in the chamber 7 so that when the element is heated, this causes the generation of vapor bubbles 12 in the ink. Accordingly, the ink 11 constitutes a bubble forming liquid. FIG. 1 shows the formation of a bubble 12 approximately 1 microsecond after generation of the thermal pulse, that is, when the bubble has just nucleated on the heater elements 10 . It will be appreciated that, as the heat is applied in the form of a pulse, all the energy necessary to generate the bubble 12 is to be supplied within that short time.
[0087] Turning briefly to FIG. 34 , there is shown a mask 13 for forming a heater 14 (as shown in FIG. 33 ) of the printhead (which heater includes the element 10 referred to above), during a lithographic process, as described in more detail below. As the mask 13 is used to form the heater 14 , the shape of various of its parts correspond to the shape of the element 10 . The mask 13 therefore provides a useful reference by which to identify various parts of the heater 14 . The heater 14 has electrodes 15 corresponding to the parts designated 15 . 34 of the mask 13 and a heater element 10 corresponding to the parts designated 10 . 34 of the mask. In operation, voltage is applied across the electrodes 15 to cause current to flow through the element 10 . The electrodes 15 are much thicker than the element 10 so that most of the electrical resistance is provided by the element. Thus, nearly all of the power consumed in operating the heater 14 is dissipated via the element 10 , in creating the thermal pulse referred to above.
[0088] When the element 10 is heated as described above, the bubble 12 forms along the length of the element, this bubble appearing, in the cross-sectional view of FIG. 1 , as four bubble portions, one for each of the element portions shown in cross section.
[0089] The bubble 12 , once generated, causes an increase in pressure within the chamber 7 , which in turn causes the ejection of a drop 16 of the ink 11 through the nozzle 3 . The rim 4 assists in directing the drop 16 as it is ejected, so as to minimize the chance of a drop misdirection.
[0090] The reason that there is only one nozzle 3 and chamber 7 per inlet passage 9 is so that the pressure wave generated within the chamber, on heating of the element 10 and forming of a bubble 12 , does not effect adjacent chambers and their corresponding nozzles.
[0091] The advantages of the heater element 10 being suspended rather than being embedded in any solid material, is discussed below.
[0092] FIGS. 2 and 3 show the unit cell 1 at two successive later stages of operation of the printhead. It can be seen that the bubble 12 generates further, and hence grows, with the resultant advancement of ink 11 through the nozzle 3 . The shape of the bubble 12 as it grows, as shown in FIG. 3 , is determined by a combination of the inertial dynamics and the surface tension of the ink 11 . The surface tension tends to minimize the surface area of the bubble 12 so that, by the time a certain amount of liquid has evaporated, the bubble is essentially disk-shaped.
[0093] The increase in pressure within the chamber 7 not only pushes ink 11 out through the nozzle 3 , but also pushes some ink back through the inlet passage 9 . However, the inlet passage 9 is approximately 200 to 300 microns in length, and is only approximately 16 microns in diameter. Hence there is a substantial viscous drag. As a result, the predominant effect of the pressure rise in the chamber 7 is to force ink out through the nozzle 3 as an ejected drop 16 , rather than back through the inlet passage 9 .
[0094] Turning now to FIG. 4 , the printhead is shown at a still further successive stage of operation, in which the ink drop 16 that is being ejected is shown during its “necking phase” before the drop breaks off. At this stage, the bubble 12 has already reached its maximum size and has then begun to collapse towards the point of collapse 17 , as reflected in more detail in FIG. 5 .
[0095] The collapsing of the bubble 12 towards the point of collapse 17 causes some ink 11 to be drawn from within the nozzle 3 (from the sides 18 of the drop), and some to be drawn from the inlet passage 9 , towards the point of collapse. Most of the ink 11 drawn in this manner is drawn from the nozzle 3 , forming an annular neck 19 at the base of the drop 16 prior to its breaking off.
[0096] The drop 16 requires a certain amount of momentum to overcome surface tension forces, in order to break off. As ink 11 is drawn from the nozzle 3 by the collapse of the bubble 12 , the diameter of the neck 19 reduces thereby reducing the amount of total surface tension holding the drop, so that the momentum of the drop as it is ejected out of the nozzle is sufficient to allow the drop to break off.
[0097] When the drop 16 breaks off, cavitation forces are caused as reflected by the arrows 20 , as the bubble 12 collapses to the point of collapse 17 . It will be noted that there are no solid surfaces in the vicinity of the point of collapse 17 on which the cavitation can have an effect.
Manufacturing Process
[0098] Relevant parts of the manufacturing process of a printhead according to embodiments of the invention are now described with reference to FIGS. 6 to 29 .
[0099] Referring to FIG. 6 , there is shown a cross-section through a silicon substrate portion 21 , being a portion of a Memjet printhead, at an intermediate stage in the production process thereof. This figure relates to that portion of the printhead corresponding to a unit cell 1 . The description of the manufacturing process that follows will be in relation to a unit cell 1 , although it will be appreciated that the process will be applied to a multitude of adjacent unit cells of which the whole printhead is composed.
[0100] FIG. 6 represents the next successive step, during the manufacturing process, after the completion of a standard CMOS fabrication process, including the fabrication of CMOS drive transistors (not shown) in the region 22 in the substrate portion 21 , and the completion of standard CMOS interconnect layers 23 and passivation layer 24 . Wiring indicated by the dashed lines 25 electrically interconnects the transistors and other drive circuitry (also not shown) and the heater element corresponding to the nozzle.
[0101] Guard rings 26 are formed in the metallization of the interconnect layers 23 to prevent ink 11 from diffusing from the region, designated 27 , where the nozzle of the unit cell 1 will be formed, through the substrate portion 21 to the region containing the wiring 25 , and corroding the CMOS circuitry disposed in the region designated 22 .
[0102] The first stage after the completion of the CMOS fabrication process consists of etching a portion of the passivation layer 24 to form the passivation recesses 29 .
[0103] FIG. 8 shows the stage of production after the etching of the interconnect layers 23 , to form an opening 30 . The opening 30 is to constitute the ink inlet passage to the chamber that will be formed later in the process.
[0104] FIG. 10 shows the stage of production after the etching of a hole 31 in the substrate portion 21 at a position where the nozzle 3 is to be formed. Later in the production process, a further hole (indicated by the dashed line 32 ) will be etched from the other side (not shown) of the substrate portion 21 to join up with the hole 31 , to complete the inlet passage to the chamber. Thus, the hole 32 will not have to be etched all the way from the other side of the substrate portion 21 to the level of the interconnect layers 23 .
[0105] If, instead, the hole 32 were to be etched all the way to the interconnect layers 23 , then to avoid the hole 32 being etched so as to destroy the transistors in the region 22 , the hole 32 would have to be etched a greater distance away from that region so as to leave a suitable margin (indicated by the arrow 34 ) for etching inaccuracies. But the etching of the hole 31 from the top of the substrate portion 21 , and the resultant shortened depth of the hole 32 , means that a lesser margin 34 need be left, and that a substantially higher packing density of nozzles can thus be achieved.
[0106] FIG. 11 shows the stage of production after a four micron thick layer 35 of a sacrificial resist has been deposited on the layer 24 . This layer 35 fills the hole 31 and now forms part of the structure of the printhead. The resist layer 35 is then exposed with certain patterns (as represented by the mask shown in FIG. 12 ) to form recesses 36 and a slot 37 . This provides for the formation of contacts for the electrodes 15 of the heater element to be formed later in the production process. The slot 37 will provide, later in the process, for the formation of the nozzle walls 6 , that will define part of the chamber 7 .
[0107] FIG. 13 shows the stage of production after the deposition, on the layer 35 , of a 0.25 micron thick layer 38 of heater material, which, in the present embodiment, is of titanium nitride.
[0108] FIG. 14 shows the stage of production after patterning and etching of the heater layer 38 to form the heater 14 , including the heater element 10 and electrodes 15 .
[0109] FIG. 16 shows the stage of production after another sacrificial resist layer 39 , about 1 micron thick, has been added.
[0110] FIG. 18 shows the stage of production after a second layer 40 of heater material has been deposited. In a preferred embodiment, this layer 40 , like the first heater layer 38 , is of 0.25 micron thick titanium nitride.
[0111] FIG. 19 then shows this second layer 40 of heater material after it has been etched to form the pattern as shown, indicated by reference numeral 41 . In this illustration, this patterned layer does not include a heater layer element 10 , and in this sense has no heater functionality. However, this layer of heater material does assist in reducing the resistance of the electrodes 15 of the heater 14 so that, in operation, less energy is consumed by the electrodes which allows greater energy consumption by, and therefore greater effectiveness of, the heater elements 10 . In the dual heater embodiment illustrated in FIG. 38 , the corresponding layer 40 does contain a heater 14 .
[0112] FIG. 21 shows the stage of production after a third layer 42 , of sacrificial resist, has been deposited. The uppermost level of this layer will constitute the inner surface of the nozzle plate 2 to be formed later. This is also the inner extent of the ejection aperture 5 of the nozzle. The height of this layer 42 must be sufficient to allow for the formation of a bubble 12 in the region designated 43 during operation of the printhead. However, the height of layer 42 determines the mass of ink that the bubble must move in order to eject a droplet. In light of this, the printhead structure of the present invention is designed such that the heater element is much closer to the ejection aperture than in prior art printheads. The mass of ink moved by the bubble is reduced. The generation of a bubble sufficient for the ejection of the desired droplet will require less energy, thereby improving efficiency.
[0113] FIG. 23 shows the stage of production after the roof layer 44 has been deposited, that is, the layer which will constitute the nozzle plate 2 . Instead of being formed from 100 micron thick polyimide film, the nozzle plate 2 is formed of silicon nitride, just 2 microns thick.
[0114] FIG. 24 shows the stage of production after the chemical vapor deposition (CVD) of silicon nitride forming the layer 44 , has been partly etched at the position designated 45 , so as to form the outside part of the nozzle rim 4 , this outside part being designated 4 . 1
[0115] FIG. 26 shows the stage of production after the CVD of silicon nitride has been etched all the way through at 46 , to complete the formation of the nozzle rim 4 and to form the ejection aperture 5 , and after the CVD silicon nitride has been removed at the position designated 47 where it is not required.
[0116] FIG. 28 shows the stage of production after a protective layer 48 of resist has been applied. After this stage, the substrate portion 21 is then ground from its other side (not shown) to reduce the substrate portion from its nominal thickness of about 800 microns to about 200 microns, and then, as foreshadowed above, to etch the hole 32 . The hole 32 is etched to a depth such that it meets the hole 31 .
[0117] Then, the sacrificial resist of each of the resist layers 35 , 39 , 42 and 48 , is removed using oxygen plasma, to form the structure shown in FIG. 30 , with walls 6 and nozzle plate 2 which together define the chamber 7 (part of the walls and nozzle plate being shown cut-away). It will be noted that this also serves to remove the resist filling the hole 31 so that this hole, together with the hole 32 (not shown in FIG. 30 ), define a passage extending from the lower side of the substrate portion 21 to the nozzle 3 , this passage serving as the ink inlet passage, generally designated 9 , to the chamber 7 .
[0118] FIG. 32 shows the printhead with the nozzle guard and chamber walls removed to clearly illustrate the vertically stacked arrangement of the heater elements 10 and the electrodes 15 .
[0119] While the above production process is used to produce the embodiment of the printhead shown in FIG. 30 , further printhead embodiments, having different heater structures, are shown in FIG. 33 , FIGS. 35 and 37 , and FIGS. 38 and 40 .
Control of Ink Drop Ejection
[0120] Referring once again to FIG. 30 , the unit cell 1 shown, as mentioned above, is shown with part of the walls 6 and nozzle plate 2 cut-away, which reveals the interior of the chamber 7 . The heater 14 is not shown cut away, so that both halves of the heater element 10 can be seen.
[0121] In operation, ink 11 passes through the ink inlet passage 9 (see FIG. 28 ) to fill the chamber 7 . Then a voltage is applied across the electrodes 15 to establish a flow of electric current through the heater element 10 . This heats the element 10 , as described above in relation to FIG. 1 , to form a vapor bubble in the ink within the chamber 7 .
[0122] The various possible structures for the heater 14 , some of which are shown in FIGS. 33 , 35 and 37 , and 38 , can result in there being many variations in the ratio of length to width of the heater elements 10 . Such variations (even though the surface area of the elements 10 may be the same) may have significant effects on the electrical resistance of the elements, and therefore on the balance between the voltage and current to achieve a certain power of the element.
[0123] Modern drive electronic components tend to require lower drive voltages than earlier versions, with lower resistances of drive transistors in their “on” state. Thus, in such drive transistors, for a given transistor area, there is a tendency to higher current capability and lower voltage tolerance in each process generation.
[0124] FIG. 36 , referred to above, shows the shape, in plan view, of a mask for forming the heater structure of the embodiment of the printhead shown in FIG. 35 . Accordingly, as FIG. 36 represents the shape of the heater element 10 of that embodiment, it is now referred to in discussing that heater element. During operation, current flows vertically into the electrodes 15 (represented by the parts designated 15 . 36 ), so that the current flow area of the electrodes is relatively large, which, in turn, results in there being a low electrical resistance. By contrast, the element 10 , represented in FIG. 36 by the part designated 10 . 36 , is long and thin, with the width of the element in this embodiment being 1 micron and the thickness being 0.25 microns.
[0125] It will be noted that the heater 14 shown in FIG. 33 has a significantly smaller element 10 than the element 10 shown in FIG. 35 , and has just a single loop 36 . Accordingly, the element 10 of FIG. 33 will have a much lower electrical resistance, and will permit a higher current flow, than the element 10 of FIG. 35 . It therefore requires a lower drive voltage to deliver a given energy to the heater 14 in a given time.
[0126] In FIG. 38 , on the other hand, the embodiment shown includes a heater 14 having two heater elements 10 . 1 and 10 . 2 corresponding to the same unit cell 1 . One of these elements 10 . 2 is twice the width as the other element 10 . 1 , with a correspondingly larger surface area. The various paths of the lower element 10 . 2 are 2 microns in width, while those of the upper element 10 . 1 are 1 micron in width. Thus the energy applied to ink in the chamber 7 by the lower element 10 . 2 is twice that applied by the upper element 10 . 1 at a given drive voltage and pulse duration. This permits a regulating of the size of vapor bubbles and hence of the size of ink drop ejected due to the bubbles.
[0127] Assuming that the energy applied to the ink by the upper element 10 . 1 is X, it will be appreciated that the energy applied by the lower element 10 . 2 is about 2×, and the energy applied by the two elements together is about 3×. Of course, the energy applied when neither element is operational, is zero. Thus, in effect, two bits of information can be printed with the one nozzle 3 .
[0128] As the above factors of energy output may not be achieved exactly in practice, some “fine tuning” of the exact sizing of the elements 10 . 1 and 10 . 2 , or of the drive voltages that are applied to them, may be required.
[0129] It will also be noted that the upper element 10 . 1 is rotated through 180° about a vertical axis relative to the lower element 10 . 2 . This is so that their electrodes 15 are not coincident, allowing independent connection to separate drive circuits.
FEATURES AND ADVANTAGES OF PARTICULAR EMBODIMENTS
[0130] Discussed below, under appropriate headings, are certain specific features of embodiments of the invention, and the advantages of these features. The features are to be considered in relation to all of the drawings pertaining to the present invention unless the context specifically excludes certain drawings, and relates to those drawings specifically referred to.
Suspended Beam Heater
[0131] With reference to FIG. 1 , and as mentioned above, the heater element 10 is in the form of a suspended beam, and this is suspended over at least a portion (designated 11 . 1 ) of the ink 11 (bubble forming liquid). The element 10 is configured in this way rather than forming part of, or being embedded in, a substrate as is the case in existing printhead systems made by various manufacturers such as Hewlett Packard, Canon and Lexmark. This constitutes a significant difference between embodiments of the present invention and the prior ink jet technologies.
[0132] The main advantage of this feature is that a higher efficiency can be achieved by avoiding the unnecessary heating of the solid material that surrounds the heater elements 10 (for example the solid material forming the chamber walls 6 , and surrounding the inlet passage 9 ) which takes place in the prior art devices. The heating of such solid material does not contribute to the formation of vapor bubbles 12 , so that the heating of such material involves the wastage of energy. The only energy which contributes in any significant sense to the generation of the bubbles 12 is that which is applied directly into the liquid which is to be heated, which liquid is typically the ink 11 .
[0133] In one preferred embodiment, as illustrated in FIG. 1 , the heater element 10 is suspended within the ink 11 (bubble forming liquid), so that this liquid surrounds the element. This is further illustrated in FIG. 41 . In another possible embodiment, as illustrated in FIG. 42 , the heater element 10 beam is suspended at the surface of the ink (bubble forming liquid) 11 , so that this liquid is only below the element rather than surrounding it, and there is air on the upper side of the element. The embodiment described in relation to FIG. 41 is preferred as the bubble 12 will form all around the element 10 unlike in the embodiment described in relation to FIG. 42 where the bubble will only form below the element. Thus the embodiment of FIG. 41 is likely to provide a more efficient operation.
[0134] As can be seen in, for example, with reference to FIGS. 30 and 31 , the heater element 10 beam is supported only on one side and is free at its opposite side, so that it constitutes a cantilever. This minimises any direct contact with, and hence reduces heat transfer to, the solid material of the nozzle.
Efficiency of the Printhead
[0135] The printhead of the present invention has a design that configures the nozzle structure for enhancing efficiency by reducing the mass of ink that needs to be displaced in order to eject a drop from the nozzle. As a result, the gas bubble displaces less than 4 nanograms of the ejectable liquid to cause the ejection of the drop. Preferably, the gas bubble displaces less than 3 nanograms. In a further preferred form, less than 2 nanograms of the ejectable liquid is displaced by the gas bubble. In a particularly preferred embodiment, the gas bubble displaces less than 1.5 nanograms of the ejectable liquid to cause the ejection of the drop.
[0136] It will be appreciated by those skilled in the art that prior art devices generally require over 5 microjoules to heat the element sufficiently to generate a vapor bubble 12 to eject an ink drop 16 . Thus, the energy requirements of the present invention are an order of magnitude lower than that of known thermal ink jet systems. This lower energy consumption allows lower operating costs, smaller power supplies, and so on, but also dramatically simplifies printhead cooling, allows higher densities of nozzles 3 , and permits printing at higher resolutions.
[0137] These advantages of the present invention are especially significant in embodiments where the individual ejected ink drops 16 , themselves, constitute the major cooling mechanism of the printhead, as described further below.
Self-Cooling of the Printhead
[0138] This feature of the invention provides that the energy applied to a heater element 10 to form a vapor bubble 12 so as to eject a drop 16 of ink 11 is removed from the printhead by a combination of the heat removed by the ejected drop itself, and the ink that is taken into the printhead from the ink reservoir (not shown). The result of this is that the net “movement” of heat will be outwards from the printhead, to provide for automatic cooling. Under these circumstances, the printhead does not require any other cooling systems.
[0139] As the ink drop 16 ejected and the amount of ink 11 drawn into the printhead to replace the ejected drop are constituted by the same type of liquid, and will essentially be of the same mass, it is convenient to express the net movement of energy as, on the one hand, the energy added by the heating of the element 10 , and on the other hand, the net removal of heat energy that results from ejecting the ink drop 16 and the intake of the replacement quantity of ink 11 . Assuming that the replacement quantity of ink 11 is at ambient temperature, the change in energy due to net movement of the ejected and replacement quantities of ink can conveniently be expressed as the heat that would be required to raise the temperature of the ejected drop 16 , if it were at ambient temperature, to the actual temperature of the drop as it is ejected.
[0140] It will be appreciated that a determination of whether the above criteria are met depends on what constitutes the ambient temperature. In the present case, the temperature that is taken to be the ambient temperature is the temperature at which ink 11 enters the printhead from the ink storage reservoir (not shown) which is connected, in fluid flow communication, to the inlet passages 9 of the printhead. Typically the ambient temperature will be the room ambient temperature, which is usually roughly 20 degrees C. (Celsius).
[0141] However, the ambient temperature may be less, if for example, the room temperature is lower, or if the ink 11 entering the printhead is refrigerated.
[0142] In one preferred embodiment, the printhead is designed to achieve complete self-cooling (i.e. where the outgoing heat energy due to the net effect of the ejected and replacement quantities of ink 11 is equal to the heat energy added by the heater element 10 ).
[0143] By way of example, assuming that the ink 11 is the bubble forming liquid and is water based, thus having a boiling point of approximately 100 degrees C., and if the ambient temperature is 40 degrees C., then there is a maximum of 60 degrees C. from the ambient temperature to the ink boiling temperature and that is the maximum temperature rise that the printhead could undergo.
[0144] It is desirable to avoid having ink temperatures within the printhead (other than at time of ink drop 16 ejection) which are very close to the boiling point of the ink 11 . If the ink 11 were at such a temperature, then temperature variations between parts of the printhead could result in some regions being above boiling point, with the unintended, and therefore undesirable, formation of vapor bubbles 12 . Accordingly, a preferred embodiment of the invention is configured such that complete self-cooling, as described above, can be achieved when the maximum temperature of the ink 11 (bubble forming liquid) in a particular nozzle chamber 7 is 10 degrees C. below its boiling point when the heating element 10 is not active.
[0145] The main advantage of the feature presently under discussion, and its various embodiments, is that it allows for a high nozzle density and for a high speed of printhead operation without requiring elaborate cooling methods for preventing undesired boiling in nozzles 3 adjacent to nozzles from which ink drops 16 are being ejected. This can allow as much as a hundred-fold increase in nozzle packing density than would be the case if such a feature, and the temperature criteria mentioned, were not present.
Areal Density of Nozzles
[0146] This feature of the invention relates to the density, by area, of the nozzles 3 on the printhead. With reference to FIG. 1 , the nozzle plate 2 has an upper surface 50 , and the present aspect of the invention relates to the packing density of nozzles 3 on that surface. More specifically, the areal density of the nozzles 3 on that surface 50 is over 10,000 nozzles per square cm of surface area.
[0147] In one preferred embodiment, the areal density exceeds 20,000 nozzles per square cm of surface area, while in another preferred embodiment, the areal density exceeds 40,000 nozzles per square cm. In a preferred embodiment, the areal density is 48 828 nozzles per square cm.
[0148] When referring to the areal density, each nozzle 3 is taken to include the drive-circuitry corresponding to the nozzle, which consists, typically, of a drive transistor, a shift register, an enable gate and clock regeneration circuitry (this circuitry not being specifically identified).
[0149] With reference to FIG. 43 in which a single unit cell 1 is shown, the dimensions of the unit cell are shown as being 32 microns in width by 64 microns in length. The nozzle 3 of the next successive row of nozzles (not shown) immediately juxtaposes this nozzle, so that, as a result of the dimension of the outer periphery of the printhead chip, there are 48,828 nozzles 3 per square cm. This is about 85 times the nozzle areal density of a typical thermal ink jet printhead, and roughly 400 times the nozzle areal density of a piezoelectric printhead.
[0150] The main advantage of a high areal density is low manufacturing cost, as the devices are batch fabricated on silicon wafers of a particular size.
[0151] The more nozzles 3 that can be accommodated in a square cm of substrate, the more nozzles can be fabricated in a single batch, which typically consists of one wafer. The cost of manufacturing a CMOS plus MEMS wafer of the type used in the printhead of the present invention is, to some extent, independent of the nature of patterns that are formed on it. Therefore if the patterns are relatively small, a relatively large number of nozzles 3 can be included. This allows more nozzles 3 and more printheads to be manufactured for the same cost than in a cases where the nozzles had a lower areal density. The cost is directly proportional to the area taken by the nozzles 3 .
Bubble Formation on Opposite Sides of Heater Element
[0152] According to the present feature, the heater 14 is configured so that when a bubble 12 forms in the ink 11 (bubble forming liquid), it forms on both sides of the heater element 10 . Preferably, it forms so as to surround the heater element 10 where the element is in the form of a suspended beam.
[0153] The formation of a bubble 12 on both sides of the heater element 10 as opposed to on one side only, can be understood with reference to FIGS. 45 and 46 . In the first of these figures, the heater element 10 is adapted for the bubble 12 to be formed only on one side as, while in the second of these figures, the element is adapted for the bubble 12 to be formed on both sides, as shown.
[0154] In a configuration such as that of FIG. 45 , the reason that the bubble 12 forms on only one side of the heater element 10 is because the element is embedded in a substrate 51 , so that the bubble cannot be formed on the particular side corresponding to the substrate. By contrast, the bubble 12 can form on both sides in the configuration of FIG. 46 as the heater element 10 here is suspended.
[0155] Of course where the heater element 10 is in the form of a suspended beam as described above in relation to FIG. 1 , the bubble 12 is allowed to form so as to surround the suspended beam element.
[0156] The advantage of the bubble 12 forming on both sides is the higher efficiency that is achievable. This is due to a reduction in heat that is wasted in heating solid materials in the vicinity of the heater element 10 , which do not contribute to formation of a bubble 12 . This is illustrated in FIG. 45 , where the arrows 52 indicate the movements of heat into the solid substrate 51 . The amount of heat lost to the substrate 51 depends on the thermal conductivity of the solid materials of the substrate relative to that of the ink 11 , which may be water based. As the thermal conductivity of water is relatively low, more than half of the heat can be expected to be absorbed by the substrate 51 rather than by the ink 11 .
Prevention of Cavitation
[0157] As described above, after a bubble 12 has been formed in a printhead according to an embodiment of the present invention, the bubble collapses towards a point of collapse 17 . According to the feature presently being addressed, the heater elements 10 are configured to form the bubbles 12 so that the points of collapse 17 towards which the bubbles collapse, are at positions spaced from the heater elements. Preferably, the printhead is configured so that there is no solid material at such points of collapse 17 . In this way cavitation, being a major problem in prior art thermal ink jet devices, is largely eliminated.
[0158] Referring to FIG. 48 , in a preferred embodiment, the heater elements 10 are configured to have parts 53 which define gaps (represented by the arrow 54 ), and to form the bubbles 12 so that the points of collapse 17 to which the bubbles collapse are located at such gaps. The advantage of this feature is that it substantially avoids cavitation damage to the heater elements 10 and other solid material.
[0159] In a standard prior art system as shown schematically in FIG. 47 , the heater element 10 is embedded in a substrate 55 , with an insulating layer 56 over the element, and a protective layer 57 over the insulating layer. When a bubble 12 is formed by the element 10 , it is formed on top of the element. When the bubble 12 collapses, as shown by the arrows 58 , all of the energy of the bubble collapse is focussed onto a very small point of collapse 17 . If the protective layer 57 were absent, then the mechanical forces due to the cavitation that would result from the focussing of this energy to the point of collapse 17 , could chip away or erode the heater element 10 . However, this is prevented by the protective layer 57 .
[0160] Typically, such a protective layer 57 is of tantalum, which oxidizes to form a very hard layer of tantalum pentoxide (Ta 2 O 5 ). Although no known materials can fully resist the effects of cavitation, if the tantalum pentoxide should be chipped away due to the cavitation, then oxidation will again occur at the underlying tantalum metal, so as to effectively repair the tantalum pentoxide layer.
[0161] Although the tantalum pentoxide functions relatively well in this regard in known thermal ink jet systems, it has certain disadvantages. One significant disadvantage is that, in effect, virtually the whole protective layer 57 (having a thickness indicated by the reference numeral 59 ) must be heated in order to transfer the required energy into the ink 11 , to heat it so as to form a bubble 12 . This layer 57 has a high thermal mass due to the very high atomic weight of the tantalum, and this reduces the efficiency of the heat transfer. Not only does this increase the amount of heat which is required at the level designated 59 to raise the temperature at the level designated 60 sufficiently to heat the ink 11 , but it also results in a substantial thermal loss to take place in the directions indicated by the arrows 61 . This disadvantage would not be present if the heater element 10 was merely supported on a surface and was not covered by the protective layer 57 .
[0162] According to the feature presently under discussion, the need for a protective layer 57 , as described above, is avoided by generating the bubble 12 so that it collapses, as illustrated in FIG. 48 , towards a point of collapse 17 at which there is no solid material, and more particularly where there is the gap 54 between parts 53 of the heater element 10 . As there is merely the ink 11 itself in this location (prior to bubble generation), there is no material that can be eroded here by the effects of cavitation. The temperature at the point of collapse 17 may reach many thousands of degrees C., as is demonstrated by the phenomenon of sonoluminesence. This will break down the ink components at that point. However, the volume of extreme temperature at the point of collapse 17 is so small that the destruction of ink components in this volume is not significant.
[0163] The generation of the bubble 12 so that it collapses towards a point of collapse 17 where there is no solid material can be achieved using heater elements 10 corresponding to that represented by the part 10 . 34 of the mask shown in FIG. 34 . The element represented is symmetrical, and has a hole represented by the reference numeral 63 at its center. When the element is heated, the bubble forms around the element (as indicated by the dashed line 64 ) and then grows so that, instead of being of annular (doughnut) shape as illustrated by the dashed lines 64 and 65 ) it spans the element including the hole 63 , the hole then being filled with the vapor that forms the bubble. The bubble 12 is thus substantially disc-shaped. When it collapses, the collapse is directed so as to minimize the surface tension surrounding the bubble 12 . This involves the bubble shape moving towards a spherical shape as far as is permitted by the dynamics that are involved. This, in turn, results in the point of collapse being in the region of the hole 63 at the center of the heater element 10 , where there is no solid material.
[0164] The heater element 10 represented by the part 10 . 31 of the mask shown in FIG. 31 is configured to achieve a similar result, with the bubble generating as indicated by the dashed line 66 , and the point of collapse to which the bubble collapses being in the hole 67 at the center of the element.
[0165] The heater element 10 represented as the part 10 . 36 of the mask shown in FIG. 36 is also configured to achieve a similar result. Where the element 10 . 36 is dimensioned such that the hole 68 is small, manufacturing inaccuracies of the heater element may affect the extent to which a bubble can be formed such that its point of collapse is in the region defined by the hole. For example, the hole may be as little as a few microns across. Where high levels of accuracy in the element 10 . 36 cannot be achieved, this may result in bubbles represented as 12 . 36 that are somewhat lopsided, so that they cannot be directed towards a point of collapse within such a small region. In such a case, with regard to the heater element represented in FIG. 36 , the central loop 49 of the element can simply be omitted, thereby increasing the size of the region in which the point of collapse of the bubble is to fall.
Chemical Vapor Deposited Nozzle Plate, and Thin Nozzle Plates
[0166] The nozzle ejection aperture 5 of each unit cell 1 extends through the nozzle plate 2 , the nozzle plate thus constituting a structure which is formed by chemical vapor deposition (CVD). In various preferred embodiments, the CVD is of silicon nitride, silicon dioxide or oxi-nitride.
[0167] The advantage of the nozzle plate 2 being formed by CVD is that it is formed in place without the requirement for assembling the nozzle plate to other components such as the walls 6 of the unit cell 1 . This is an important advantage because the assembly of the nozzle plate 2 that would otherwise be required can be difficult to effect and can involve potentially complex issues. Such issues include the potential mismatch of thermal expansion between the nozzle plate 2 and the parts to which it would be assembled, the difficulty of successfully keeping components aligned to each other, keeping them planar, and so on, during the curing process of the adhesive which bonds the nozzle plate 2 to the other parts.
[0168] The issue of thermal expansion is a significant factor in the prior art, which limits the size of ink jets that can be manufactured. This is because the difference in the coefficient of thermal expansion between, for example, a nickel nozzle plate and a substrate to which the nozzle plate is connected, where this substrate is of silicon, is quite substantial. Consequently, over as small a distance as that occupied by, say, 1000 nozzles, the relative thermal expansion that occurs between the respective parts, in being heated from the ambient temperature to the curing temperature required for bonding the parts together, can cause a dimension mismatch of significantly greater than a whole nozzle length. This would be significantly detrimental for such devices.
[0169] Another problem addressed by the features of the invention presently under discussion, at least in embodiments thereof, is that, in prior art devices, nozzle plates that need to be assembled are generally laminated onto the remainder of the printhead under conditions of relatively high stress. This can result in breakages or undesirable deformations of the devices. The depositing of the nozzle plate 2 by CVD in embodiments of the present invention avoids this.
[0170] A further advantage of the present features of the invention, at least in embodiments thereof, is their compatibility with existing semiconductor manufacturing processes. Depositing a nozzle plate 2 by CVD allows the nozzle plate to be included in the printhead at the scale of normal silicon wafer production, using processes normally used for semi-conductor manufacture.
[0171] Existing thermal ink jet or bubble jet systems experience pressure transients, during the bubble generation phase, of up to 100 atmospheres. If the nozzle plates 2 in such devices were applied by CVD, then to withstand such pressure transients, a substantial thickness of CVD nozzle plate would be required. As would be understood by those skilled in the art, such thicknesses of deposited nozzle plates would give rise certain problems as discussed below.
[0172] For example, the thickness of nitride sufficient to withstand a 100 atmosphere pressure in the nozzle chamber 7 may be, say, 10 microns. With reference to FIG. 49 , which shows a unit cell 1 that is not in accordance with the present invention, and which has such a thick nozzle plate 2 , it will be appreciated that such a thickness can result in problems relating to drop ejection. In this case, due to the thickness of nozzle plate 2 , the fluidic drag exerted by the nozzle 3 as the ink 11 is ejected therethrough results in significant losses in the efficiency of the device.
[0173] Another problem that would exist in the case of such a thick nozzle plate 2 , relates to the actual etching process. This is assuming that the nozzle 3 is etched, as shown, perpendicular to the wafer 8 of the substrate portion, for example using a standard plasma etching. This would typically require more than 10 microns of resist 69 to be applied. To expose that thickness of resist 69 , the required level of resolution becomes difficult to achieve, as the focal depth of the stepper that is used to expose the resist is relatively small. Although it would be possible to expose this relevant depth of resist 69 using x-rays, this would be a relatively costly process.
[0174] A further problem that would exist with such a thick nozzle plate 2 in a case where a 10 micron thick layer of nitride were CVD deposited on a silicon substrate wafer, is that, because of the difference in thermal expansion between the CVD layer and the substrate, as well as the inherent stress of within thick deposited layer, the wafer could be caused to bow to such a degree that further steps in the lithographic process would become impractical. Thus, a 10 micron thick nozzle plate 2 is possible but (unlike in the present invention), disadvantageous.
[0175] With reference to FIG. 50 , in a Memjet thermal ink ejection device according to an embodiment of the present invention, the CVD nitride nozzle plate layer 2 is only 2 microns thick. Therefore the fluidic drag through the nozzle 3 is not particularly significant and is therefore not a major cause of loss.
[0176] Furthermore, the etch time, and the resist thickness required to etch nozzles 3 in such a nozzle plate 2 , and the stress on the substrate wafer 8 , will not be excessive.
[0177] The relatively thin nozzle plate 2 in this invention is enabled as the pressure generated in the chamber 7 is only approximately 1 atmosphere and not 100 atmospheres as in prior art devices, as mentioned above.
[0178] There are many factors which contribute to the significant reduction in pressure transient required to eject drops 16 in this system. These include:
[0000] 1. small size of chamber 7 ;
2. accurate fabrication of nozzle 3 and chamber 7 ;
3. stability of drop ejection at low drop velocities;
4. very low fluidic and thermal crosstalk between nozzles 3 ;
5. optimum nozzle size to bubble area;
6. low fluidic drag through thin (2 micron) nozzle 3 ;
7. low pressure loss due to ink ejection through the inlet 9 ;
8. self-cooling operation.
[0179] As mentioned above in relation the process described in terms of FIGS. 6 to 31 , the etching of the 2-micron thick nozzle plate layer 2 involves two relevant stages. One such stage involves the etching of the region designated 45 in FIGS. 24 and 50 , to form a recess outside of what will become the nozzle rim 4 . The other such stage involves a further etch, in the region designated 46 in FIGS. 26 and 50 , which actually forms the ejection aperture 5 and finishes the rim 4 .
Nozzle Plate Thicknesses
[0180] As addressed above in relation to the formation of the nozzle plate 2 by CVD, and with the advantages described in that regard, the nozzle plates in the present invention are thinner than in the prior art. More particularly, the nozzle plates 2 are less than 10 microns thick. In one preferred embodiment, the nozzle plate 2 of each unit cell 1 is less than 5 microns thick, while in another preferred embodiment, it is less than 2.5 microns thick. Indeed, a preferred thickness for the nozzle plate 2 is 2 microns thick.
Heater Elements Formed in Different Layers
[0181] According to the present feature, there is a plurality of heater elements 10 disposed within the chamber 7 of each unit cell 1 . The elements 10 , which are formed by the lithographic process as described above in relation to FIG. 6 to 31 , are formed in respective layers.
[0182] In preferred embodiments, as shown in FIGS. 38 , 40 and 51 , the heater elements 10 . 1 and 10 . 2 in the chamber 7 , are of different sizes relative to each other.
[0183] Also as will be appreciated with reference to the above description of the lithographic process, each heater element 10 . 1 , 10 . 2 is formed by at least one step of that process, the lithographic steps relating to each one of the elements 10 . 1 being distinct from those relating to the other element 10 . 2 .
[0184] The elements 10 . 1 , 10 . 2 are preferably sized relative to each other, as reflected schematically in the diagram of FIG. 51 , such that they can achieve binary weighted ink drop volumes, that is, so that they can cause ink drops 16 having different, binary weighted volumes to be ejected through the nozzle 3 of the particular unit cell 1 . The achievement of the binary weighting of the volumes of the ink drops 16 is determined by the relative sizes of the elements 10 . 1 and 10 . 2 . In FIG. 51 , the area of the bottom heater element 10 . 2 in contact with the ink 11 is twice that of top heater element 10 . 1 .
[0185] One known prior art device, patented by Canon, and illustrated schematically in FIG. 52 , also has two heater elements 10 . 1 and 10 . 2 for each nozzle, and these are also sized on a binary basis (i.e. to produce drops 16 with binary weighted volumes). These elements 10 . 1 , 10 . 2 are formed in a single layer, adjacent to each other in the nozzle chamber 7 . It will be appreciated that the bubble 12 . 1 formed by the small element 10 . 1 , only, is relatively small, while that 12 . 2 formed by the large element 10 . 2 , only, is relatively large. The bubble generated by the combined effects of the two elements, when they are actuated simultaneously, is designated 12 . 3 . Three differently sized ink drops 16 will be caused to be ejected by the three respective bubbles 12 . 1 , 12 . 2 and 12 . 3 .
[0186] It will be appreciated that the size of the elements 10 . 1 and 10 . 2 themselves are not required to be binary weighted to cause the ejection of drops 16 having different sizes or the ejection of useful combinations of drops. Indeed, the binary weighting may well not be represented precisely by the area of the elements 10 . 1 , 10 . 2 themselves. In sizing the elements 10 . 1 , 10 . 2 to achieve binary weighted drop volumes, the fluidic characteristics surrounding the generation of bubbles 12 , the drop dynamics characteristics, the quantity of liquid that is drawing back into the chamber 7 from the nozzle 3 once a drop 16 has broken off, and so forth, must be considered. Accordingly, the actual ratio of the surface areas of the elements 10 . 1 , 10 . 2 , or the performance of the two heaters, needs to be adjusted in practice to achieve the desired binary weighted drop volumes.
[0187] Where the size of the heater elements 10 . 1 , 10 . 2 is fixed and where the ratio of their surface areas is therefore fixed, the relative sizes of ejected drops 16 may be adjusted by adjusting the supply voltages to the two elements. This can also be achieved by adjusting the duration of the operation pulses of the elements 10 . 1 , 10 . 2 —i.e. their pulse widths. However, the pulse widths cannot exceed a certain amount of time, because once a bubble 12 has nucleated on the surface of an element 10 . 1 , 10 . 2 , then any duration of pulse width after that time will be of little or no effect.
[0188] On the other hand, the low thermal mass of the heater elements 10 . 1 , 10 . 2 allows them to be heated to reach, very quickly, the temperature at which bubbles 12 are formed and at which drops 16 are ejected. While the maximum effective pulse width is limited, by the onset of bubble nucleation, typically to around 0.5 microseconds, the minimum pulse width is limited only by the available current drive and the current density that can be tolerated by the heater elements 10 . 1 , 10 . 2 .
[0189] As shown in FIG. 51 , the two heaters elements 10 . 1 , 10 . 2 are connected to two respective drive circuits 70 . Although these circuits 70 may be identical to each other, a further adjustment can be effected by way of these circuits, for example by sizing the drive transistor (not shown) connected to the lower element 10 . 2 , which is the high current element, larger than that connected to the upper element 10 . 1 . If, for example, the relative currents provided to the respective elements 10 . 1 , 10 . 2 are in the ratio 2:1, the drive transistor of the circuit 70 connected to the lower element 10 . 2 would typically be twice the width of the drive transistor (also not shown) of the circuit 70 connected to the other element 10 . 1 .
[0190] In the prior art described in relation to FIG. 52 , the heater elements 10 . 1 , 10 . 2 , which are in the same layer, are produced simultaneously in the same step of the lithographic manufacturing process. In the embodiment of the present invention illustrated in FIG. 51 , the two heaters elements 10 . 1 , 10 . 2 , as mentioned above, are formed one after the other. Indeed, as described in the process illustrated with reference to FIGS. 6 to 31 , the material to form the element 10 . 2 is deposited and is then etched in the lithographic process, whereafter a sacrificial layer 39 is deposited on top of that element, and then the material for the other element 10 . 1 is deposited so that the sacrificial layer is between the two heater element layers. The layer of the second element 10 . 1 is etched by a second lithographic step, and the sacrificial layer 39 is removed.
[0191] Referring once again to the different sizes of the heater elements 10 . 1 and 10 . 2 , as mentioned above, this has the advantage that it enables the elements to be sized so as to achieve multiple, binary weighted drop volumes from one nozzle 3 .
[0192] It will be appreciated that, where multiple drop volumes can be achieved, and especially if they are binary weighted, then photographic quality can be obtained while using fewer printed dots, and at a lower print resolution.
[0193] Furthermore, under the same circumstances, higher speed printing can be achieved. That is, instead of just ejecting one drop 14 and then waiting for the nozzle 3 to refill, the equivalent of one, two, or three drops might be ejected. Assuming that the available refill speed of the nozzle 3 is not a limiting factor, ink ejection, and hence printing, up to three times faster, may be achieved. In practice, however, the nozzle refill time will typically be a limiting factor. In this case, the nozzle 3 will take slightly longer to refill when a triple volume of drop 16 (relative to the minimum size drop) has been ejected than when only a minimum volume drop has been ejected. However, in practice it will not take as much as three times as long to refill. This is due to the inertial dynamics and the surface tension of the ink 11 .
[0194] Referring to FIG. 53 , there is shown, schematically, a pair of adjacent unit cells 1 . 1 and 1 . 2 , the cell on the left 1 . 1 representing the nozzle 3 after a larger volume of drop 16 has been ejected, and that on the right 1 . 2 , after a drop of smaller volume has been ejected. In the case of the larger drop 16 , the curvature of the air bubble 71 that has formed inside the partially emptied nozzle 3 . 1 is larger than in the case of air bubble 72 that has formed after the smaller volume drop has been ejected from the nozzle 3 . 2 of the other unit cell 1 . 2 .
[0195] The higher curvature of the air bubble 71 in the unit cell 1 . 1 results in a greater surface tension force which tends to draw the ink 11 , from the refill passage 9 towards the nozzle 3 and into the chamber 7 . 1 , as indicated by the arrow 73 . This gives rise to a shorter refilling time. As the chamber 7 . 1 refills, it reaches a stage, designated 74 , where the condition is similar to that in the adjacent unit cell 1 . 2 . In this condition, the chamber 7 . 1 of the unit cell 1 . 1 is partially refilled and the surface tension force has therefore reduced. This results in the refill speed slowing down even though, at this stage, when this condition is reached in that unit cell 1 . 1 , a flow of liquid into the chamber 7 . 1 , with its associated momentum, has been established. The overall effect of this is that, although it takes longer to completely fill the chamber 7 . 1 and nozzle 3 . 1 from a time when the air bubble 71 is present than from when the condition 74 is present, even if the volume to be refilled is three times larger, it does not take as much as three times longer to refill the chamber 7 . 1 and nozzle 3 . 1 .
[0000] Heater Elements Formed from Materials Constituted by Elements with Low Atomic-Numbers
[0196] This feature involves the heater elements 10 being formed of solid material, at least 90% of which, by weight, is constituted by one or more periodic elements having an atomic number below 50. In a preferred embodiment the atomic weight is below 30, while in another embodiment the atomic weight is below 23.
[0197] The advantage of a low atomic number is that the atoms of that material have a lower mass, and therefore less energy is required to raise the temperature of the heater elements 10 . This is because, as will be understood by those skilled in the art, the temperature of an article is essentially related to the state of movement of the nuclei of the atoms. Accordingly, it will require more energy to raise the temperature, and thereby induce such a nucleus movement, in a material with atoms having heavier nuclei that in a material having atoms with lighter nuclei.
[0198] Materials currently used for the heater elements of thermal ink jet systems include tantalum aluminum alloy (for example used by Hewlett Packard), and hafnium boride (for example used by Canon). Tantalum and hafnium have atomic numbers 73 and 72, respectively, while the material used in the Memjet heater elements 10 of the present invention is titanium nitride. Titanium has an atomic number of 22 and nitrogen has an atomic number of 7, these materials therefore being significantly lighter than those of the relevant prior art device materials.
[0199] Boron and aluminum, which form part of hafnium boride and tantalum aluminum, respectively, like nitrogen, are relatively light materials. However, the density of tantalum nitride is 16.3 g/cm 3 , while that of titanium nitride (which includes titanium in place of tantalum) is 5.22 g/cm 3 . Thus, because tantalum nitride has a density of approximately three times that of the titanium nitride, titanium nitride will require approximately three time less energy to heat than tantalum nitride. As will be understood by a person skilled in the art, the difference in energy in a material at two different temperatures is represented by the following equation:
[0000] E=ΔT×C p ×V OL ×ρ,
[0000] where ΔT represents the temperature difference, C p is the specific heat capacity, V OL is the volume, and ρ is the density of the material. Although the density is not determined only by the atomic numbers as it is also a function of the lattice constants, the density is strongly influenced by the atomic numbers of the materials involved, and hence is a key aspect of the feature under discussion.
Low Heater Mass
[0200] This feature involves the heater elements 10 being configured such that the mass of solid material of each heater element that is heated above the boiling point of the bubble forming liquid (i.e. the ink 11 in this embodiment) to heat the ink so as to generate bubbles 12 therein to cause an ink drop 16 to be ejected, is less than 10 nanograms.
[0201] In one preferred embodiment, the mass is less that 2 nanograms, in another embodiment the mass is less than 500 picograms, and in yet another embodiment the mass is less than 250 picograms.
[0202] The above feature constitutes a significant advantage over prior art inkjet systems, as it results in an increased efficiency as a result of the reduction in energy lost in heating the solid materials of the heater elements 10 . This feature is enabled due to the use of heater element materials having low densities, due to the relatively small size of the elements 10 , and due to the heater elements being in the form of suspended beams which are not embedded in other materials, as illustrated, for example, in FIG. 1 .
[0203] FIG. 34 shows the shape, in plan view, of a mask for forming the heater structure of the embodiment of the printhead shown in FIG. 33 . Accordingly, as FIG. 34 represents the shape of the heater element 10 of that embodiment, it is now referred to in discussing that heater element. The heater element as represented by reference numeral 10 . 34 in FIG. 34 has just a single loop 49 which is 2 microns wide and 0.25 microns thick. It has a 6 micron outer radius and a 4 micron inner radius. The total heater mass is 82 picograms. The corresponding element 10 . 2 similarly represented by reference numeral 10 . 39 in FIG. 39 has a mass of 229.6 picograms and that heater element represented by reference numeral 10 . 36 in FIG. 36 has a mass of 225.5 picograms.
[0204] When the elements 10 . 1 , 10 . 2 represented in FIGS. 38 and 39 , for example, are used in practice, the total mass of material of each such element which is in thermal contact with the ink 11 (being the bubble forming liquid in this embodiment) that is raised to a temperature above that of the boiling point of the ink, will be slightly higher than the above discussed masses as the elements will be coated with an electrically insulating, chemically inert, thermally conductive material. This coating increases, to some extent, the total mass of material raised to the higher temperature.
Conformally Coated Heater Element
[0205] This feature involves each element 10 being covered by a conformal protective coating, this coating having been applied to all sides of the element simultaneously so that the coating is seamless. The coating 10 , preferably, is electrically non-conductive, is chemically inert and has a high thermal conductivity. In one preferred embodiment, the coating is of aluminum nitride, in another embodiment it is of diamond-like carbon (DLC), and in yet another embodiment it is of boron nitride.
[0206] Referring to FIGS. 54 and 55 , there are shown schematic representations of a prior art heater element 10 that is not conformally coated as discussed above, but which has been deposited on a substrate 78 and which, in the typical manner, has then been conformally coated on one side with a CVD material, designated 76 . In contrast, the coating referred to above in the present instance, as reflected schematically in FIG. 56 , this coating being designated 77 , involves conformally coating the element on all sides simultaneously. However, this conformal coating 77 on all sides can only be achieved if the element 10 , when being so coated, is a structure isolated from other structures—i.e. in the form of a suspended beam, so that there is access to all of the sides of the element.
[0207] It is to be understood that when reference is made to conformally coating the element 10 on all sides, this excludes the ends of the element (suspended beam) which are joined to the electrodes 15 as indicated diagrammatically in FIG. 57 . In other words, what is meant by conformally coating the element 10 on all sides is, essentially, that the element is fully surrounded by the conformal coating along the length of the element.
[0208] The primary advantage of conformally coating the heater element 10 may be understood with reference, once again, to FIGS. 54 and 55 . As can be seen, when the conformal coating 76 is applied, the substrate 78 on which the heater element 10 was deposited (i.e. formed) effectively constitutes the coating for the element on the side opposite the conformally applied coating. The depositing of the conformal coating 76 on the heater element 10 which is, in turn, supported on the substrate 78 , results in a seam 79 being formed. This seam 79 may constitute a weak point, where oxides and other undesirable products might form, or where delamination may occur. Indeed, in the case of the heater element 10 of FIGS. 54 and 55 , where etching is conducted to separate the heater element and its coating 76 from the substrate 78 below, so as to render the element in the form of a suspended beam, ingress of liquid or hydroxyl ions may result, even though such materials could not penetrate the actual material of the coating 76 , or of the substrate 78 .
[0209] The materials mentioned above (i.e. aluminum nitride or diamond-like carbon (DLC)) are suitable for use in the conformal coating 77 of the present invention as illustrated in FIG. 56 due to their desirably high thermal conductivities, their high level of chemical inertness, and the fact that they are electrically non-conductive. Another suitable material, for these purposes, is boron nitride, also referred to above. Although the choice of material used for the coating 77 is important in relation to achieving the desired performance characteristics, materials other than those mentioned, where they have suitable characteristics, may be used instead.
[0000] Example Printer in which the Printhead is Used
[0210] The components described above form part of a printhead assembly shown in FIG. 62 to 69 . The printhead assembly 19 is used in a printer system 140 shown in FIG. 70 . The printhead assembly 19 includes a number of printhead modules 80 shown in detail in FIGS. 58 to 61 . These aspects are described below.
[0211] Referring briefly to FIG. 44 , the array of nozzles 3 shown is disposed on the printhead chip (not shown), with drive transistors, drive shift registers, and so on (not shown), included on the same chip, which reduces the number of connections required on the chip.
[0212] FIGS. 58 and 59 show an exploded view and a non-exploded view, respectively, a printhead module assembly 80 which includes a MEMS printhead chip assembly 81 (also referred to below as a chip). On a typical chip assembly 81 such as that shown, there are 7680 nozzles, which are spaced so as to be capable of printing with a resolution of 1600 dots per inch. The chip 81 is also configured to eject 6 different colors or types of ink 11 .
[0213] A flexible printed circuit board (PCB) 82 is electrically connected to the chip 81 , for supplying both power and data to the chip. The chip 81 is bonded onto a stainless-steel upper layer sheet 83 , so as to overlie an array of holes 84 etched in this sheet. The chip 81 itself is a multi-layer stack of silicon which has ink channels (not shown) in the bottom layer of silicon 85 , these channels being aligned with the holes 84 .
[0214] The chip 81 is approximately 1 mm in width and 21 mm in length. This length is determined by the width of the field of the stepper that is used to fabricate the chip 81 . The sheet 83 has channels 86 (only some of which are shown as hidden detail) which are etched on the underside of the sheet as shown in FIG. 58 . The channels 86 extend as shown so that their ends align with holes 87 in a mid-layer 88 . The channels 86 align with respective holes 87 . The holes 87 , in turn, align with channels 89 in a lower layer 90 . Each channel 89 carries a different respective color of ink, except for the last channel, designated 91 . This last channel 91 is an air channel and is aligned with further holes 92 in the mid-layer 88 , which in turn are aligned with further holes 93 in the upper layer sheet 83 . These holes 93 are aligned with the inner parts 94 of slots 95 in a top channel layer 96 , so that these inner parts are aligned with, and therefore in fluid-flow communication with, the air channel 91 , as indicated by the dashed line 97 .
[0215] The lower layer 90 has holes 98 opening into the channels 89 and channel 91 . Compressed filtered air from an air source (not shown) enters the channel 91 through the relevant hole 98 , and then passes through the holes 92 and 93 and slots 95 , in the mid layer 88 , the sheet 83 and the top channel layer 96 , respectively, and is then blown into the side 99 of the chip assembly 81 , from where it is forced out, at 100 , through a nozzle guard 101 which covers the nozzles, to keep the nozzles clear of paper dust. Differently colored inks 11 (not shown) pass through the holes 98 of the lower layer 90 , into the channels 89 , and then through respective holes 87 , then along respective channels 86 in the underside of the upper layer sheet 83 , through respective holes 84 of that sheet, and then through the slots 95 , to the chip 81 . It will be noted that there are just seven of the holes 98 in the lower layer 90 (one for each color of ink and one for the compressed air) via which the ink and air is passed to the chip 81 , the ink being directed to the 7680 nozzles on the chip.
[0216] FIG. 60 , in which a side view of the printhead module assembly 80 of FIGS. 58 and 59 is schematically shown, is now referred to. The center layer 102 of the chip assembly is the layer where the 7680 nozzles and their associated drive circuitry is disposed. The top layer of the chip assembly, which constitutes the nozzle guard 101 , enables the filtered compressed air to be directed so as to keep the nozzle guard holes 104 (which are represented schematically by dashed lines) clear of paper dust.
[0217] The lower layer 105 is of silicon and has ink channels etched in it. These ink channels are aligned with the holes 84 in the stainless steel upper layer sheet 83 . The sheet 83 receives ink and compressed air from the lower layer 90 as described above, and then directs the ink and air to the chip 81 . The need to funnel the ink and air from where it is received by the lower layer 90 , via the mid-layer 88 and upper layer 83 to the chip assembly 81 , is because it would otherwise be impractical to align the large number (7680) of very small nozzles 3 with the larger, less accurate holes 98 in the lower layer 90 .
[0218] The flex PCB 82 is connected to the shift registers and other circuitry (not shown) located on the layer 102 of chip assembly 81 . The chip assembly 81 is bonded by wires 106 onto the PCB flex and these wires are then encapsulated in an epoxy 107 . To effect this encapsulating, a dam 108 is provided. This allows the epoxy 107 to be applied to fill the space between the dam 108 and the chip assembly 81 so that the wires 106 are embedded in the epoxy. Once the epoxy 107 has hardened, it protects the wire bonding structure from contamination by paper and dust, and from mechanical contact.
[0219] Referring to FIG. 62 , there is shown schematically, in an exploded view, a printhead assembly 19 , which includes, among other components, printhead module assemblies 80 as described above. The printhead assembly 19 is configured for a page-width printer, suitable for A4 or US letter type paper.
[0220] The printhead assembly 19 includes eleven of the printhead modules assemblies 80 , which are glued onto a substrate channel 110 in the form of a bent metal plate. A series of groups of seven holes each, designated by the reference numerals 111 , are provided to supply the 6 different colors of ink and the compressed air to the chip assemblies 81 . An extruded flexible ink hose 112 is glued into place in the channel 110 . It will be noted that the hose 112 includes holes 113 therein. These holes 113 are not present when the hose 112 is first connected to the channel 110 , but are formed thereafter by way of melting, by forcing a hot wire structure (not shown) through the holes 111 , which holes then serve as guides to fix the positions at which the holes 113 are melted. When the printhead assembly 19 is assembled, the holes 113 are in fluid-flow communication with the holes 98 in the lower layer 90 of each printhead module assembly 80 , via holes 114 (which make up the groups 111 in the channel 110 ).
[0221] The hose 112 defines parallel channels 115 which extend the length of the hose. At one end 116 , the hose 112 is connected to ink containers (not shown), and at the opposite end 117 , there is provided a channel extrusion cap 118 , which serves to plug, and thereby close, that end of the hose.
[0222] A metal top support plate 119 supports and locates the channel 110 and hose 112 , and serves as a back plate for these. The channel 110 and hose 112 , in turn, exert pressure onto an assembly 120 which includes flex printed circuits. The plate 119 has tabs 121 which extend through notches 122 in the downwardly extending wall 123 of the channel 110 , to locate the channel and plate with respect to each other.
[0223] An extrusion 124 is provided to locate copper bus bars 125 . Although the energy required to operate a printhead according to the present invention is an order of magnitude lower than that of known thermal ink jet printers, there are a total of about 88,000 nozzles in the printhead array, and this is approximately 160 times the number of nozzles that are typically found in typical printheads. As the nozzles in the present invention may be operational (i.e. may fire) on a continuous basis during operation, the total power consumption will be an order of magnitude higher than that in such known printheads, and the current requirements will, accordingly, be high, even though the power consumption per nozzle will be an order of magnitude lower than that in the known printheads. The busbars 125 are suitable for providing for such power requirements, and have power leads 126 soldered to them.
[0224] Compressible conductive strips 127 are provided to abut with contacts 128 on the upperside, as shown, of the lower parts of the flex PCBs 82 of the printhead module assemblies 80 . The PCBs 82 extend from the chip assemblies 81 , around the channel 110 , the support plate 119 , the extrusion 124 and busbars 126 , to a position below the strips 127 so that the contacts 128 are positioned below, and in contact with, the strips 127 .
[0225] Each PCB 82 is double-sided and plated-through. Data connections 129 (indicated schematically by dashed lines), which are located on the outer surface of the PCB 82 abut with contact spots 130 (only some of which are shown schematically) on a flex PCB 131 which, in turn, includes a data bus and edge connectors 132 which are formed as part of the flex itself. Data is fed to the PCBs 131 via the edge connectors 132 .
[0226] A metal plate 133 is provided so that it, together with the channel 110 , can keep all of the components of the printhead assembly 19 together. In this regard, the channel 110 includes twist tabs 134 which extend through slots 135 in the plate 133 when the assembly 19 is put together, and are then twisted through approximately 45 degrees to prevent them from being withdrawn through the slots.
[0227] By way of summary, with reference to FIG. 68 , the printhead assembly 19 is shown in an assembled state. Ink and compressed air are supplied via the hose 112 at 136 , power is supplied via the leads 126 , and data is provided to the printhead chip assemblies 81 via the edge connectors 132 . The printhead chip assemblies 81 are located on the eleven printhead module assemblies 80 , which include the PCBs 82 .
[0228] Mounting holes 137 are provided for mounting the printhead assembly 19 in place in a printer (not shown). The effective length of the printhead assembly 19 , represented by the distance 138 , is just over the width of an A4 page (that is, about 8.5 inches).
[0229] Referring to FIG. 69 , there is shown, schematically, a cross-section through the assembled printhead 19 . From this, the position of a silicon stack forming a chip assembly 81 can clearly be seen, as can a longitudinal section through the ink and air supply hose 112 . Also clear to see is the abutment of the compressible strip 127 which makes contact above with the busbars 125 , and below with the lower part of a flex PCB 82 extending from a the chip assembly 81 . The twist tabs 134 which extend through the slots 135 in the metal plate 133 can also be seen, including their twisted configuration, represented by the dashed line 139 .
Printer System
[0230] Referring to FIG. 70 , there is shown a block diagram illustrating a printhead system 140 according to an embodiment of the invention.
[0231] Shown in the block diagram is the printhead 141 , a power supply 142 to the printhead, an ink supply 143 , and print data 144 (represented by the arrow) which is fed to the printhead as it ejects ink, at 145 , onto print media in the form, for example, of paper 146 .
[0232] Media transport rollers 147 are provided to transport the paper 146 past the printhead 141 . A media pick up mechanism 148 is configured to withdraw a sheet of paper 146 from a media tray 149 .
[0233] The power supply 142 is for providing DC voltage which is a standard type of supply in printer devices.
[0234] The ink supply 143 is from ink cartridges (not shown) and, typically various types of information will be provided, at 150 , about the ink supply, such as the amount of ink remaining. This information is provided via a system controller 151 which is connected to a user interface 152 . The interface 152 typically consists of a number of buttons (not shown), such as a “print” button, “page advance” button, an so on. The system controller 151 also controls a motor 153 that is provided for driving the media pick up mechanism 148 and a motor 154 for driving the media transport rollers 147 .
[0235] It is necessary for the system controller 151 to identify when a sheet of paper 146 is moving past the printhead 141 , so that printing can be effected at the correct time. This time can be related to a specific time that has elapsed after the media pick up mechanism 148 has picked up the sheet of paper 146 . Preferably, however, a paper sensor (not shown) is provided, which is connected to the system controller 151 so that when the sheet of paper 146 reaches a certain position relative to the printhead 141 , the system controller can effect printing. Printing is effected by triggering a print data formatter 155 which provides the print data 144 to the printhead 141 . It will therefore be appreciated that the system controller 151 must also interact with the print data formatter 155 .
[0236] The print data 144 emanates from an external computer (not shown) connected at 156 , and may be transmitted via any of a number of different connection means, such as a USB connection, an ETHERNET connection, a IEEE1394 connection otherwise known as firewire, or a parallel connection. A data communications module 157 provides this data to the print data formatter 155 and provides control information to the system controller 151 .
FEATURES AND ADVANTAGES OF FURTHER EMBODIMENTS
[0237] FIGS. 71 to 94 show further embodiments of unit cells 1 for thermal inkjet printheads, each embodiment having its own particular functional advantages. These advantages will be discussed in detail below, with reference to each individual embodiment. However, the basic construction of each embodiment is best shown in FIGS. 72 , 74 , 76 and 79 . The manufacturing process is substantially the same as that described above in relation to FIGS. 6 to 31 and for consistency, the same reference numerals are used in FIGS. 71 to 94 to indicate corresponding components. In the interests of brevity, the fabrication stages have been shown for the unit cell of FIG. 78 only (see FIGS. 80 to 90 ). It will be appreciated that the other unit cells will use the same fabrication stages with different masking. Again, the deposition of successive layers shown in FIGS. 80 to 90 need not be described in detail below given that the lithographic process largely corresponds to that shown in FIGS. 6 to 31 .
[0238] Referring to FIGS. 71 and 72 , the unit cell 1 shown has the chamber 7 , ink supply passage 32 and the nozzle rim 4 positioned mid way along the length of the unit cell 1 . As best seen in FIG. 72 , the drive circuitry is partially on one side of the chamber 7 with the remainder on the opposing side of the chamber. The drive circuitry 22 controls the operation of the heater 14 through vias in the integrated circuit metallisation layers of the interconnect 23 . The interconnect 23 has a raised metal layer on its top surface. Passivation layer 24 is formed in top of the interconnect 23 but leaves areas of the raised metal layer exposed. Electrodes 15 of the heater 14 contact the exposed metal areas to supply power to the element 10 .
[0239] Alternatively, the drive circuitry 22 for one unit cell is not on opposing sides of the heater element that it controls. All the drive circuitry 22 for the heater 14 of one unit cell is in a single, undivided area that is offset from the heater. That is, the drive circuitry 22 is partially overlaid by one of the electrodes 15 of the heater 14 that it is controlling, and partially overlaid by one or more of the heater electrodes 15 from adjacent unit cells. In this situation, the center of the drive circuitry 22 is less than 200 microns from the center of the associate nozzle aperture 5 . In most Memjet printheads of this type, the offset is less than 100 microns and in many cases less than 50 microns, preferably less than 30 microns.
[0240] Configuring the nozzle components so that there is significant overlap between the electrodes and the drive circuitry provides a compact design with high nozzle density (nozzles per unit area of the nozzle plate 2 ). This also improves the efficiency of the printhead by shortening the length of the conductors from the circuitry to the electrodes. The shorter conductors have less resistance and therefore dissipate less energy.
[0241] The high degree of overlap between the electrodes 15 and the drive circuitry 22 also allows more vias between the heater material and the CMOS metalization layers of the interconnect 23 . As best shown in FIGS. 79 and 80 , the passivation layer 24 has an array of vias to establish an electrical connection with the heater 14 . More vias lowers the resistance between the heater electrodes 15 and the interconnect layer 23 which reduces power losses.
[0242] In FIGS. 73 and 74 , the unit cell 1 is the same as that of FIGS. 71 and 72 apart from the heater element 10 . The heater element 10 has a bubble nucleation section 158 with a smaller cross section than the remainder of the element. The bubble nucleation section 158 has a greater resistance and heats to a temperature above the boiling point of the ink before the remainder of the element 10 . The gas bubble nucleates at this region and subsequently grows to surround the rest of the element 10 . By controlling the bubble nucleation and growth, the trajectory of the ejected drop is more predictable.
[0243] The heater element 10 is configured to accommodate thermal expansion in a specific manner. As heater elements expand, they will deform to relieve the strain. Elements such as that shown in FIGS. 71 and 72 will bow out of the plane of lamination because its thickness is the thinnest cross sectional dimension and therefore has the least bending resistance. Repeated bending of the element can lead to the formation of cracks, especially at sharp corners, which can ultimately lead to failure. The heater element 10 shown in FIGS. 73 and 74 is configured so that the thermal expansion is relieved by rotation of the bubble nucleation section 158 , and slightly splaying the sections leading to the electrodes 15 , in preference to bowing out of the plane of lamination. The geometry of the element is such that miniscule bending within the plane of lamination is sufficient to relieve the strain of thermal expansion, and such bending occurs in preference to bowing. This gives the heater element greater longevity and reliability by minimizing bend regions, which are prone to oxidation and cracking.
[0244] Referring to FIGS. 75 and 76 , the heater element 10 used in this unit cell 1 has a serpentine or ‘double omega’ shape. This configuration keeps the gas bubble centered on the axis of the nozzle. A single omega is a simple geometric shape which is beneficial from a fabrication perspective. However the gap 159 between the ends of the heater element means that the heating of the ink in the chamber is slightly asymmetrical. As a result, the gas bubble is slightly skewed to the side opposite the gap 159 . This can in turn affect the trajectory of the ejected drop. The double omega shape provides the heater element with the gap 160 to compensate for the gap 159 so that the symmetry and position of the bubble within the chamber is better controlled and the ejected drop trajectory is more reliable.
[0245] FIG. 77 shows a heater element 10 with a single omega shape. As discussed above, the simplicity of this shape has significant advantages during lithographic fabrication. It can be a single current path that is relatively wide and therefore less affected by any inherent inaccuracies in the deposition of the heater material. The inherent inaccuracies of the equipment used to deposit the heater material result in variations in the dimensions of the element. However, these tolerances are fixed values so the resulting variations in the dimensions of a relatively wide component are proportionally less than the variations for a thinner component. It will be appreciated that proportionally large changes of components dimensions will have a greater effect on their intended function. Therefore the performance characteristics of a relatively wide heater element are more reliable than a thinner one.
[0246] The omega shape directs current flow around the axis of the nozzle aperture 5 . This gives good bubble alignment with the aperture for better ejection of drops while ensuring that the bubble collapse point is not on the heater element 10 . As discussed above, this avoids problems caused by cavitation.
[0247] Referring to FIGS. 78 to 91 , another embodiment of the unit cell 1 is shown together with several stages of the etching and deposition fabrication process. In this embodiment, the heater element 10 is suspended from opposing sides of the chamber. This allows it to be symmetrical about two planes that intersect along the axis of the nozzle aperture 5 . This configuration provides a drop trajectory along the axis of the nozzle aperture 5 while avoiding the cavitation problems discussed above. FIGS. 92 and 93 show other variations of this type of heater element 10 .
[0248] FIG. 93 shows a unit cell 1 that has the nozzle aperture 5 and the heater element 10 offset from the center of the nozzle chamber 7 . Consequently, the nozzle chamber 7 is larger than the previous embodiments. The heater 14 has two different electrodes 15 with the right hand electrode 15 extending well into the nozzle chamber 7 to support one side of the heater element 10 . This reduces the area of the vias contacting the electrodes which can increase the electrode resistance and therefore the power losses. However, laterally offsetting the heater element from the ink inlet 31 increases the fluidic drag retarding flow back through the inlet 31 and ink supply passage 32 . The fluidic drag through the nozzle aperture 5 comparatively much smaller so little energy is lost to a reverse flow of ink through the inlet when a gas bubble form on the element 10 .
[0249] The unit cell 1 shown in FIG. 94 also has a relatively large chamber 7 which again reduces the surface area of the electrodes in contact with the vias leading to the interconnect layer 23 . However, the larger chamber 7 allows several heater elements 10 offset from the nozzle aperture 5 . The arrangement shown uses two heater elements 10 ; one on either side of the chamber 7 . Other designs use three or more elements in the chamber. Gas bubbles nucleate from opposing sides of the nozzle aperture and converge to form a single bubble. The bubble formed is symmetrical about at least one plane extending along the nozzle axis. This enhances the control of the symmetry and position of the bubble within the chamber 7 and therefore the ejected drop trajectory is more reliable.
[0250] Although the invention is described above with reference to specific embodiments, it will be understood by those skilled in the art that the invention may be embodied in many other forms. For example, although the above embodiments refer to the heater elements being electrically actuated, non-electrically actuated elements may also be used in embodiments, where appropriate.
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Provided is a pagewidth printhead assembly having a plurality of printhead modules. Each of these modules includes a printhead integrated circuit (IC) having a plurality of ink ejection nozzles, and an ink distribution assembly formed from a stack of ink distribution layers. Each layer defines apertures therein at predetermined locations, with the layers laminated together so that the apertures complementarily define ink distribution channels to the printhead IC. Each module also includes a tape automated bonding (TAB) film connected to the printhead IC for arranging said IC in signal communication with a controller of the printhead assembly.
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CROSS REFERENCE
This application claims priority from a provisional patent application entitled “Method and Circuits for Analyzing USB Data Traffic Using a Hardware USB Analyzer on a Single USB Host Controller” filed on Mar. 31, 2008 and having an Application No. 61/041,080. Said application is incorporated herein by reference.
FIELD OF INVENTION
This invention relates to methods for analyzing USB data traffic, and, in particular, to methods for capturing USB data traffic using a USB analyzer on a single USB host controller.
BACKGROUND
Universal Serial Bus (USB) is a serial bus standard used for connecting peripheral devices to a host computer. A USB system comprises a USB host, a plurality of downstream USB ports, and one or more peripheral devices. A USB host may have multiple USB host controllers (the “host controllers”), wherein each host controller may provide for one or more USB ports.
Specifically, the USB 2.0 architecture offers high-speed communications, and is capable of connecting multiple devices to a hub that is further connected to a port of the host computer. The USB 2.0 architecture employs a unidirectional broadcast system. In such a system, when a host controller or hub sends a packet, all devices downstream from the originating point of the data will receive the packet. When the host controller communicates with a specific device, it must include the address of the device in the Token packet. Upstream traffic (i.e., the responses from the devices) is only received by the host controller and hubs that are directly connected on the return path to the host controller.
This feature of the USB architecture is especially significant for USB analyzers, which communicate to an analysis computer through the USB system. FIG. 1 illustrates a typical setup for connecting an analyzer to a USB system, wherein the analyzer and a device are connected to the same host controller. An analyzer 12 is setup to monitor the communications between a host controller 10 and a device 14 . The analyzer 12 can be setup such that the host controller 10 and the device 14 are unaware of the analyzer's presence on the communication line.
Since the analyzer 12 and the device 14 are connected to the same host controller 10 , the analyzer 12 will receive traffic (e.g., packet 16 ) intended for itself and for the device on the communication port 11 and on the monitor port 15 . Since packets intended for the communication port 11 of the analyzer 12 are also perceived on the monitor port 15 , this creates a positive feedback loop. Every time the computer requests data from the analyzer 12 , it actually creates more traffic on the monitor port 15 to be sent back to the computer. The traffic can overwhelm the user with unnecessary data and will also put unnecessary load on the analyzer's buffer memory and the analysis computer. This is especially true when the analyzer 12 sends large volumes of analysis data back to the analysis computer simultaneously to when the traffic is being captured.
It should be noted that this positive feedback occurs only during particular configurations of the analyzer 12 and device 14 on a single host controller 10 . High-speed (HS) communication devices are electrically isolated from full-speed (FS) and low-speed (LS) devices, even if connected to the same host controller. Thus, packets to the analyzer 12 will only be perceived on the monitor port 15 if the monitor port 15 is HS and the communication port 11 is HS, or if they are both not HS.
FIG. 2 illustrates the data traffic at various times for an analyzer and a device on the same host controller. Each connection to the host controller 10 effectively has a logical “Send” and “Receive” unit. All packets sent by the host controller 10 (see times t 0 and t 2 ) are received by all attached peripherals (i.e., the device 14 and the analyzer 12 ). The responses from the peripherals (see times t 1 and t 3 ) are only seen on the physical communication interface between the particular peripheral and the host controller 10 .
When the host controller 10 sends a packet with the data “PKT2ANL” to the analyzer 12 at time t 2 , the analyzer 12 receives the packet on its receive logical port (of the communication port 11 ), as well as on its monitor port 15 . Therefore, when the analyzer 12 responds with the monitored data at time t 3 , that piece of data, “PKT2ANL”, is unnecessarily present in the analyzer response. If the host controller 10 is sending many packets to the analyzer 12 , then this has the potential of overloading the captured analysis traffic with unnecessary information, and can also take up bandwidth in the analyzer's response at time t 3 .
Previous products and technologies combated this issue in one of two ways: they either avoided the issue entirely by insisting the user put the USB analyzer on a separate host controller, or they required the user of the analyzer to know the device address of the analyzer beforehand and set up a filter for it.
Using a separate host controller for the analysis computer is optimal in all cases; it reduces the load on that host controller, and allows both the analyzer and the device under test to have more available bandwidth. However, this situation is not always possible or practical, as it requires the user to include additional hardware on the analysis computer or to obtain another USB capable computer; thereby requiring a total of two computers. Therefore, this requirement excludes users from efficiently using the analyzer in such a situation, and does not address the problem.
Some products give the ability to create a hardware filter that will serve a similar purpose. The filter can be configured to discard all data intended for a specific device address. In this way, the analyzer and the device under test can be on the same host controller without overloading the capture buffers. However, these products require the user to know the device address of the analyzer in order to configure the filter. This filter would potentially have to be reconfigured each time the analyzer is used since the device address of the analyzer can change every time it is plugged into a computer. While serving a similar purpose to the present invention, this approach also puts unnecessary strain on the user to maintain the functionality of the filter.
Therefore, it is desirable to provide methods for analyzing USB data traffic using a USB analyzer on a single USB host controller by automatically filtering the USB data traffic.
SUMMARY OF INVENTION
An object of this invention is to provide methods for recognizing packets received on a monitor port intended for an analyzer's device address and then discarding those packets.
Another object of this invention is to provide methods for analyzing USB data traffic without requiring the analyzer to be on a separate bus or requiring a manually configured filter.
Yet another object of this invention is to provide methods for an easy and maintainable interface for a user of an analyzer to automatically filter USB traffic.
Briefly, USB data traffic for a monitored device is captured by a USB analyzer, wherein the monitored device and the USB analyzer utilize only one USB host controller, comprising the steps of: storing an analyzer address associated with the USB analyzer and the speed of the analyzer's communication port; reading a USB packet; and filtering the read packet as a function of the stored analyzer address and its communication speed.
An advantage of this invention is that methods for recognizing packets received on a monitor port intended for an analyzer's device address and then discarding those packets are provided.
Another advantage of this invention is that methods for analyzing USB data traffic without requiring the analyzer to be on a separate bus or requiring a manually configured filter are provided.
Yet another advantage is that methods for an easy and maintainable interface for a user of an analyzer to automatically filter USB traffic are provided.
DESCRIPTION OF THE DRAWINGS
The foregoing and other objects, aspects, and advantages of the invention will be better understood from the following detailed description of the preferred embodiment of the invention when taken in conjunction with the accompanying drawings in which:
FIG. 1 illustrates a typical setup for connecting an analyzer to a USB system, wherein the analyzer and a device are connected to the same host controller.
FIG. 2 illustrates USB data traffic at various times for an analyzer and a device connected to the same host controller.
FIGS. 3 a - 3 b illustrate a flow chart for a preferred embodiment of the invention for capturing USB data traffic for an analyzer and a device connected to the same host controller.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Presently preferred embodiments of the present invention provide methods for effectively monitoring USB data traffic on a single USB host controller by implementing a preferably hardware based filter that removes packets from a monitor port intended for the analyzer. These packets are removed in order to minimize the load on the capture buffers. Furthermore, a graphical interface for this filter is provided to greatly simplify the use of the analyzer. To apply this filter, the graphical interface can have a check box to enable this filter, a mechanism to call a single function with a single constant in a programming API, or other user interface mechanisms to enable this filter. This filter can remain valid and functional so long as the settings are saved, even if the device address of the analyzer changes.
In the preferred embodiment of the present invention, the filtering mechanism also takes into account the speed of the monitored bus. The USB protocol is defined in such a way that on a single host controller the device address space (meaning the set of possible device addresses) of full-speed (FS) and low-speed (LS) communication is separate to that of high-speed (HS). Therefore, it is possible for HS devices to have the same device address of FS or LS devices on the same host controller. Unintentional filtering can therefore occur when the analyzer is connected to a HS bus and monitoring FS/LS devices on a single host controller, or vice-versa. Therefore the speed of the monitored bus should be checked against the speed of the communication bus.
For example, if the analyzer's device address is set to 0x01 and it is communicating at HS, it is possible that a FS device being monitored will also have a device address of 0x01, even if on the same host controller. If self-filtering was enabled, and the speed of the bus was not taken into account, then the user would not see any monitored traffic (as all packets would match that device address and be filtered out). Therefore, to aid in this situation the analyzer would take into account its own communication speed and that of the monitored bus. Only if the device address and the speed of communication match would the packet would be filtered out.
The speed of the monitor port would be detected automatically through mechanisms not relevant to this invention. The speed of communication port is determined before the capture begins. It could therefore be automatically detected by the analyzer, or transmitted to the analyzer through other mechanisms during the capture start-up process.
Using this mechanism, users could safely analyze USB with a single host controller, even as they test multiple devices of any speed, during a single capture.
FIGS. 3 a - 3 b illustrate a flow chart for a preferred embodiment of the invention for capturing USB data traffic for an analyzer and a device on the same host controller. When an analyzer is connected to a host controller via a USB cable 30 , the analyzer is enumerated 32 . During the enumeration 32 , the host controller allocates an address to the analyzer in order to prepare for transmission of data to the analyzer and for the reception of data from the analyzer.
Upon enumeration of the USB analyzer 32 , the analyzer stores its address for future use 34 , as well as its communication speed. In an alternative embodiment, the analyzer's device address does not need to be stored upon enumeration. It can also be determined by the analysis computer, and then transmitted to the analyzer upon starting the capture of USB data traffic. Similarly, the analyzer's communication speed could be configured the same way.
The analyzer can then be configured with a single input from the user via a user interface to enable (or disable) the filtering of packets intended for the analyzer's device address 36 .
When the capture is started 38 , the analyzer checks if the filtering of its device address is enabled 40 . The analyzer can check if the filter is enabled at the beginning of the USB data capture, or, alternatively, it can check whether the filter is enabled at the reception of each packet.
If the filter is not enabled 40 , then the analyzer allows all packets through to the rest of the system. The analyzer will continuously read USB data from the stream 42 , write it to the buffer 44 , and check again to see if filtering is enabled 40 .
If the filter is enabled 40 , then special filtering techniques can be used to remove those packets intended for the analyzer from the captured data stream. In one example of such special filtering techniques, each packet in the USB data traffic is read 46 to determine whether it is a Token packet identifier 48 (herein referred to as a “Token PID”). If it is not a Token PID 48 , or it is a Token PID that does not match the analyzer's device address 52 or if the speed does not match, then the analyzer writes the data to an outbound buffer 50 , and reads the next piece of USB data 40 . In comparing the speed of the communication port and the monitor port, they are considered matched if the communication port is HS and the monitor port is HS, or if the communication port is not HS and the monitor port is not HS.
However, if the packet is a Token PID 48 that matches the analyzer's device address 52 and the communication speed of the analyzer, then the analyzer does not write that data to the outbound buffer. Instead, it transitions to a new state and reads the next piece of USB data 54 . Once in this new state, the analyzer will not write any of the new USB data into the buffer until a new Token PID is received that does not match the analyzer's device address (since all interim non-Token packets are taken to be intended for the analyzer).
After the next piece of USB data is read, the analyzer determines whether the read USB data is a Token PID 56 . If the data is a Token PID, then the requested device address in the Token PID is compared to the analyzer's address and speed to determine if the addresses match 52 . If the addresses and speed do not match, then the data is written to the buffer 50 . If the addresses and speed match, the analyzer does not write that data to the outbound buffer, and the next USB data is read 54 .
If the read USB data is not a Token PID, then it is determined whether the data is a corrupted PID 58 . If the data is a corrupted PID, then the data is written to the buffer 50 . If the data is not a corrupted PID, then the next USB data is read 54 .
In an alternative embodiment, the analyzer can filter only a subset of packets (e.g., those packets only matching certain packet types) intended for its device address.
The data in the buffer is then transmitted to the analysis computer via the host controller and thereby the USB traffic to the device can be seen on the analysis computer and analyzed. As a general case, data to the analyzer itself would be filtered out; and, as an option, traffic to the analyzer can also be transmitted to the analysis computer if so desired.
It is important to note that other products and technologies employ display filters to aid with the visualization of the data. This is not to be confused with the type of filtering presented by this invention. Display filters work only on already captured data, and only filter what has already been downloaded to the analysis computer. This invention filters the packets before they reach the capture buffer: thus, reducing the hardware buffer usage, the load on the analysis computer, and the intrusiveness of the analyzer. Display filters cannot prevent the capture buffer from being overloaded and exhausted by the unnecessary traffic described previously.
While the present invention has been described with reference to certain preferred embodiments or methods, it is to be understood that the present invention is not limited to such specific embodiments or methods. Rather, it is the inventor's contention that the invention be understood and construed in its broadest meaning as reflected by the following claims. Thus, these claims are to be understood as incorporating not only the preferred methods described herein but all those other and further alterations and modifications as would be apparent to those ordinary skilled in the art.
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A method is described for capturing USB data traffic for a monitored device by a USB analyzer using a single USB host controller. It comprises the steps of: generating and storing an address and communication speed associated with the USB analyzer; reading a USB packet; discarding selected read packets based on the stored analyzer address and communication speed; and transmitting the remaining packets to an analysis computer.
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BACKGROUND
[0001] 1. Technical Field
[0002] The present disclosure relates to goods delivery mechanisms, and particularly to a goods delivery mechanism in an automatic vending machine.
[0003] 2. Description of Related Art
[0004] In an automatic vending machine, a delivery assembly is used for pushing goods out of a goods channel. The delivery assembly includes a large helical coil and a motor. The goods are placed on the coil. The motor rotates the coil to move the goods out of the goods channel. In known vending machines, the coil can accommodate only one item of goods because a mounting angle of the coil is not adjustable.
[0005] Therefore, there is room for improvement within the art.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] Many aspects of the 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 embodiments. Moreover, in the drawings, like reference numerals designate corresponding parts throughout the several views.
[0007] FIG. 1 is exploded, isometric view of an embodiment of a goods delivery assembly.
[0008] FIG. 2 is similar to FIG. 1 , but viewed from another aspect.
[0009] FIG. 3 is an enlarged view of an encircled portion III of FIG. 1 .
[0010] FIG. 4 is an assembled view of the goods delivery assembly of FIG. 1 .
DETAILED DESCRIPTION
[0011] The disclosure is illustrated by way of example and not by way of limitation in the figures of the accompanying drawings in which like references indicate similar elements. 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.”
[0012] Referring to FIGS. 1 to 3 , an embodiment of a goods delivery assembly for a vending machine includes a plate 10 , a casing 20 , a motor 30 , a splined driving shaft 40 driven by the motor 30 , a first gear 50 , a second gear 60 , and a coil 80 for receiving goods thereon.
[0013] The plate 10 defines a through hole 11 extending through the plate 10 . The plate 10 includes an outer side 13 and an inner side 14 . Four fixing pins 12 are located on the outer side 13 and around the through hole 11 .
[0014] The motor 30 is mounted in the casing 20 . The casing 20 defines four fixing holes 21 corresponding to the four fixing pins 12 of the plate 10 .
[0015] The splined driving shaft 40 is rotated by the motor 30 . A plurality of splines 41 is located on periphery of the shaft 40 . A flat is machined across the distal end of two top splines 41 to form a first engaging cutout 411 . A similar and opposing flat is machined across the distal end of two bottom splines 41 to form a second engaging cutout 412 . A connecting post 43 protrudes from an end of the shaft 40 . The connecting post 43 is hollow to define a securing hole 431 . A diameter of the shaft 40 is smaller than a diameter of the through hole 11 .
[0016] The first gear 50 includes a fixing side 51 facing the plate 10 and a first engaging side 52 facing the second gear 60 . A center portion of first gear 50 defines a first connecting hole 56 corresponding to the connecting post 43 . Two bars 511 are formed on the fixing side 51 . A rounded swelling 521 ) protrudes from the first engaging side 52 . A plurality of teeth 523 is formed on the first engaging side 52 to surround and frame the rounded swelling 521 .
[0017] The second gear 60 includes a second engaging side 62 facing to the first engaging side 52 of the first gear 50 . The second gear 60 defines a second connecting hole 66 corresponding to the connecting post 43 . The second engaging side 62 defines a rounded depression 621 ( ) corresponding in shape to the rounded swelling 521 of the first gear 50 . A plurality of second teeth 623 is formed on the second engaging side 62 to surround and frame the rounded depression 621 . A radial mounting hole 63 is defined on periphery of the second gear 60 . An extending direction of the mounting hole 63 is perpendicular to an extending direction of the second connecting hole 66 . The mounting hole 63 and the connecting hole 66 are not interconnected.
[0018] Referring to FIGS. 1 to 4 , in assembly, the four fixing pins 12 of the plate 10 are inserted in the four fixing holes 21 of the casing 20 to mount the casing 20 on the inner side 13 of the plate 13 . The shaft 40 is inserted in the through hole 11 to protrude in the inner side 14 .
[0019] The first gear 50 is moved towards the shaft 40 with the first engaging side 52 facing the shaft 40 . The connecting post 411 of the shaft 40 is inserted in the first connecting hole 56 of the first gear 60 , and the two bars 511 of the first gear 50 slide over and engage the first engaging cutout 411 and the second engaging cutout 412 , to lock the first gear 50 on the shaft 40 . The first gear 50 is then rotatable together with the shaft 40 .
[0020] The second gear 60 is moved towards the first gear 50 with the second engaging side 62 facing the first engaging side 52 . The connecting post 411 of the shaft 40 is inserted in the second connecting hole 66 of the second gear 60 . The rounded swelling 521 of the first gear 50 engages with the rounded depression 621 of the second gear 60 .
[0021] The second teeth 623 of the second gear 60 are engaged in the first teeth 523 of the first gear 50 . The second gear 60 is thus rotatable by the first gear 50 . A securing stick 90 is inserted in the securing hole 431 of the connecting post 43 to mount the first gear 50 and the second gear 60 on the shaft 40 . Finally, one end of the coil 80 is inserted in the mounting hole 63 to mount the coil 80 on the second gear 60 . The goods delivery assembly is thereby assembled completely.
[0022] When a mounting angle of the coil 80 needs to be adjusted, the securing stick 90 is detached from the securing hole 431 . The second teeth 623 of the second gear 60 can engage in the first teeth 523 of the first gear 50 at other angles as the rounded swelling 521 rides within the rounded depression 621 substantially in the manner of a ball joint. Therefore, the mounting angle of the coil 80 is adjustable.
[0023] It is to be understood, however, that even though numerous characteristics and advantages of the embodiments have been set forth in the foregoing description, together with details of the structure and functions of the embodiments, the disclosure is illustrative only, and changes may be made in detail, especially in the matters of shape, size, and arrangement of parts within the principles of the present disclosure to the full extent indicated by the broad general meaning of the terms in which the appended claims are expressed.
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A goods delivery assembly for a vending machine includes a motor, a shaft, a first gear, a second gear, and a coil to hold goods. Peripheral teeth and a shallow ball joint between the two gears enables the second gear to continue to be rotated by the first driving gear at angles which are not coaxial with the first gear, to achieve adjustability of the mounting angle of the coil for holding different goods.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention is directed to orthopedic knee braces and particularly those designed to provide medial (varus) and lateral (valgus) compensation.
2. Description of Related Art
Published U.S. Patent Application No. 2002/0183672 A1 discloses an orthopedic knee brace with adjustable length struts. Length adjustment is achieved via a telescopic adjustment assembly but no provision is made for medial or lateral adjustment of the length adjustment mechanism cannot be used for that purpose without producing binding of the joint mechanism.
A self-aligning adjustable orthopedic knee brace is disclosed in U.S. Pat. No. 6,387,066 B1. The brace of this patent has a self-aligning polycentric joint which utilizes an apertured spherical bearing element and an annular concave seat in which the bearing element is freely rotatable so as to permit not only anterior-posterior pivoting of the femoral and tibial arms with respect to each other, but also medial-lateral relative movement. Additionally, the femoral (upper) arm has a length adjustment arrangement with an adjustment screw, the head of which is rotatably retained in the top end of the femoral arm and the other of which is threaded into the facing end an adjustment arm so that rotation of the screw either draws the adjustment arm toward femoral arm or displaces it away from it. By adjustment of the arms, the angle of inclination of femoral half of the brace can be adjusted relative to the tibial half, the spherical polycentric joint allowing for the laterally or medially directed inclination without producing binding during posterior-anterior motion. However, the problem with the use of a spheric polycentric joint is that it imparts an inherent weakness to the brace in that it is not constrained against transverse rotation, i.e., rotation in a horizontal plan, and thus allows a degree of twisting between the femur and tibia. Furthermore, a joint of this type cannot duplicate the correct natural movement of the knee, such as is obtainable by the joints as disclosed in U.S. Pat. Nos. 4,773,404; 4,890,607; 5,259,832; and 5,330,418.
SUMMARY OF THE INVENTION
Therefore, it is a primary object of the present invention to provide orthopedic knee brace which will allow lateral-medial compensation to be obtained while still enabling the use of known joint mechanism which will constrain the leg to execute the correct natural movement of the knee.
In accordance with the invention, this object is achieved by separating the lateral-medial compensation and anterior posterior movement functions. More specifically, the present invention utilizes a pair of hinges, one of which provides for movement in a posterior-anterior plane and the other which provides for movement in a medial-lateral plane. In this way, any conventional knee joint mechanism may be employed and movement of the leg can be properly constrained to execute a prescribed motion.
These and other objects, features and advantages will become apparent from the following detailed description of a preferred embodiment when viewed in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side view of a knee brace in accordance with a preferred embodiment of the invention;
FIG. 2 is a perspective view of the knee brace shown in FIG. 1 ;
FIG. 3 is an exploded view of the joint mechanism of the FIG. 1 knee brace;
FIGS. 4 & 5 each show a perspective view of a respective version of the length adjustment mechanism of the FIG. 1 knee brace; and
FIGS. 6–8 show the FIG. 1 knee brace in neutral, medially shifted and laterally shifted positions, respectively.
DETAILED DESCRIPTION OF THE INVENTION
With reference to FIGS. 1 & 2 , it can be seen that knee brace 1 of the present invention, as is typical, has a medial femoral arm 3 and a lateral side femoral arm 5 which are connected, respectively, to a medial tibial arm 7 and a lateral side tibial arm 9 . In particular, an upper crossbar 11 connects the medial femoral arm 3 and lateral femoral arm 5 at a front side of the brace, and a pair of lower crossbars 12 connect the medial and lateral tibial arms 7 , 9 at a front side of the brace. Additionally, upper and lower straps 13 , 14 are provided for detachably securing the brace 1 on a leg of a user at the thigh and calf areas. In this regard, it is noted that, at least in the context of the present invention, it is important to provide at least a pair straps 13 , 14 running between medial and lateral tibial arms, or other equivalent structure, in order to establish a fixed anchoring of the brace relative to the leg for reasons described more specifically below.
A medial side joint mechanism 16 couples the medial side femoral arm 3 to the medial side tibial arm 7 , and a lateral side joint mechanism 17 couples the lateral side femoral arm 5 to the lateral side tibial arm 9 . Each of the joint mechanisms 16 , 17 comprise upper and lower hinges 19 , 20 , the lower hinges 20 enabling relative movement between the femoral and tibial arms in posterior-anterior planes and the upper hinges 19 enabling relative movement between the femoral and tibial arms in medial-lateral planes.
The upper hinges 19 are unicentric hinges and the lower hinges 20 are polycentric. Each of the upper hinges 19 preferably comprises a pin 22 that is engaged in pin-receiving openings 23 of the femoral arms and 24 of the joint mechanisms. While the lower hinges 20 can be of any known polycentric type, it is advantageous to use which duplicates the natural motion of the knee by providing a means for constraining the tibia to slide rearwardly relative to the femur for a predetermined distance during an initial range of flexion of the knee from a straight leg position, and beyond the initial range of flexion to, thereafter, rotate relative thereto in a predetermined arcuate path as is the case for the joints as disclosed in U.S. Pat. Nos. 4,773,404; 4,890,607; 5,259,832; and 5,330,418, all of which are hereby incorporated by reference.
A lower hinge construction for the joint mechanism that is particularly advantageous is one of the type described in U.S. Pat. No. 5,259,832, which comprises a four bar linkage. With reference to FIG. 3 the four bar linkage forming the joint mechanism 17 of the preferred embodiment of the present invention will be described.
Firstly, to provide self-lubricating bearings which will also prevent, e.g., aluminum links from reacting with titanium arms, male plastic bearing elements 27 , 28 are inserted into the openings 30 a , 30 b of the tibial arms 7 , 9 and openings 31 a , 31 b of a lower part of the upper hinges 19 , respectively. Bearing retainers 33 , 34 are then snapped onto ends of the bearing elements 27 , 28 which have passed through and out of the openings 30 a , 30 b , and 31 a , 30 b.
A first pivot link is formed by link elements 36 , 37 , which are secured together by rivets 38 after the male link element 36 has been insert through openings 30 a and 31 a and female link element 37 has been mounted over the ends of the link element 36 which have passed through and out of the openings 30 a , 31 a , thus forming first and second pivot points. Alternatively, the rivets 38 can be omitted and other fastening methods used, such as crimping of the projecting ends of the male link element 36 . After attachment of the first pivot link, the hinge cover 40 , which is C-shaped or clam shell-shaped, is slid over the area of the openings 30 a , 30 b , and 31 a , 30 b and the first pivot link. Then, rivets 42 are inserted into the openings 43 , 44 of the hinge cover 40 , through the openings 30 b and 31 b , and back out though the corresponding openings 43 , 44 at the opposite side of the hinge cover 40 , after which they are fixed in place. Thus, the portion of the hinge cover 40 between the rivets 42 constitutes the second pivot link of the four bar linkage forming the polycentric lower hinges 17 with the rivets 42 forming third and fourth pivot points.
In accordance with the concept of U.S. Pat. No. 5,259,832, an angle of intersection between an imaginary line drawn through the first and second pivot points of first pivot link and an imaginary line drawn through the third and fourth pivot points of the second pivot link is at least 24° throughout a full range of flexion from a straight leg position to a fully flexed position.
In accordance with the invention, at least one of the femoral arms 3 , 5 has a length adjustment mechanism. In the case of an off the shelf (OTS) knee brace, both of the femoral arms 3 , 5 , would normally be provided with a length adjustment mechanism, as is the case for the knee brace 1 shown in FIG. 2 . On the other hand, a custom fitted knee brace will normally require a length adjustment mechanism in only one of the femoral arms 3 , 5 and the range of adjustability provided will not be as great since adjustability will be required only for fine-tuning purposes, as opposed to the case of an OTS model where it will function to a greater extent to provide a proper fit and proper medial-lateral loading, e.g., up to 1.5″ of height adjustment and up to 18° of medial/lateral angular adjustment.
While various types of length adjustment mechanisms are known and may be used in accordance with the present invention, it is preferred that the length adjustment mechanism be a slide mechanism. In particular, the slide mechanism 45 illustrated in FIGS. 1–4 comprises a slotted guide 46 and a slider 47 which is fixable at selected locations along the length of the slotted guide 46 by loosening the screws 48 to free the slotted guide 46 for adjustment movement relative to the slider 47 and then re-tightening the screws 48 when the desired adjustment position has been reached. The slotted guide 46 is formed as an extension of an upper part of the upper hinge 19 of the joint mechanism 16 , 17 . The slotted guide 46 is received in a recess 50 that is formed in a side of a respective one of the femoral arms 3 , 5 . The slider 47 is a link member that is slidably received in the slot of the slotted guide 46 but is fixed relative to the respective femoral arm 3 , 5 by the pair of screws 48 which are threaded into the link member and extend through the side of the respective femoral arm 3 , 5 via apertures formed in the base wall of the recess 50 .
Alternatively, as shown in FIG. 5 , the slotted guide 46 ′ formed as an extension of an upper part of said joint mechanism is telescopically received within an interior space of the respective femoral arm 3 , 5 . In this case, the slider is only a single screw 48 is used which extends through the slot of the slotted guide 46 ′ between and through opposite sides of the respective femoral arm. Since there is no separate slider as in the embodiment of FIG. 4 , a nut 49 is threaded onto the end of the screw. Tightening of the nut on screw 48 resiliently draws the opposed walls of the hollow portion of the femoral arm 3 , 5 together so as to clamp the slotted guide 46 ′ therebetween, and loosening of the nut 49 on the screw 48 allows the opposed walls to move back to their unstressed positions, freeing the slotted guide to move in and out of the femoral arm 3 , 5 . This construction is particular useful for a custom fitted knee brace where a lesser degree of sliding movement is required and a more finished look may be desired given the extra cost of a custom fitted brace.
FIGS. 6–8 show examples of the operation of the length adjustment mechanisms 45 and double hinge joint mechanism of the present invention with the OTS knee brace of the invention. FIG. 6 shows the situation where both length adjustment mechanisms 45 are fully extend in a neutral angular position. FIG. 7 shows the medial side adjustment mechanism 45 maximally extended and the lateral side length adjustment mechanism 45 maximally retracted resulting in a maximally lateral angular correction of about 18°, the femoral arms 3 , 5 pivoting about the unicentric hinges 19 . FIG. 8 shows the lateral side adjustment mechanism 45 maximally extended and the medial side length adjustment mechanism 45 maximally retracted resulting in a maximally medial angular correction of about 18°, the femoral arms 3 , 5 pivoting about the unicentric hinges 19 . Because of the action of the unicentric hinges 19 , lateral/medial loads that could produce binding of the polycentric hinges 16 , 17 , are not transmitted to the polycentric hinges so that the can move freely despite and angular corrections that are set.
FIGS. 6–8 show examples of the operation of the length adjustment mechanisms 45 and double hinge joint mechanism of the present invention with the OTS knee brace of the invention. FIG. 6 shows the situation where both length adjustment mechanisms 45 are fully extend in a neutral angular position. FIG. 7 shows the medial side adjustment mechanism 45 maximally extended and the lateral side length adjustment mechanism 45 maximally retracted resulting in a maximally lateral angular correction of about 18°, the femoral arms 3 , 5 pivoting about the unicentric hinges 19 . FIG. 8 shows the lateral side adjustment mechanism 45 maximally extended and the medial side length adjustment mechanism 45 maximally retracted resulting in a maximally medial angular correction of about 18°, the femoral arms 3 , 5 pivoting about the unicentric hinges 19 . Because of the action of the unicentric hinges 19 , lateral/medial loads that could produce binding of the polycentric hinges 16 , 17 , are not transmitted to the polycentric hinges so that they can move freely despite any angular corrections that are set.
While preferred embodiments of the invention have been shown and described, it should be appreciated that the invention is not limited to the specifics of these embodiments. To the contrary, numerous variations and modifications within the scope of the disclosed concepts will be apparent to those of ordinary skill, e.g, through the use of different types of hinge mechanisms, different types of adjustment mechanisms and different manners for attachment of the brace to a wearer's leg, as well as the provision of various ancillary features, such as angular adjustment stops. As such, the invention should be considered as being fully commensurate with the scope of the appended claims.
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An orthopedic knee brace which will allow lateral-medial compensation to be obtained while still enabling the use of known joint mechanism which will constrain the leg to execute the correct natural movement of the knee by separating lateral-medial compensation and anterior posterior movement functions. More specifically, the present invention utilizes a pair of hinges, one of which provides for movement in a posterior-anterior plane and the other which provides for movement in a medial-lateral plane. In this way, any conventional knee joint mechanism may be employed and movement of the leg can be properly constrained to execute a prescribed motion.
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CROSS REFERENCES TO CO-PENDING APPLICATIONS
[0001] None.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention is for a railroad gate release mechanism, and in particular, is for a railroad gate release mechanism which allows for maintaining of structural integrity of a railroad grade crossing arm during and subsequent to being struck by an automotive vehicle. Although a railroad gate release mechanism is described, the release mechanism can be incorporated for other uses such as, but not limited to, parking lot gates, restricted access gates, road closure gates, toll gates, and the like.
[0004] 2. Description of the Prior Art
[0005] Railroad crossing grades are protected by railroad grade crossing arms which are stored substantially in a vertical position and which are actuated by railroad gate actuators which reorient the crossing arms to a horizontal position across a railroad grade crossing to warn operators of vehicles of oncoming train traffic and to physically place a barrier in the form of a crossing arm at both sides of the railroad grade crossing to prevent passage of a vehicle into the railroad grade crossing. Motorists unaware of the movement of a crossing arm may impinge the crossing arm to the extent that physical damage occurs where the crossing arm is broken and parted from the railroad gate actuator. Such an occurrence can compromise the safety of the railroad grade crossing in that other motorists will not be warned of impending danger due to the destruction of the crossing arm. Such occurrences compromise safety, as well as add a financial maintenance burden.
SUMMARY OF THE INVENTION
[0006] The general purpose of the present invention is to provide a railroad gate release mechanism.
[0007] According to one embodiment of the present invention, there is provided a railroad gate release mechanism for attachment between a railroad gate actuator and a crossing arm including opposing channel-shaped brackets which attach to a railroad gate actuator and which also serve as mounting structure for other components of the railroad gate release mechanism. A pivotable arm assembly, to which a crossing arm is attached, pivotally mounts between bearing plates located on the inwardly facing surfaces of the opposing channel-shaped brackets. The pivotable arm assembly is influenced by a detent and plunger arrangement which maintains a perpendicular relationship of the pivotable arm assembly and the attached crossing arm with respect to the railroad gate actuator until acted upon by outside forces, such as a vehicle impinging the crossing arm. Such impingement causes the railroad gate release mechanism, with the attached crossing arm, to pivotally overcome the influence of the detent and plunger arrangement and to swing substantially horizontally out of the way of the impinging vehicle without functional damage to the crossing arm. Such pivotal breaking away substantially reduces the possibility of breakage of the crossing arm, as little bending moment is actually applied to the crossing arm itself due to the substantially unrestricted movement allowed by the railroad gate release mechanism. Subsequent to such impingement and when the vehicle has ceased to contact the crossing arm, spring assemblies function to return the pivotable arm assembly of the railroad gate release mechanism, with the attached crossing arm, to the detented position to continue to offer gated protection at the crossing grade. A shock absorber allows for rapid rate pivoting of the pivotable arm assembly in one direction during impingement and allows for a slower rate return of the pivotable arm assembly in the return direction subsequent to impingement. A centering spring assists in returning of the pivotable aria assembly to the detented position.
[0008] One significant aspect and feature of the present invention is a railroad gate release mechanism which secures between the mount arms of a railroad gate actuator and a crossing arm.
[0009] Another significant aspect and feature of the present invention is a railroad gate release mechanism which when impinged releasably allows breakaway pivoting in two directions of a crossing arm from a normal and detented position to prevent damage to the crossing arm.
[0010] Another significant aspect and feature of the present invention is a railroad gate release mechanism which allows return pivoting of a crossing arm to a normal and detented position subsequent to breakaway pivoting caused by impingement.
[0011] Still another significant aspect and feature of the present invention is a railroad gate release mechanism which offers grade crossing protection subsequent to crossing arm impingement.
[0012] Yet another significant aspect and feature of the present invention is the use of cables attached to a pivotable arm assembly which connect to springs in spring assemblies which are compressed during impingement with the front side of a crossing arm to subsequently power the return of the pivotable arm assembly and attached crossing arm to an original and detented position.
[0013] A further significant aspect and feature of the present invention is the use of a shock absorber which allows rapid deployment and release of a pivotable arm assembly and attached crossing arm during impingement and which allows return of the pivotable arm assembly and attached crossing arm at a slower rate subsequent to impingement, whereby the slower return rate reduces return overshoot of the pivotable arm assembly and the crossing arm.
[0014] A still further significant aspect and feature of the present invention is the use of a centering spring assembly which urges the pivotable arm assembly into a normal and detented position when the crossing arm is impinged from the rear side.
[0015] Having thus described an embodiment of the present invention and set forth significant aspects and features thereof, it is the principal object of the present invention to provide a railroad gate release mechanism.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] Other objects of the present invention and many of the attendant advantages of the present invention will be readily appreciated as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings, in which like reference numerals designate like parts throughout the figures thereof and wherein:
[0017] [0017]FIG. 1 illustrates an isometric view of a railroad gate release mechanism, the present invention, along with portions of mount arms and a crossing arm which are associated therewith in use;
[0018] [0018]FIG. 2 illustrates the railroad gate release mechanism with an upper bracket removed;
[0019] [0019]FIG. 3 illustrates a rear isometric view of the elements of FIG. 2;
[0020] [0020]FIG. 4 illustrates an isometric view of the pivotable arm assembly;
[0021] [0021]FIG. 5 illustrates an end view of the railroad gate release mechanism;
[0022] [0022]FIG. 6 illustrates a side view of the railroad gate release mechanism;
[0023] [0023]FIG. 7 illustrates a top view of the railroad gate release mechanism in partial cutaway showing its normal position when in use; and,
[0024] [0024]FIG. 8 illustrates a top view of the railroad gate release mechanism in partial cutaway showing how it moves when the crossing arm is impinged by a vehicle or other object.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0025] [0025]FIG. 1 illustrates an isometric view of the railroad gate release mechanism 10 , the present invention, shown in the position which it has between mount arms 20 and 22 of a railroad gate actuator and a crossing arm 12 when the crossing arm 12 is in the horizontal position, such as for stopping of traffic at a railroad grade crossing.
[0026] [0026]FIG. 2 illustrates the railroad gate release mechanism 10 with an upper bracket 14 removed for the purpose of clarity. With respect to FIGS. 1 and 2, the invention is further described. Partial or fully visible components of the railroad gate release mechanism 10 include opposing upper and lower brackets 14 and 16 each having a plurality of mounting holes 18 a - 18 n for attachment to the mount arms 20 and 22 of a railroad gate actuator, as well as other holes for mounting of other components thereto. Opposing upper and lower bearing plates 24 and 26 suitably secure to the inwardly facing surfaces of the upper and lower brackets 14 and 16 to accommodate a vertically oriented pivot pin 28 and a pivotable arm assembly 30 . The pivotable arm assembly 30 aligns between the upper and lower brackets 14 and 16 and is pivotally secured therebetween by the pivot pin 28 . The pivotable arm assembly 30 includes, in part, an arm 50 and opposing geometrically configured and horizontally aligned upper and a lower swing plates 32 and 34 . Arm 50 serves as a mount for the crossing arm 12 , shown in FIG. 1. One end of the lower swing plate 34 is in the shape of an arc to which opposing cable guide plates 36 and 38 are opposingly and suitably secured. The cable guide plates 36 and 38 extend beyond the arced end of the lower swing plate 34 to form a cable channel 40 therebetween. A semi-circular detent 42 is comprised of semi-circular cutouts in each of the cable guide plates 36 and 38 the combination of which forms detent 42 . The upper swing plate 32 is fashioned similarly to the lower swing plate 34 and includes opposing cable guide plates 44 and 46 to form a cable channel 48 . Brace plates 49 and 51 (FIG. 4) also align between the upper swing plate 32 and the lower swing plate 34 and abut opposing sides of a right arm plate 52 . The arm 50 aligns and suitably secures between the upper swing plate 32 and the lower swing plate 34 . The arm 50 includes the right arm plate 52 aligned between the full length of the upper swing plate 32 and the lower swing plate 34 . The right arm plate 52 extends outwardly beyond the upper swing plate 32 and the lower swing plate 34 and, as such, serves as a mount for a left arm plate 54 and spacer bars 56 and 58 disposed therebetween. A portion of the right arm plate 52 extends along the length of the upper swing plate 32 and the lower swing plate 34 . A right brace plate 62 and a left brace plate 64 are mounted vertically between the upper bracket 14 and the lower bracket 16 . A plunger housing 66 including a spring loaded movable plunger 68 mounts to the right brace plate 62 . The plunger 68 engages the detent 42 of the pivotable arm assembly 30 to maintain the position of the pivotable arm assembly 30 where the crossing arm 12 is extended across a grade crossing. The left brace plate 64 also serves as a mounting plate for upper and lower spring assemblies 70 and 72 , a shock absorber 74 , and a centering spring assembly 76 .
[0027] [0027]FIG. 3 illustrates a rear isometric view of the elements of FIG. 2. Illustrated in particular is the relationship of the pivotable arm assembly 30 to the upper and lower spring assemblies 70 and 72 , the centering spring assembly 76 , and the shock absorber 74 . Opposing mounting brackets 78 and 80 align and suitably secure into slots 82 and 84 , respectively, in the left brace plate 64 . One end of the shock absorber 74 pivotally secures to the mounting brackets 78 and 80 , and the other end of the shock absorber 74 pivotally secures to a pair of mounting brackets on the arm 50 . The shock absorber 74 when moved to the compressed position allows rapid movement of the pivotable arm assembly 30 and allows a slower rate of movement when returning to the extended position to suitably control the return rate of the pivotable arm assembly 30 subsequent to impingement of the crossing arm 12 . The horizontally oriented upper and lower spring assemblies 70 and 72 align and suitably secure in bores 86 and 88 in the left brace plate 64 . One end of cables 90 and 92 secure by ball ends 94 and 96 (FIG. 2) and align in the cable channels 40 and 48 of the lower and upper swing plates 34 and 32 , respectively. The other ends of the cables 90 and 92 secure to circular plates 98 and, 100 located inside of the lower and upper spring assemblies 72 and 70 . Springs 102 and 104 are located interior to the lower and upper spring assemblies 72 and 70 between the circular plates 98 and 100 and the inward facing ends 106 and 108 of the lower and upper spring assemblies 72 and 70 . Movement of the pivotable arm assembly 30 including its arm 50 in a direction as indicated by arrow 110 causes compression of the springs 102 and 104 to provide for subsequent spring powered action of the pivotable arm assembly 30 to return the pivotable arm assembly 30 to its normal detented position subsequent to impingement of the crossing arm 12 .
[0028] [0028]FIG. 4 illustrates an isometric view of the pivotable arm assembly 30 . Illustrated in particular are the tabbed brace plates 49 and 51 extending vertically and secured between the upper swing plate 32 and the lower swing plate 34 . One set of mounting brackets 112 secures at one end of the right arm plate 52 to serve as a mount for one end of the centering spring assembly 76 (FIG. 3), and another set of mounting brackets 114 secures at a mid-position on the left arm plate 54 to serve as a mount for one end of the shock absorber 74 of FIG. 1.
[0029] [0029]FIG. 5 illustrates an end view of the railroad gate release mechanism 10 . A rectangular hole 65 is provided in the right mounting plate 62 to accommodate the plunger 68 and to accommodate other mounting geometry of the plunger housing 66 .
[0030] [0030]FIG. 6 illustrates a side view of the railroad gate release mechanism 10 , where all numerals correspond to those elements previously described.
[0031] [0031]FIG. 7 illustrates a top view of the railroad gate release mechanism 10 in partial cutaway showing its normal position when in use, where all numerals correspond to those elements previously described. The cable guide plate 44 and underlying cable guide plate 46 are shown in partial cutaway to reveal the detent 42 in the lower swing plate 34 of the pivotable arm assembly 30 . The spring loaded plunger 68 engages the detent 42 of the pivotable arm assembly 30 to maintain the position of the pivotable arm assembly 30 where the crossing arm 12 (FIG. 1) is extended across a grade crossing. The spring loaded plunger 68 is of sufficient strength to maintain the pivotable arm assembly 30 including its arm 50 and an attached crossing arm 12 in the desired orientation during raising and lowering and to maintain the desired orientation extending across the crossing grade unless impinged by a vehicle.
[0032] [0032]FIG. 8 illustrates a top view of the railroad gate release mechanism 10 in partial cutaway and best illustrates the mode of operation of the railroad gate release mechanism 10 , where all numerals correspond to those elements previously described. Pivotal arm relief is provided for front side or rear side impingement of the attached crossing arm 12 . Impingement of the front side of the attached crossing arm 12 by a vehicle or other object forces pivoting of the pivotable arm assembly 30 about the pivot pin 28 , as shown by arrow 110 . Such pivoting allows, for purposes of example and illustration, rotation of 40° of the pivoting arm assembly 30 about the pivot pin 28 . Such forced pivoting causes disengagement of the spring loaded plunger 68 from the detent 42 of the pivotable arm assembly 30 , thus allowing the pivotable arm assembly 30 and attached crossing arm 12 to pivot, thereby preserving the integrity of the attached crossing arm 12 . Pivoting of the pivotable arm assembly 30 and attached crossing arm 12 is allowed at a suitable and rapid rate and is not greatly influenced by the shock absorber 74 . However, return of the pivotable arm assembly 30 and attached crossing arm 12 to the detented position is influenced by the shock absorber 74 which acts to allow return pivoting at a rate much less than that during impingement-caused pivoting. During impingement-caused pivoting of the pivotable arm assembly 30 and attached crossing arm 12 , spring 104 in the upper spring assembly 70 and spring 102 in the lower spring assembly 72 are compressed by the movement of the cables 92 and 90 , respectively, which are attached in the cable channels 48 and 40 located on the ends of the upper swing plate 32 and the lower swing plate 34 , respectively. Such spring compression provides force to return the pivotable arm assembly 30 and attached crossing arm 12 towards and into the detented position at a controlled rate as provided by the shock absorber 74 , as previously described.
[0033] Impingement of the rear side of the attached crossing arm 12 provides for disengagement of the spring loaded plunger 68 from the detent 42 of the pivotable arm assembly 30 , thus allowing the pivotable arm assembly 30 and attached crossing arm 12 to pivot, thereby preserving the integrity of the crossing arm 12 . Such pivoting allows, for purposes of example and illustration, rotation of 15° of the pivoting arm assembly 30 about the pivot pin 28 as generally shown by arrow 116 . The centering spring assembly 76 urges and assists the pivotable arm assembly 30 to return to a normal and detented position.
RAILROAD GATE RELEASE MECHANISM PARTS LIST 10 railroad gate 49 brace plate release mechanism 50 arm 12 crossing arm 51 brace plate 14 upper bracket 52 right arm plate 16 lower bracket 54 left arm plate 18a-n mounting holes 56 spacer bar 20 mount arm 58 spacer bar 22 mount arm 62 right brace plate 24 upper bearing 64 left brace plate plate 65 rectangular hole 26 lower bearing 66 plunger housing plate 68 plunger 28 pivot pin 70 upper spring 30 pivotable arm assembly assembly 72 lower spring 32 upper swing plate assembly 34 lower swing plate 74 shock absorber 36 cable guide plate 76 centering spring 38 cable guide plate assembly 40 cable channel 78 mounting bracket 42 detent 80 mounting bracket 44 cable guide plate 82 slot 46 cable guide plate 84 slot 48 cable channel 86 bore 88 bore 90 cable 92 cable 94 ball end 96 ball end 98 circular plate 100 circular plate 102 spring 104 spring 106 end 108 end 110 arrow 112 mounting bracket set 114 mounting bracket set 116 arrow
[0034] Various modifications can be made to the present invention without departing from the apparent scope hereof:
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The invention is a railroad gate release mechanism which attaches between the mount arms of a railroad gate actuator and a crossing arm to prevent breakage of the crossing arm due to impingement by a vehicle. A pivotable arm assembly allows released movement in two directions of the crossing arm in reaction to impingement and returns the crossing arm to the original and detented position subsequent to impingement to maintain grade crossing protection. Spring assemblies, a shock absorber and a spring centering assembly act to return the pivotable arm assembly and attached crossing arm to the normal detented position.
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BACKGROUND OF THE INVENTION
The present invention relates to a trigger control means for moveable toys, and more particularly to a mechanical trigger control means which can trigger moveable toys to start their various actions.
Most moveable toys are actuated by the driving force of a coil spring, spiral spring or cell motor, which can manipulate only one or two simple actions rather than many actions, such as a forward, backward, or reciprocal movement, and/or a limited rotation. A moveable toy which can perform various actions is usually controlled by a complicated electric-circuit. The electric-circuit is not only too expensive to produce but also too difficult to operate safely; it is not fit for a child or even a youth, only an adult. A new mode of plastic model toy which is primarily driven by a plurality of springs has been provided. In addition to the above-mentioned movements and rotation, the toy can perform a number of actions by being actuated by the driving force of springs which are adapted to be separately and manually activated at any time or in any sequence. Whenever a certain button is pushed, the driving force reserved in a certain spring will be triggered and released to start a certain action.
Although the above-mentioned mechanically moveable toy which is driven by springs, cell motors or the like is cheap in cost and safe to operate, but it is difficult for a child to push a button disposed on a toy to trigger the driving force reserved in a spring when the toy is moving or carrying out another action.
SUMMARY OF THE INVENTION
Therefore, the object of the present invention is to provide a trigger control means for a moveable toy which is able to perform various actions, and which constitutes a mechanical structure and is adapted to automatically trigger the actions of the toy in sequence.
Firstly, the present invention provides a toy comprising: a main body for defining the toy; a frame disposed within the main body; at least one acting means being able to reserve energy for generating an acting force and having a member for triggering the acting force; and a trigger control means installed in the frame and adapted to reserve energy for generating a rotating force, by which the member of the above-mentioned acting means can be actuated and the acting force of the acting means can be triggered and released.
The above-mentioned toy is preferably a moveable toy, such as a toy car, which has a rotating means, such as a means comprised of wheels, said rotating means being actuated by the driving means installed in the above-mentioned trigger control means which can generate a rotating force via a gear train which is adapted to reduce and transmit the rotating force to the rotating means.
Secondly, the present invention further provides a trigger control means for the above-mentioned toy, comprising: at least one self-retrievable rocking arm having a fulcrum, a first end disposed in one side of the fulcrum which is adapted to actuate the member of the above-mentioned acting means when the rocking arm is rocked, and a second end disposed in the other side of the same; a cam means adapted to be driven by the rotating force transmitted via the gear train, which includes a rotatable cam drum having a cam surface adapted to rock the second end of the rocking arm when the cam drum is in a rotating state.
In addition, because the toy has a plurality of acting means, the trigger control means can be constructed to have a plurality of rocking arms, and the cam drum can be configured to have a cam surface which can rock the second ends of the plurality of rocking arms in a certain sequence when the cam drum is in a rotating state.
In the above-mentioned construction, while the primary action of the rotating means is actuated by the driving means, such as a spiral spring, the trigger control means of the present invention can simultaneously reduce the rotation speed of the rotating force supplied from the rotating means by its gear set, and transmit the speed-reduced force to the cam gear of its transmission means to rotate the cam gear for a certain angle and ascend the two-bar linkage from a folded state to a straight state by means of the relationship between the pin for pivoting the two bars of the linkage and the guiding channel formed on the cam gear so as to put the idle gear which is pivoted in the free end ft one of the bar to the position where the gear member of the cam drum and the output gear of the above-mentioned gear set can be engaged by means of the same . Then, by means of friction transmission, the cam drum can be rotated by the gear member at an appropriate speed. Further, by means of the tongues protruded from the cam drum, the rocking arms can be rocked in sequence, and in this way, the acting means can be intermittently triggered in sequence. When the cam drum has rotated a certain number of revolutions, one end of the cam drum, which is composed of a set of friction plates, will be braked, and the friction plate for driving the cam drum, which is engaged with the friction plate installed in the other end of the same, will slip off the engagement, because the input force is larger than the engagement for driving the cam drum and smaller than that for braking the same. Thus, the cam drum will be braked and the rotation will cease while the other actions of the toy are still carried out. In addition, when a rotating force which is larger than the engagement for braking the cam drum is applied to the same, the cam drum will slip off the engagement and be rotated. Therefore, the orientation of the cam drum can be changed and the triggering sequence of the trigger control means can be shifted. That is, a toy having the trigger control means installed therein can carry out various actions in a selected sequence which can be shifted.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention is illustrated by way of examples in the accompanying drawings, in which:
FIG. 1a is a perspective view of a preferred embodiment according to the present invention, wherein the main construction of the embodiment is shown by an enlarged and exploded view;
FIG. 1b is a plan view of the embodiment shown in FIG. 1a;
FIG. 2 is an assembled view of the embodiment shown in FIG. 1a;
FIG. 3 is an enlarged view illustrating another exemplary relationship between the friction plates 32-37 or 33-38 shown in FIG. 1a;
FIG. 4 and FIG. 5 are views respectively showing the orientation of the stopper 12 before and after the rotation of the cam drum 31;
FIG. 6 is an enlarged sectional view illustrating another exemplary construction for driving the cam-drum 31;
FIG. 7 is an enlarged partially sectional view illustrating another exemplary construction for transiting the trigger sequence of the cam drum, wherein the portion adjacent to the friction plate 37 is also shown;
FIG. 8 and FIGS. 9A, 9B, and 9C are perspective views illustrating the operational relationships of two exemplary moveable toys used in the above-mentioned embodiment; and
FIGS. 10A, 10B and 10C and FIGS. 11A, 11B and 11C are perspective views of two examples for illustrating the performance of moveable toys which have two trigger control means installed therein.
DETAILED DESCRIPTION OF THE INVENTION
Referring to FIG. 1a and FIG. 1b, there is a frame 1 shaped as a housing. The frame 1 has a driving means 11 installed on one internal wall of it. Within the driving means 11, there is a spiral spring 22 installed. A transmission means 2 having an idle gear 233 and a gear set 23 are installed within the frame 1 extensively from the rear portion to the middle portion. The gear set 23 is adapted to receive the output of the driving means 11, to reduce the rotation speed of the output, to constantly transmit the output to the rotating means of a toy, such as the wheels of a toy car, and to output with a rotation speed which is appropriate to the trigger control means when the brake is released. The idle gear 233 is not adapted to be actuated immediately, instead, after a period, the transmission means 2 is started by the gear set 23. In addition, within the frame 1, there is a cam means 3 installed in the front side of the same. As shown in the top portion of FIG. 1a, the view of the cam means 3 is exploded and enlarged for the convenience of illustration. Above the cam means 3, there is a trigger means 4 constructed by four rocking arms 41, one end of each rocking arm 41 is in contact with the cam drum 31 of the cam means 3. The spiral spring 22 is adapted to be wound up by a rotatable member 21, such as a thumb handle or a wheel of a toy car.
The gear set 23 is composed of a series of gears, the construction of which may be generally conventional, but as stated hereinbefore, which must be adapted to receive the output of the spiral spring 11, to constantly transmit the output with an appropriate rotation speed, to the rotating means of a toy, such as the wheels of a toy car, and to drive the transmission means 2 and the cam means 3 with an appropriate speed.
The transmission means 2 comprises a cam gear 234 for receiving and lagging the rotating force supplied via a pinion 234b which is coupled in an output shaft of the gear set 23. On one side cf the cam gear 234, there is a guiding channel 234a shaped along the periphery as an opened annulus, one end of which is opened and the other is closed. The transmission means 2 further comprises a two-bar linkage constructed by links 231, 232 which are rotatably and slidably linked together via a long slot by a pin 235. The link 231 is further rotatably borne by the same axle with which the rotating means 21 is borne. In the other end of the link 232 the above-mentioned idle gear 233 is pivoted, and, in addition, the middle point of the link 232 is further pivoted in the frame 1. Although it is not shown in the figures, the pin 235 is made of a flexible material, the internal end of which is adapted to press the periphery of the cam gear 234 and to enter the guiding channel 234a. Usually, the two-bar linkage is in folded state, as shown in FIG. 1a. When the cam gear 234 is rotated by the pinion 234b, the pin 235 will enter at the opened end of the guiding channel 234a and relatively move along the same, then finally be pushed upwardly by the closed end of the same to the upper position in which the two-bar linkage will be in straight state as shown in FIG. 2. In this way, the idle gear 233 will be moved to the cam means 3. In addition, the free end of the link 231 has an idle gear 231a pivoted therein by means of a pin. The idle gear 231a usually engages with the pinion 234b and the cam gear 234, and transmits the rotation which is transmitted from the gear set 23. Thusly, as the end pivoted with the link 232 is rotated, the gears 234 and 234b will be disengaged.
In respect to the cam means 3 disposed in the front side of the frame 1, it comprises a shaft 35, the free end of which has a thumb knob 34 fixed therein. Fitted along the shaft 35, there is a hollow, cylinderical cam drum 31, friction plates 32, 33 respectively disposed in the sides of the cam-drum 31, which are axially slidably fitted with the same, a friction plate 37 for braking the cam-drum 31, which is frictionally fitted with the friction plate 32, and a friction plate 38 for driving the cam-drum 31, which is frictionally fitted with the friction plate 33. On the external surface of the cam drum 31, there are four protruding tongues 311 formed apart with angular intervals. In this embodiment, the axial intervals of the tongues 311 are equal, but they are not limited by that. The internal surface of the cam drum 31 has splines 312 formed thereon. In addition, there are protrusions 322, 332 respectively formed in the periphery of the friction plates 32, 33, which are slidably inserted into the splines 312. Within the cam drum 31, an extension spring 36 is further installed between the friction plates 32, 33, causing the friction plates 32, 33 to be pressed outwardly. The outward walls of the friction plates 32, 33 respectively have spherical protrusions 321 and 331 for engaging with the spherical concaves 371, 381 correspondly formed on the inward walls of the friction plates 37, 38. In this embodiment, the heights of the protrusions 321 and the concaves 371 respectively formed on the friction plates 32 and 37 are about 0.8 mm, and the height of the protrusions 331 and the concaves 382 are about 0.4 mm. The friction plate 32 is fixed in the shaft 35 so as to be rotated by means of the thumb knob 34. Further, a lug 372 is radially formed in the periphery of the friction plate 37 so that the rotation can be ceased in every round by a stopper 12 protruded from the frame 1, which is disposed in a position which can block the rotating of the lug 372. Additionally, there is a gear member 382 formed in the other side of the friction plate 38 which is frictionally fitted with the friction plate 33 for driving the cam drum. When the idle gear 233 pivoted in the free end of the link 232 is moved into the gap between the gear member 382 and an output gear 236 of the above-mentioned gear set 23, and engaged with them, the cam-drum 31 will be rotated.
The trigger means 4 is composed of four L-shaped rocking arms 41(hereinafter the actuating ends of them will be referred to as A, B, C, D ) the elbow portions of which are pivoted in series in the frame 1 by means of a pin. One portion 412 of each arm (hereinafter referred to as first portion ) is adapted to actuate a member of acting means (not shown ), and the other portion 411 (hereinafter referred to as second portions) makes contact with the external surface of the cam-drum 31. In this way, a first portion 412 will be rocked counterclockwise when the corresponding second portion 411 is pushed by a tongue 311 formed on the rotating cam drum 31.
The operation of the embodiment will be illustrated hereunder.
When the spiral spring 22 is wound by rotating the rotating means 21, the link 231 will be rotated counterclockwise and the idle gear 231a will be engaged with the cam gear 234 and the pinion 234b so as to transmit the rotation of the gear set 23. On the other hand, the link 232 will be rotated clockwise and the idle gear 233 will be disengaged from the gear member 382 and the gear 236. The protruded end of the pin 235 will simultaneously escape from the guiding channel 234a via the opened end of the same. Thusly, the ends of the links 231, 232, which are mutually pivoted together, wil1 descend to the lower position folded as shown in FIG. 1a.
When the rotating force of the spiral spring 22 is emitted via the gear set 23, the primary action, such as rotating the wheels of a toy car, will be carried out and the car will be moved. As the toy car is in moving state, the rotating force of the spiral spring 22 will be transmitted via the gear set 23, and its rotation speed will be reduced by the same. In this way, the pinion 234b wil1 be rotated so that the cam gear 234 will then be rotated by means of the idle gear 231a. The overall output of the spiral spring 22 and the reduction ratio of the gear set 3 are preferably that the cam gear 234 will be rotated about one round when the primary action has carried out one stroke. According to the above-mentioned action mode, the rotation speed of the pinion 234b and the output speed of the gear 236 can be selected appropriately.
As the cam gear 234 is in a rotating state, the pin 235, by which the links 231, 232 are rotatably borne together therein, will enter at the opened end of the guiding channel 234a and then will be upwardly pushed by the closed end of the same so that the two-bar linkage can ascend to the upper position in which the links 231, 232 are in unfolded state. In this way, the idle gear 231a will be moved to the state in which the rotating force of the gear set 23 can not be transmitted and the rotation of the cam gear 231a will cease. As to the idle gear 233 in the other end of the linkage, it will descend to the engaged state by which the gear member 382 of the cam means 3 can be rotated by means of the gear 236.
The input of the gear member 382 will then be transmitted to the friction plate 38 and rotate the same so that the cam drum 31 will be rotated by means of the friction plate 33 which is frictionally fitted with the friction plate 38 by the engagement between the protrusions 331 and the concaves 381 and also simultaneously rotated with the same. When the cam drum 31 is in a rotating state, the tongues 311 formed thereon will be moved along their circumferential orbit and respectively rock the corresponding arms 41 by pushing the second portions 411 of the same in sequence so that the members for triggering the acting means, such as the buttons for triggering various actions of a toy, will be actuated in sequence by the first ends 412 of the arms 41.
When the cam drum 31 is rotated one round and the actions are all finished, the lug 372 protruded from the friction plate 37, which is frictionally fitted with the friction plate 32 by the engagement between the protrusions 321 and the concaves 371, wil1 be rotated from the position S where it is disposed under the stopper 12, as shown in FIG. 4, to the position E in which it is disposed above the same, as shown in FIG. 5, and stopped by the stopper 12. However, by that time, the rotating force is transmitted via the gear member 382 to the friction plate 38. In this way, the friction plate 38 will escape from the engagement formed between the protrusions 381 and the concaves 331 which respectively have the height of 0.5 mm, because upon the same compression force of the spring 36, the engagement is far weaker than that formed between the protrusions 321 of the friction plate 32 and the concaves 371 of the friction plate 37 which respectively have the height of 0.8 mm.
It is worthy of note that the relative position of the cam drum 31 can be regulated by means of the thumb knob 34. When the thumb knob 34 is rotated, the friction plate 32 will slip o±f the engagement formed between the protrusions 321 and the concaves 371, because the lug 372 of the friction plate 37 is blocked by the stopper 12. In this way, the triggering sequence of the rocking arms 41 which is actuated by the tongues 311 formed on the cam-drum 31 can be shifted, such as from A, B, C, D to B, C, D, A or C, D, A, B . . . etc.
In addition, the lug 372 of the friction plate 37 can be rotated opposite to the position S shown in FIG. 4 by means of a transmission means which can be actuated by the rotating means 21. Of course, any means which can be actuated via the shaft 35 by rotating the thumb knob 34 is also preferred.
FIG. 3 shows an enlarged view illustrating another exemplary relationship between the friction plates 32-37 or 33-38. As shown in the figure, one of the friction plates 32 or 33 has one-way gear teeth 324 radially formed thereon, and the other 37 or 38 has the same teeth 374 formed thereon except that they are formed in an opposite circumferential direction, so that the gears can be engagingly moved together in one way because the friction plates 32, 33 are outwardly compressed by the spring 36.
FIG. 6 shows an enlarged sectional view illustrating another exemplary construction for driving the cam drum. As shown in the figure, inside the opened end there are internal gear teeth 313 formed on the internal peripheral wall of the cam drum 31a. In addition, there is a plate 38a for driving the cam drum 31, which has a gear member 382 formed on one side and an insert 38 formed on the other side the insert being installed inside the cam drum 31a and having a pair of claws 383, 383 flexibly protruded from its periphery and engaged with the gear teeth 313. The plate for braking the cam drum 31 can also be made to be of the same construction which can carry out the same performance as that of the above-mentioned embodiment. In the figure, the numerals 385, 385 are marked for the cavities of the claws 383, 383 which are formed for increasing the flexibility of them.
In addition, the plate 37a for braking the cam drum 31 can also be constructed to resemble the structure shown in FIG. 7. As shown in the figure, the cam drum 31 has an end plate with a square-shaped neck 317 sleeved around the shaft 35. There are a pair of parallel ribs 374, 374 flexibly formed on the corresponding side of the plate 37a, by which the neck 314 can be engaged therebetween. Thusly, the plate 37a can be rotated and stopped simultaneously with the cam drum 31. However, when the thumb knob 34 is strongly rotated as the lug 372 formed in the periphery of the plate 37a is blocked by the stopper 12, the ribs 374, 374 will be deformed by the torsional force of the square neck 314 and pushed out from the frames 373. In this way, the cam drum 31 can be rotated by means of the thumb knob 34 while the plate 37a is stopped by the stopper 12. That is, the relative orientation of the cam drum 31 can be regulated, and the sequence of the trigger means 4, which is actuated by the tongues 311 protruding from the cam drum 31, can be shifted by rotating the thumb knob 34.
Hereinafter, several exemplary toys using the trigger control means wil1 be illustrated.
FIG. 8 shows a toy trailer 10 which has missile apparatuses 102, 103, 105, 106 respectively installed in its four corners. The four members for triggering the four missile apparatuses 102, 103, 105, 106 are adapted to make contact with the four actuating ends A, B, C, D of the rocking arms 41. Therefore, they can be controllably triggered by the trigger control means according to the present invention.
FIGS. 9A, 9B and 9C show a toy car which is composed of a parent car and two child cars. By means of the trigger control means 14, first, the child car disposed in the top portion of the parent car will be descended to the front portion, second, the other child car disposed in the rear portion will be ejected, third, the one now descended in the front portion will be ejected, then, the parent car itself will be moved forwardly. The numerals marked in the figure show the acting procedures mentioned hereinbefore.
FIGS. 10A, 10B and 10C and 11A, 11B and 11C respectively show the action series of exemplary toys which are controllably triggered by two sets of the trigger control means according to the present invention. For example, when the button I is pushed, the toy will be moved and its shape will be changed, and then, when the button II is pushed, the legs of the toy will be extended and the toy will be moved by the same.
As shown in the above-mentioned embodiment, the trigger control means of the present invention can reduce the rotation speed of the rotating force supplied from a rotating means, such as a spiral spring, by its gear set, and transmit the speed-reduced force to its cam gear to raise the two- bar linkage from a folded state to a straight state by means of the relationship between the pin for pivoting the two bars of the linkage and the guiding channel formed on the cam gear. Then, by means of the friction transmission, the cam drum can be rotated while the cam gear is stopped. Further, by means of the tongues protruded from the cam drum, the rocking arms can be rocked in sequence. In this way, the acting means can be controllably triggered in sequence. That is, a moveable toy having a trigger control means installed therein can controllably trigger its acting means by means of such a mechanical construction.
While the invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not to be limited to the disclosed embodiment, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the broadest interpretation so as to encompass all such modifications and equivalent arrangements.
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This invention provides a moveable toy with a trigger control mechanism which has: a main body for defining the toy; a frame disposed within the main body; at least one acting means being able to reserve energy for generating an acting force and having a member for triggering the acting force; and a trigger control means installed in the frame and adapted to reserve energy for generating a rotating force by which the member of the above-mentioned acting means can be actuated and the acting force of the acting means can be triggered and released.
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BACKGROUND OF THE INVENTION
1. Field of Invention
This invention relates to determining the magnitude and phase of an ac signal in less than one cycle even with dc offset present. More particularly, the invention discloses a method and apparatus for generating samples of sinusoidal current or voltage which are then used in a mathematical solution described in the invention to determine magnitude and phase. It is particularly useful in the presence of dc offset. Use of relatively few samples with a fast response time is disclosed. The invention is described in connection with protective relays.
2. Background Information
It is often necessary in electric power transmission systems to compute the magnitude and phase of the line current or voltage. Such computations are performed, for example, in protective relays.
In the case of protective distance relays, components are placed at each terminal of the protected line segment, these components analyze line currents and voltages to determine the location of a fault and trip circuit breakers at the respective terminals to isolate a fault determined to be between terminals. The invention can be used in such a relay system to measure the current and voltage.
The calculation of line voltage and line current as well as the phase is often made more difficult by the presence of dc offset. DC offset, such as could occur when a transformer is brought on line, can cause false trips in certain protective relays.
It is known that transient exponential noise can be reduced by substituting a compensated signal for the noise using linear approximations of the exponential component. Pending U.S. Patent Application Ser. No. 207,354 discloses a method and apparatus for reducing transient exponential noise in a sinusoidal signal by determining from digital samples of the signal the slope and initial ordinate value of a linear approximation of the transient exponential noise. The invention derives compensated values of current and voltage directly from digital samples of the waveform, and provides such compensated values from the beginning of the transient within one-half cycle of transient initiation plus one additional sample interval The compensation involves deriving the slope of the linear approximation of the exponential component of the transient by adding the magnitudes of each of a first pair of digital samples for instants spaced one-half cycle apart to produce a sum, subtracting from this sum the magnitude of each of a second pair of digital samples also one-half cycle apart and spaced from a corresponding one of the first pair of digital samples by a preselected number to produce a result.
The ordinate value of the linear approximation of the exponential component of the transient is determined by calculating the average of the magnitudes of the first pair of digital samples and adding to that average the sum of the magnitudes of the first pair minus the sum of the magnitude of the second pair divided by the number of intervals between corresponding samples in the first and second pairs of samples.
The method and apparatus discussed above does not involve calculation of magnitude and phase from alternate samples which are spaced by ninety electrical degrees of the waveform. In addition, there remains a need for a method and apparatus for accurate calculation of magnitude and phase in the presence of dc offset using relatively few samples and having a response time of less than one-half cycle.
As can be seen from the above, there is a need in many applications for a technique for rapidly analyzing waveforms, preferably in less than one power cycle. Further, the calculation must be made on-line with relatively modest hardware if it is to be cost competitive.
SUMMARY OF THE INVENTION
These and other needs are satisfied by the invention which is directed to a closed-form mathematical solution to the difficulty in measurement of magnitude and phase described above. The present invention provides for accurate determination of magnitude and phase even in the presence of dc offset.
The invention assumes sinusoidal currents and voltages. The invention is based on generating samples of the relevant electrical parameter, i.e., either current or voltage, with alternate samples separated by ninety electrical degrees of the line current or voltage, as the case may be. For computational purposes, those alternate samples are paired. For example, a first sample is generated which may be the first component of a first pair, the next sample is generated which would be the first component of a second pair, a third sample is generated at ninety electrical degrees of the line current or voltage from the first sample and that third sample would be the second component of the first pair. Another sample is then generated ninety electrical degrees apart from the second sample, and this completes the second pair, and so on. This generating sequence continues as long as the invention is in use.
Under certain conditions, which are described more fully hereinbelow, eight samples (four pairs) are required for performing the calculation of magnitude and phase Under other conditions, four samples (two pairs) are sufficient. In the latter case, the mathematical computation is continuously performed on the four most recent samples. In the former case, the computation would be continuously performed on the eight most recent samples. As a new sample is generated the oldest sample is discarded and the computation, which is described in detail below, is performed on the newest samples.
As mentioned above, the invention is directed to an ac electric power transmission system having sinusoidal currents and voltages which may also have decaying dc offset. The invention involves generating digitized samples of current or voltages at the predetermined intervals and performing certain calculations using pairs of the samples to determine the dc offset and the magnitude of the desired electrical parameter (i.e. current or voltage). In a preferred form the samples are generated at intervals of forty-five degrees of the waveform, and alternate samples are paired for the purpose of calculation of magnitude and phase.
If required in the application of the present invention, the magnitude as determined may be compared to a predetermined value and if it is equal to or in excess of that predetermined value, a signal is generated to trigger a desired event, such as tripping a circuit breaker.
In addition, the invention includes circuitry discussed in further detail herein which allows the calculation process to continue as new samples are generated.
BRIEF DESCRIPTION OF THE DRAWINGS
A full understanding of the invention can be gained from the following description of the preferred embodiments when read in conjunction with the accompanying drawings in which:
FIG. 1 is a waveform diagram indicating current, dc offset, and indicating a set of sample points for the electric power system with which one preferred embodiment of the invention may be used.
FIG. 2 is a diagram of a circuit incorporating the invention.
FIG. 3 is a flow chart of a suitable microcomputer program which can be used to implement the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 illustrates the sinusoidal waveform 1 of the current in a typical electric power transmission system with which a preferred embodiment of the invention may be used. The current is depicted by waveform 1 and the samples 2 are taken at predetermined intervals. FIG. 1 also depicts dc offset present in the current of the system, which can be induced, for instance by switching a reactive load onto the system. The dc offset Δ having decay constant α is decaying as depicted by line 4 The magnitude I of the peak value of the current of waveform 1 may be described in the following equation:
i.sub.k =I sin θ'Δ.sub.k Eq. (1)
where i k represents the instantaneous value of the sample;
I represents the peak value of the sinusoidal component;
θ represents the phase angle at the first sampled point; and
Δ k represents the dc offset of the Kth sample.
As mentioned above pairs of samples are generated with the samples in each pair 90 electrical degrees of the current fundamental frequency apart. Successive samples are taken within ninety degrees of the preceding sample. In the preferred form, two interleaved pairs spaced 45 electrical degrees apart are used. The samples are taken continuously at 45 degree intervals with the four most recent samples retained so that a new calculation can be made every 45 degrees. As can be seen from FIG. 1, the minimum response time in the preferred form will be slightly more than 3/8 of a cycle. This would include the computational speed of the hardware which would depend upon the microprocessor used in the application. In the exemplary embodiment, a conventional 16-bit general purpose processor is contemplated which would require approximately 200 microseconds to perform the algorithm of the present invention. It should be understood that other processing units may be used which could be faster or slower in computing the algorithm. As noted above, successive samples must be taken within ninety degrees of the preceding sample. This means that the maximum response time is slightly less than 1/2 cycle.
The samples so generated are used in the above equation as follows:
i.sub.1 =I sin θ+Δ.sub.1
i.sub.2 =I (sin θ+.sup.π /4)+Δ.sub.2
i.sub.3 =I (sin θ+.sup.π /2)+Δ.sub.3, or i.sub.3 =I cos θ+Δ.sub.3
i.sub.4 =I (sin θ+.sup.3π /4)+Δ.sub.4, or i.sub.4 =I cos (θ+.sup.π /4)+Δ.sub.4 Eq. (2)
squaring both sides and summing, and using the identity:
sin.sup.2 θ+cos.sup.2 θ=1
The following may be obtained:
(i.sub.1 -Δ.sub.1).sup.2 +(i.sub.3 -Δ.sub.3).sup.2 =I.sup.2
(i.sub.2 -Δ.sub.2).sup.2 +(i.sub.4 -Δ.sub.4).sup.2 =I.sup.2Eq. (3)
It is known that where samples are taken at equal intervals, the decaying dc offset Δ k at any point in time may be described as follows:
Δ.sub.k =α.sup.(k-1) ×Δ Eq. (4)
where α is the per-unit decay between samples .If samples are not taken at equal intervals, then K cannot be assumed to be equal to 1, 2, 3, 4 . . . etc. Instead K would have to be incremented differently and this would be known to one skilled in the art. Returning to equations (3), substituting as above for Δ k and eliminating I 2 yields ##EQU1## It can be seen that this is a quadratic equation for Δ. It can be solved if the decay constant α is known.
Alternatively, in cases where there is a comparatively long dc offset, the decay in one-half cycle is negligible. In such a case, the assumption may be made that α is equal to 1. In that case, equation (5) becomes: ##EQU2## Δ is then calculated from equation (6). Now, the magnitude I can be calculated from equation (3) above. The phase angle θ can be calculated from equation (2) above.
If, on the other hand, α is not known and if it were determined that in the application the error in assuming α to be equal to one would be too great, then four additional samples would be required to yield two equations (5) with two unknowns which can be solved for α and then for Δ. Thereafter, magnitude I can be calculated from equation (3) and the phase angle θ can be calculated from equation (2).
The sampling algorithm set forth above allows
determination of magnitude and phase with as few as four samples of current or voltage to be taken in less than 1/2 cycle of the powerline.
Application of the invention to a protective relay in an ac electric power transmission system is depicted in the circuit diagram of FIG. 2 While a single phase circuit is shown in FIG. 2, it should be understood that the invention would actually be used in conjunction with a three phase system and an identical circuit as shown in FIG. 2 would be present for each phase of the system. The microcomputer (discussed below) would perform the relevant calculations for each phase
Referring now to FIG. 2, in one embodiment of the invention, transmission line 5 has first phase current i having a sinusoidal waveform Current transformer 6 generates a current proportional to the current in the line 5.
Samples of current for use in the calculation of magnitude and phase are generated as follows: the ac current i is converted into a dc current by full wave rectifier 8. Resistor 9 converts the rectified output current from rectifier 8 to a voltage signal which is proportional to the magnitude of the current in the line. Unipolar analog-to-digital converter 10 accepts the positive voltage and generates at output 14 digitized samples representative of the amplitude of the current. Microcomputer 12 receives the digitized samples as inputs and is suitably programmed, as discussed hereinbelow, to perform the calculations required to produce the magnitude and phase of the current. Microcomputer 12 controls the sampling rate at which analog-to-digital converter 10 generates samples of the current for use in the calculations by a pulse sent to input 15 of analog-to-digital converter 10.
Microcomputer 12 must also receive information regarding the sign of the current. In the exemplary embodiment of the invention, the voltage V D across the ac inputs to the full wave bridge rectifier 8, is applied to a comparator 16 which compares V D to ground to generate a logic signal representative of the sign of i. It can be seen that when i is positive, the logic signal is equal to +5 V applied through resister 19. When i is negative, the logic signal is pulled to ground. This logic signal provides information about the sign of the current to input 13 of microcomputer 12.
Alternatively, an analog-to-digital converter in a bipolar mode (not shown) could be used. This would avoid the necessity of full wave rectifier 8. Both sign and amplitude would be generated from such an analog-to-digital converter.
Using the information about amplitude and sign, microcomputer 12 performs the calculations described above to generate present values for magnitude, phase and dc offset. In the preferred embodiment, the invention may be used in a protective relay system. Microcomputer 12 could be suitably programmed as discussed below to further perform a comparison of the magnitude of current to a predetermined value. If the magnitude of current exceeds this predetermined value, microcomputer 12 would generate a high output signal which would effect a response in the system. For example, the invention may be used in conjunction with an overcurrent relay in which the value of the magnitude of the current is compared to a set point and if it exceeds that set point, the output signal is high. This would ultimately effect an interruption of the system, by tripping a circuit breaker, for example
In the exemplary embodiment, the output 18 of microcomputer 12 is applied to the gate of a FET 20. FET 20 is turned on when the output of the microcomputer 12 goes high. When FET 20 is turned on, coil 22 is energized and normally open contact 26 is closed Trip coil 24, in turn, becomes energized. This trips breaker 25 and the system is thereby protected.
In other applications, it is desired to measure the voltage in the system in addition to or in place of the current. As shown in FIG. 2 the circuit may also include appropriate components adapted to generate samples of voltage and perform calculations on voltage samples. In such a case potential transformer 23 is placed on line 5. The amplitude of the voltage of one phase would be generated by applying the output of potential transformer 23 to a suitable voltage input circuit 35. Voltage input circuit 35 would include elements similar to those contained in the circuit in relation to current transformer 6. For example, the voltage output would be full-wave-rectified and a suitable resistance would be placed across the output of the resistance (not shown). This would be applied to a unipolar analog-to-digital converter which would thereby generate the magnitude information which would be provided to input 37 of microcomputer 12. Sign information would be generated by a combination similar to comparator 16 and resistor 19 as discussed above and this signal would provide sign information to input 36 of microcomputer 12.
Preferably samples would be generated at intervals of forty-five degrees of the line voltage Microcomputer 12 would perform the calculations of magnitude and phase. In addition, microcomputer 12 could be adapted to further perform a comparison function or a monitoring function as required in the relevant application
Referring now to FIG. 3, the flow chart of a suitable program for microcomputer 12 of FIG. 2 is shown. Timer interrupt subroutine 27 regulates the intervals at which the calculations are performed. The samples, i k , are generated as inputs to the microcomputer 28. Each sample is stored, 29, as it is generated. Depending upon the circumstances of the relevant application of the invention the four or eight most recently stored samples are always retained. As a new sample is stored, the least recent sample is discarded. At 30, the dc offset Δ is calculated using the four most recent samples, i 1 , i 2 , i 3 and i 4 , in equation (6). In one embodiment of the invention, the magnitude of current I is then calculated, at 31, using equations (3). In another application, four more samples would be required to solve two equations (5) with two unknowns. Then the magnitude of the current I could be calculated using equation (3) as discussed in detail above.
A comparison may be made between I and a predetermined value, I trip , 32. If the value is greater than I trip , then a suitable trip subroutine 33, which would be known to one skilled in the art, is called.
It should be understood that the invention may also be used to monitor currents and voltages and does not necessarily require the comparison of magnitude to a predetermined value.
While specific embodiments of the invention have been described in detail, it will be appreciated by those skilled in the art that various modifications and alternatives to those details could be developed in light of the overall teachings of the disclosure. Accordingly, the particular arrangements disclosed are meant to be illustrative only and not limiting as to the scope of the invention which is to be given the full breadth of the appended claims and any and all equivalents thereof.
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A method and apparatus for rapidly analyzing ac waveforms containing dc offset by generating digitized samples of the waveform to be analyzed with alternate samples separated by ninety electrical degrees. Alternate samples are paired for calculation of the magnitude and phase of the waveform. A suitable microcomputer performs a calculation using pairs of the most recently generated samples. Using the pairs of samples, the microcomputer calculates the dc offset, and the peak magnitude of the waveform which may be voltage or current. The phase angle of the waveform can also be calculated if required. The method and apparatus are particularly useful with protective systems where the calculation is necessary to determine whether there is a fault on an electric power transmission line. In addition, the effects of dc offset are eliminated and thereby false trips are avoided. A reliable system having a fast response time at relatively modest cost is provided.
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This application is a continuation application of application Ser. No. 08/174,318, filed 30 Dec. 1993 now U.S. Pat. No. 5,618,601.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to methods for controlling the delamination within contoured laminated structures and to the structures for carrying out such methods, and more particularly to such methods and structures for limiting or preventing delamination within laminated structures comprising at least one facing laminate and a plurality of spaced ribs attached thereto, and that is either adapted to be configured into a curved shape, thereby maintaining a desired appearance of the laminated structure, or remains in a flat, non-distorted condition to be used to cover a flat surface area.
2. Related Art
The development and subsequent proliferation of high impact decorative surface materials has prompted many changes in the cabinet and architectural industry. These changes included new adhesives, tools, fasteners and assembly techniques. The substrate cores of choice for lamination are composition board for flat panels and papers or plywood for contours.
In most cases, the flat, average size panels are easy to laminate, handle and assemble and are relatively stable. This is not the case when using large panels, contours or closed loop designs. Although many decorative surface materials are durable and flexible, most fabricators are reluctant to produce contoured structures because rigid contoured components are not compatible with flat-line production systems and require special hands-on labor, intensive handling, laminating and assembly methods.
As an additional deterrent to the use of such panel structures is that all of the wood base cores expand and contract in response to the atmosphere at different rates of movement than the surface sheet. This dynamic tension is potentially damaging to the surface sheet and glue line or both.
Laminated strips, including at least an outer surface strip having scuff-resistance characteristics, for example, and a desired eye appeal, and a core material, are formed over partially or fully curved structural surfaces such as columns, pillars, kitchen counters, etc., and permanently retained by the use of an adhesive between the inner surface of the laminated strip and the structural surface. The deformation of the laminated strip to form the desired contour shape produces stresses and strains tending to distort the laminated strip, separating it from the structural surface--a process called leveraged delamination. These forces and stresses are primarily caused by a lever and fulcrum action resulting from the bending of the laminated strip to conform to the structural surface, although changes in temperature and humidity are also contributing factors in the build-up of structural stress. Such delamination degrades the surface appearance of the laminated strip and may even adversely affect the adhesion of the laminated strip to the structural surface depending on the severity of the forces causing the delamination. The forces and stresses causing delamination increase with the degree of bending of the laminated strip to conform it to the shape of the structural surface.
The phenomena of delamination is determined by parameters such as the strength of the adhesive, the laminated strip and the structural surface. If the laminated strip is weaker than the adhesive, for example, the laminated strip will distort or tear before delamination occurs. However, if the adhesive is weak, then delamination will occur before distortion or tearing of the laminated strip. It is thus obviously desirable to design the laminated strip and select the adhesive to provide a controlled delamination of the laminated strip to prevent distortion or damage thereto.
U.S. Pat. No. 5,232,762, issued to the same inventor as the subject application, relates to a structural element for initial, substantially flat attachment to the surfaces of high impact sheet materials, and adapted for attachment to curved surfaces and includes a first resilient, semi-flexible, sheet material having a given length and width; a second, flexible sheet material of substantially the same width as the first sheet material; a plurality of parallely-spaced, independent preformed rib members sandwiched between the first and second sheet material and each rib member extending substantially across the width of the first and second sheet material and fixedly attached to both the first and second sheet material by an adhesive with the first and second sheet material being flat, the width and height of the preformed rib members and the distance between adjacent rib members determining the limit of bending of the first or second sheet material; and at least one of the first and second sheet material being shearable, thereby enabling areas and the degree of bending within the areas of the first and second sheet material to be determined by the selective cutting of only the at least one sheet in the spaces formed between the plurality of rib members. In an alternative embodiment only one sheet of flexible mateiral is used and the bending of the structural element is determined solely by the spacing between the rib members and their height and width.
U.S. Pat. No. 4,536,427 relates to laminated contoured structures in which the yieldability of the adhesive material between a facing sheet and the core material enables "contouring" of the laminated structure. The adhesive used remains pliable or toffee-like to allow the necessary separation between the scrim and the core.
U.S. Pat. No. 3,540,967 discloses contour-core structures in which the adhesive material between a scrim and the core is dislodged to enable the structure to conform to a curved-shape surface.
Controlling the properties of the adhesive is also an important factor in preventing "telegraphing" or the creation of flex lines or cracking in the laminated strip. Too strong an adhesive preventing delamination results in such cracking or the creation of flux lines in the outer surface of the laminated strip.
Thus, it is desirable to control the delamination of the adhesive from the structural surface and/or control the delamination of the laminated structure from the adhesive in order to prevent the aforementioned problems from occurring. As is evident from the above discussion, prior attempts to achieve controlled delamination rely entirely on the selection of a proper adhesive. Very little consideration has been given to the flexibility of the laminated strip itself in controlling the delamination of the laminated strip from the structural surface.
SUMMARY OF THE INVENTION
KERFKORE is a registered trademark pertaining to laminate structures of the type described herein and is owned by the same inventor as the present application.
The KERFKORE structure of the invention can be uniformly laminated, milled and drilled using flat-line mass production machines and stored flat for later selective constrained cold forming of core and surface sheet simultaneously into stabilized contoured panel elements suitable for attachment to "coreless" type cabinet and architectural framing.
The basic structure of the invention comprises a structural element for attachment to curved surfaces in which a plurality of parallely-spaced, independently preformed rib members are sandwiched between at least two, first and second sheet material members; with the rib members extending substantially across the width of the first and second sheet material members and fixedly attached to both the first and second sheet material members by adhesive material with the structure being flat, the width and height of the preformed rib members, the distance between adjacent rib members and the strength of the adhesive determining the limit of bending of the first and second sheet material members. At least one of the first and second sheet members being shearable, thereby enabling areas and the degree of bending within said areas of the first or second sheet material to be determined by the selective cutting of only one of the at least one sheet in the spaces formed between the plurality of rib members.
An alternate manner of describing the laminate structure of the invention is to define it as being a pliantly diffusive, composite structure formed of an initially flat, selectively flexible composite structure disposed for pliantly, spontaneous, fractional, intermittent diffusion and comprising a surface sheet of high impact, semi-rigid material bonded flat to a diffuse, segmented plurality of structural material extending substantially across the expanse of the surface sheet material with the segments being spaced and sized in a pattern rendering tenuous the otherwise permanent flat bond against flexing tensions of the surface sheet material and limiting the surface sheet flexing angle of interference to minus 20 degrees between adjacent segments in at least one direction, the flexing of the complete assemblage resultant in fractional intermittent detachment between elements of the composite structure, thus dispersing potentially damaging concentrations of stress and preserving the structural integrity and smooth visual continuity of the originally flat composite structure either in repititous flexing motion as a curved sliding door or in a fixed position as a contoured structure.
A primary object of the present invention is to control the delamination of a flat laminated structure (basically as defined above) caused by bending to be conformed into the curved contour of a structural surface by increasing the flexibility of the laminated strip structure to reduce the stresses and forces tending to induce the delamination.
Another object of the invention is to provide both a course and a fine adjustment of the bendability of the laminated strip by varying the size and spacing of the ribs in the core of the laminated strip to obtain a course bendability adjustment, and to provide severable connecting ribs within the rib elements for obtaining a fine bendability adjustment of the laminated strip.
It is a further object of the invention to provide a method and structure for obtaining a selectable, variable bendability adjustment of the laminated strip by selectively scoring a laminated sheet of the laminated strip between the spaced ribs.
Yet another object of the invention is to provide a method and structure for controlling delamination in laminated structures as disclosed herein by using a compressed latex paper scrim between the facing laminate of the laminated structure and the structural surface to absorb certain of the stresses and forces causing delamination to aid in obtaining the desired contour of the laminated structure.
And still another object of the invention is to provide variable-width scoring of a backing sheet in the laminated sheet structure in conjunction with the size and spacing of the ribs in the core structure of the laminated strip to control delamination.
Another purpose of this invention is to provide a group of structural substrate reinforcement cores of different cross-sections but similar purpose when in bonded combination with high impact surfacing materials such as, high pressure laminates, sheet metals and the like suitable for attachment to cabinet and architectureal framing or as self-contained, closed loop, monoformed structures engineered to be instrinsically subservient to and dynamically influenced by said surface sheets at rest in the initial flat condition, in mechanically forced motion, under the sustained stress of curved configurations, or atmospherically induced dimensional changes.
Imperative to the feasibility and functionality of laminated core structures such as described herein, there is the control of the perpetual dynamic tension between the essential elements contained in laminated components, core, adhesives and the surface sheet(s).
When tenuously bonded to surface sheet the core maintains permanent dynamic equilibrium between the three elements.
A flat and unstressed core produces impalpable adjustments dictated by the surface sheet due to atmospheric changes.
When the flat core sheet is moved from a flat condition to a contoured condition, there is a mechanical lever and fulcrum effect that tends to peel the surface sheet away from portions of the segments to dispose concentrations of stress, which action can be designated as leveraged delaminations.
The conventional method of producing grooved or mitered panels comprises two phases, namely, (1) simply bond the flexible sheet to an unmilled panel and (2) cut completely through to the sheet in "one pass". The cutters are usually pointed and adjusted to lightly score the sheet (especially if it is metal) to weaken and define each ply point.
The objective in producing KERFKORE is to avoid weakening, or in any way scoring, the sheet facing material at the flex point area.
To eliminate the damaging effect from the close proximity of the cutters to the sheet and to reduce flex point gap variations due to worn cutters, the raw panel is partially scored in one pass before laminating and then cut through on a second pass after laminating.
BRIEF DESCRIPTION OF THE DRAWINGS
The above objects, features and advantages of the invention are readily apparent from the following description of preferred embodiments of the best mode of carrying out the invention when taken in conjunction with the following drawings, wherein:
FIG. 1 shows a plurality of rib members adhered to a facing sheet with suitable spacing to control delamination in a basic laminated structure in accordance with the present invention;
FIGS. 2a and 2b shown the various causes and effects of delamination between the rib and laminate facing sheet of a laminate structure;
FIG. 3a illustrates the use of a compressed latex paper scrim between the laminate-sheet-facing material and the spaced ribs to obtain delamination control in accordance with the present invention; FIG. 3b is an enlarged view of a section of a laminate constructed in accordance with the invention illustrating the principle of leveraged delamination; FIG. 3c is another enlarged view of a laminate constructed in accordance with the invention illustrating the principle of leveraged delamination with a doubly bent or compund bent laminate; FIG. 3d is a modified embodiment in which the laminate includes alternately-directed through cuts as a means of controlling the delamination of the laminate structure; and FIG. 3e is a further modified embodiment in which the laminate includes alternately-reverse-directed through cuts as a means of controlling the delamination of the laminate structure;
FIG. 4 is a cross-sectional view of a laminate structure showing the rib connectors between adjacent ribs forming the core of a laminate structure for obtaining a fine adjustment of the bendability characteristic of the laminate structure in accordance with the invention;
FIG. 5 illustrates the manner in which a laminate sheet in the laminate structure can be scored to alter the bendability characteristic of the laminate structure to control contouring of the laminated core structure in accordance with the present invention;
FIG. 6a is an exploded cross-sectional side view of a laminate structure in accordance with one embodiment of the invention illustrating a triangularly-shaped notch; and FIG. 6b is a cross section of the structure of FIG. 6a;
FIG. 7a is an exemplary embodiment of a multiple web KERFKORE sheet and FIG. 7b shows a detail of the sheet structure; FIG. 7c is another exemplary embodiment of the invention showing a multi-layered web structure; and FIG. 7d illustrates the manner in which the webs are scored to enable the multi-layered structure to bend; and
FIG. 8a shows a laminated structure in accordance with the invention in which the structure is reversible depending upon the size of the radius of the bend and which can accommodate an accessory attachment; and FIG. 8b illustrates the use of the accessory attachment.
DETAILED DESCRIPTION
The basic construction of a sublaminate structure which is used to form laminate structures in accordance with the invention is shown in FIG. 1a. As shown in FIG. 1a, the plurality of rib members 20 are attached to a high impact laminate-facing-sheet 22 by a suitable adhesive to form a flat sublaminate structure 24. Sublaminate structure 24 is intended to be used in both a flat or a curved configuration, i.e. to be fastened to an essentially flat surface or to be bent to conform to a curved surface so that in both instances the laminate structure forms a facing providing a smooth desired appearance having high resistance to being gouged, marred or otherwise damaged. The width w, height h and spacing s of the rib members 20 are all factors determining the upper limit of bending of the sublaminate structure 24 where that structure is to be used to conform to a curved surface.
Additional factors controlling the degree of bending of the laminate structure 24 are the flexibility of the high impact laminate-facing-sheet member 22 and the strength of the adhesive used to attach the plurality of rib members 20 to the laminate-facing-sheet member.
For the purposes of the invention, it is assumed that one of ordinary skill in the art will recognize that it is necessary that the flexibility of the laminated-facing-sheet material 22 must be such that it can be bent to the maximum radius without producing any distortion in the appearance of the laminate-facing-sheet material such as would occur by cracking, telegraphing or actual severance of the laminate facing sheet from the substrate. The laminate structures in accordance with the invention are capable of being bent with at least a three inch radius.
Thus the factors affecting the bendability of a laminate sheet-facing material in accordance with the invention are the height h and width w of the rib elements 20, the spacing s between the rib elements and the adhesion between the rib members 20 and the facing-sheet 22. The adhesion between the rib members 20 and the facing-sheet 22 is in turn determined by the strength of the adhesive used to attach the rib members to the facing-sheet and the leverage applied by the bending of the facing-sheet 22 to the adhesive and the rib members.
The spacing s between the rib members 20 and the height h of the rib members are selected to accommodate the maximum bending radius necessary for the particular application of the laminate structure 24. It is apparent that the greater the height h and the width w of the rib members 20 the greater must the spacing s be between the adjacent rib members.
It is also apparent that the greater the width w of the rib members 20, the greater will be the leverage force applied by the sheet-facing material 22 to delaminate or separate the rib members from the sheet-facing material 20 for any given radius of bending of the sublaminate structure 24. Moreover, the greater the radius r of bending of the sublaminate structure 24, the greater will be the leverage force tending to delaminate or separate the rib members 20 from the sheet-facing material 22 for any given width w of the rib members. Furthermore, for any given width w of the rib members 20 and the radius r of bending of the sublaminate structure 24, the strength of the adhesive bonding between the rib members 20 and the sheet-facing material 22 will determine the delamination of the rib members from the sheet-facing material. Thus, the adhesive bonding must not exceed the fracture strength of the sheet-facing material, thereby enabling a controlled delamination to occur so that the basic sublaminate structure 24 can be bent to the desired radius without fracturing the surface sheet-facing material 22. Also, the adhesion bond must be of sufficient strength to enable the rib members 20 outside the area of bending of the sheet-facing material 22 to remain bonded thereto.
However, for purposes of describing the practical limits of the maximum bending radius R, it is more convenient to define the maximum bending radius R as a function of the angle between adjacent rib members with respect to the thickness of the rib members as shown in Examples I, II and III below as opposed to defining a great number of relationships between the spacing s, height h and width w of the rib members.
As shown in Example I, with a 13/4" height h of the rib members it is practical to obtain an approximate maximum angle of 5 degrees between adjacent rib members at the point of maximum bending of the laminate substrate. In Example II, with a rib member height h of 7/8" a range of between 6-12 degrees angle between the adjacent rib members is possible. Finally, in Example III with a rib member height h of 7/16" an approximate maximum angle of 17 degrees between adjacent rib members is possible.
It will be apparent to those skilled in the art of laminated structures that other relationships between these parameters will produce laminated structures in accordance with the invention.
The various structural causes and effects of controlling delamination between the rib and laminated-sheet facing material of a basic sublaminate structure generally of the type used in the invention are illustrated in FIGS. 2a and 2b for the purpose of demonstrating the factors affecting delamination. FIG. 1a illustrates a desired delamination of the rib member 20 from the facing sheet material 22 as caused by the leverage produced between the ends of the rib member by curvature of the sheet-facing material to a desired radius. A space 23 is produced by the separation of the rib member 20 from the sheet-facing material 22; however, the rib member remains attached, or at least in abutting relationship at end portions 21, with the sheet-facing material. In the event that the radius of bending of the sublaminate structure 24 is greater than that shown in FIG. 1a, it is desirable that delamination occur between several rib members 20 and the sheet facing material 22 with contact remaining at the outer edges of the delaminated rib members and the sheet-facing material.
FIG. 1b illustrates an instance in which improper delamination has occurred whereby the sheet-facing material 22 remains attached to the rib member 20 in an area between two delaminated areas 19. Such improper delamination most likely results from a too flexible sheet-facing material 22 accompanied by the use of too strong an adhesive, thereby enabling a fracture 25 to occur in the sheet-facing material.
The controlled delamination techniques of the present invention enable a wider variation in the constraints placed on the height h, width w and spacing s parameters as discussed above. For example, it is apparent as shown in FIG. 2a that if the spacing s is too narrow for the degree of bending (radius r ) the respective edges 26, 27 of adjoining rib members 20 will abut prior to the completion of the bending of the sublaminate structure 24 so that increased delamination pressure will be applied to the adhesion between the rib member(s) 20 and the sheet facing material 22. This will cause additional delamination between the rib member(s) 20 and the sheet-facing material 22.
To enable such delamination to occur without damage to either the rib members 20 or the sheet facing material 22, it is readily apparent that the adhesive bond between the rib members and the surface sheet-facing material 22 must be of less strength than the fracture or shearing strength of either the rib members or the sheet facing material. In the case where the sublaminate structure 24 includes only an adhesive between the rib members 20 and the sheet facing material 22, only the strength of the adhesive is available as the factor controlling the delamination (assuming a given rib member, sheet-facing material, and width w, height h and spacing s between the rib members).
However, in accordance with another embodiment of the invention, the basic sublaminate structure 24 illustrated in FIG. 1a may be modified to include a backing web member between the plurality of rib members and the sheet-facing material as shown in FIG. 3a. As illustrated in FIG. 3a a compressed latex paper scrim 30 is formed between sheet-facing material 22 and rib members 20 with the adhesive 32 bonding the scrim 30 to the individual rib members 20. Thus when the modified sublaminate structure 24' is bent to form a given radius r, the scrim 30 separates from the sheet facing material 22 to provide the controlled delamination necessary to enable the sublaminate structure 24' to achieve the desired bending radius as shown at areas 33, 34 between the affected adjacent rib members 20 and in the delamination control area 35. In areas 33, 34 the scrim 30 laterally yields to the changing dimensions of the sheet facing material 22 caused by the bending radius r. To obtain this result the adhesion between the scrim 30 and the sheet-facing material 20 must be less than the adhesion between the scrim 30 and the plurality of rib members 20.
The practical effect of this embodiment of the invention is that the constraints on the strength of the adhesive bond between the sheet-facing material 22 and the rib members is divided, thereby enabling the adhesion between the scrim 30 and the rib members 22 to be different than that between the sheet-facing material 22 and the scrim 30. This affords a greater flexibility in the selection of the adhesives than with the first embodiment of FIG. 1 without the scrim and wherein there is only one adhesive. Therefore, the adhesive strength is determined by the different adhesion between the adhesive and the sheet-facing material and the adhesion between the adhesive and the individual rib members.
FIG. 3b represents an enlarged view of a cross section of a laminate substrate in accordance with the invention and illustrating leveraging action of the surface sheet 22' along the contacting surface 23 between the surface sheet 22' and the rib member 20' which produces a maximum stress point at the edge 25 of the rib member which stress is controlled by the angle of interference 27 between adjacent rib members 20' as shown in the drawing. It is apparent that the larger the angle of interference 27 the larger the maximum stress that is produced to cause delamination of the laminate substrate.
FIG. 3c illustrates the two different types of delamination produced in a laminate substrate according to the invention and which is subjected to a double bending moment such that delamination is produced in the center of a rib member 20" with compressive forces existing at each corner 25" of the rib member 20". At the right hand side of the laminate structure delamination occurs at each corner 29 of the rib member 20" with a compressive force existing in the middle of the rib member 20". Thus, the location of the compressive forces enables the laminate substrate to endure a reverse bending as illustrated in the Figure.
FIG. 3d illustrates a modified embodiment of the laminate substrate of the invention in which the rib member 20'" is a core material in which alternate through cuts are made to enable the laminate substrate to be contoured and wherein the delamination effects are just the opposite of those previously described with respect to FIGS. 3b and 3c. As seen in FIG. 3d, the delamination occurs in a space 33 opposite a through cut on the opposite side of the laminate and between the through cuts which are involved in producing the bending of the laminate substrate.
FIG. 3e illustrates a further embodiment of the invention which represents a modification of the embodiment shown in FIG. 3d. The rib member 20"" is a core material in which the alternate through cuts are made opposite to that shown in FIG. 3d and wherein the delamination occurs in a space 33', approximately in the middle of a rib member. The intermediate cuts 34 provide bi-level bend radii; and primary and secondary flex points 35 and 36 are respectively provided. This modification provides more flex points per linear measure without reducing the bonding surface and requires less delamination by allowing the rib members to camber between primary flex points and thus maintain more contact with the surface sheet.
In a further modified embodiment of the invention as shown in FIG. 4, the sublaminate structure 24 of FIG. 1 is modified by including webbing 40 between adjacent rib members 20, which webbing decreases the flexibility or bending of the thus formed sublaminate structure 24". The flexibility of the sublaminate structure 24" can be selectively increased by selectively severing particular webs 40 between the rib members in those areas where bending of the sublaminate structure is required in accordance with the manner in which the sublaminate structure is to be conformed to a curved shape. In FIG. 4 the webs 40 are shown at approximately the midpoints of the rib members 20. However, it is understood that the webs 40 may be formed at other regions of the rib members to alter the flexible characteristics of the sublaminate structure 24".
In a preferred embodiment of the invention as shown in FIG. 5, the laminate structure of FIG. 1 includes a backing member 42 which includes scored sections 44 between adjacent rib members 20. The bendability of the thus formed sublaminate structure 24a is determined by severing the backing member 42 at selected scored sections 44 as shown at regions 46 to obtain the desired flexibility of the sublaminate structure to be bent into a desired curved shape. This preferred embodiment of the invention may further be modified by including the web-linked rib member structure of FIG. 4 as the basic rib element instead of the individual rib member structure of FIG. 1. In FIG. 5, the severed sections 44 include bent-in portions 48 of the backing member 42 which limits the bendability of the laminate structure as that structure is bent to a desired radius.
The embodiment of FIG. 5 may also be modified to increase the bendability of the laminate structure 24a by multiple cutting of the scored sections 44 to increase the width of the selected scored sections. An increased cut width may also be obtained by using a wider cutting implement. The increased cut width of the scored sections enables the laminate structure 24a to bend to a greater extent than with a narrower cut width.
In a further embodiment of the invention illustrated in FIG. 7a, the laminate structure 24b comprises a high-impact surface sheet, a latex type paper strip 52 attached by adhesive 54 to the surface sheet and sandwiched between the surface sheet 50 and a flexible core material 56 which includes cutout sections 58 having notched portions 60 each having a peak portion 62 around which the latex type paper strip extends as shown in FIG. 6a. The substrate 24b is completed with a backer sheet 64 preventing bending of the substrate 24b unless the backing sheet 64 is cut as shown in FIG. 6b at portions 66.
The notched portions 60 enable the laminate substrate 24b to bend at peaked portions 62 at which portions the latex type paper 52 is compressed as indicated at 66. During bending of the laminate substrate 24b, the surface sheet 50, adhesive 54 and latex type paper 56 expand as indicated at 68. The same components of the laminates substrate 24b undergo compression as indicated at 70.
As indicated in FIG. 6b by forces 72, 74 applied to the laminate substrate beyond the area of cutout portions 66 of backer sheet 64, the laminate substrate 24b will tend to bend in a downward direction to form a desired bend radius. The cutout portions may be formed by simply cutting the backing sheet to remove the necessary portion of the backing sheet 64.
FIG. 7a illustrates a modified embodiment of that described above with respect to FIG. 4 and involves the addition of a backing sheet 76 to the opposite side of the laminate substrate 24c to which the surface sheet 22 is attached. A flexible laminate substrate is formed at desired locations by selectively cutting web sections 40 and the associated portion of the backing sheet 76 as indicated at 78 and 80, respectively.
FIGS. 7c and 7d illustrate the manner in which sublaminate substrates individually formed of rib members 82, 82' and 82" and a backing sheet 84, 84' and 84", respectively are stacked on top of one another and attached by an adhesive between a respective backing sheet and the adjacent rib member to form a sublaminate structure 24d. A surface sheet 86 is bonded to the top of sublaminate substrate 24d and the resulting laminate substrate 88 is made flexible by cutting through the backing sheets 84, 84' and 84" as illustrated in FIG. 7d at portions 90, 92 and 94.
In the modified embodiment of the invention shown in FIG. 8a a sublaminate structure 24e is formed of rib members each having a notch 98 formed on each side of the rib member and the rib members 96 are attached or bonded to a backing sheet 100. An accessory attachment 102 in the form of an "H" includes opposed gripping edges 103 at each end of the legs of the "H" as shown in FIG. 8a. The sublaminate structure 24e is then provided with a surface sheet (not shown) bonded either over the backing sheet 100 or attached to cover the open ends of the rib members opposite the backing sheet. With the backing sheet attached to sublaminate structure 24e over the backing sheet 100 the flexibility of the resultant laminate substrate is limited so that it will bend in a smaller radius than will the resultant laminate substrate formed with the surface sheet over the sublaminate substrate 24e opposite the backing sheet 100. In the latter circumstance, the bendability of the laminate substrate is obtained by severing the backing sheet along selected sections 104 between the rib members 96, as described above with respect to the embodiment of the invention disclosed in FIG. 5. In the former circumstance, the flexibility of the laminate structure is provided by the separation between the rib members as discussed above with respect to the embodiments of the invention disclosed in FIGS. 1 and 4.
In the embodiment of FIG. 8a wherein the surface sheet is applied to the sublaminate structure 24e opposite the backing sheet 100, accessory 102 may be attached to the offset projections 106 on each of rib members 96 by cutting through the backing sheet 100 along the associated severance regions 104 and passing the appropriate end of the attachment 102 into engagement with the desired rib member 96.
As shown in FIG. 8b, two sublaminate structures 24e' and 24e" may be attached together via the engagement of engagement projections 103' with severed web members 106, 108. In this embodiment it is understood that sublaminate structure 24e is attached to attachment 102 shown in FIG. 8b.
The embodiments of the invention described herein are intended for the purpose of illustrating the structure and function of the invention. Those skilled in the art of facing structures will recognize that the embodiments described herein are capable of modification and thus the scope of invention described herein is not to be limited to the specific exemplary embodiments of the invention described, but the scope of the invention is to be determined by the claims appended hereto and the equivalents to which the claimed structures are entitled.
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A structural element made of a high impact sheet material, a resilient, semi-flexible core material, and a plurality of independent, preformed parallely-spaced rib members extending substantially across the width of said sheet material and fixedly attached thereto by an adhesive with said sheet material being flat, said plurality of rib members having adjacent, confronting side surfaces substantially parallel to one another, the forces created by bending of the structural element producing fractional detachment between at least some of said rib members and said sheet material being controlled by the width and height of said rib members and the distance between adjacent rib members and thereby determining the limit of bending of said structural element, thereby enabling a smooth surface of said high impact sheet material by preventing ripples and ridge lines therein with the bending of said structural element.
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CROSS REFERENCE TO RELATED APPLICATION
This application claims priority under 35 U.S.C. §119(e) to U.S. Provisional Patent Application Ser. No. 60/916,409, filed May 7, 2007 entitled, CLAMP ASSEMBLY FOR SLIDING CLAMP.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a sliding clamp and, more specifically, to an improved clamping assembly for a sliding clamp.
2. Background Information
As shown in FIGS. 1 and 2 , a sliding clamp typically includes an elongated bar 1 , a stationary jaw assembly 2 , and a clamp assembly 3 . The sliding clamp further includes a sliding jaw (not shown). The two jaw assemblies are coupled to the bar 1 . The sliding jaw assembly is structured to slide over, essentially, the length of the bar. The sliding jaw assembly includes a locking assembly structured to limit the direction of travel of the sliding jaw assembly. That is, when the locking assembly is engaged, the sliding jaw assembly may not be moved away from the stationary jaw assembly 2 . The stationary jaw assembly 2 does not travel over the length of the bar 1 but may be moved a short distance longitudinally along the bar 1 . The stationary jaw assembly 2 includes a cam follower 4 . The stationary jaw assembly moves in response to actuation of the clamp assembly 3 . It is noted that the word “stationary” is not used in a strict sense, but rather indicates that the stationary jaw assembly's 1 range of motion is very limited relative to the sliding jaw assembly.
The clamp assembly 3 is coupled to the bar and includes a cam member 5 and a cam actuator 6 . The cam member 5 has, generally, a flat body with a pivot point 7 , a first flat side 8 , a second flat side 9 , and a transition between the flat sides. The first flat side 8 is located closer to the pivot point 7 than the second flat side 9 . The cam member 5 is coupled to the bar at the pivot point 7 . Thus, the cam member 5 is structured to pivot relative to the bar 1 between a first position and a second position. In the first position, the first flat side 8 is adjacent to, and engages, the stationary jaw assembly cam follower 4 . In the second position, the second flat side 9 is adjacent to, and engages, the stationary jaw assembly cam follower 4 . Because the second flat side 9 is disposed further from the pivot point 7 than the first flat side 8 , when the cam member 5 is in the second position, the stationary jaw assembly 2 is shifted longitudinally toward the sliding jaw assembly. Further, because the cam flat sides 8 , 9 engage a flat surface on the stationary jaw assembly 2 , the cam member 5 tends not to rotate without actuation. The cam member 5 is actuated by the cam actuator 6 which is, typically, an elongated handle.
In use, the sliding jaw assembly is initially spaced from the stationary jaw assembly 2 and the clamp assembly cam member 5 is in the first position. A user places the object(s) to be clamped between separated jaw assemblies and in contact with the stationary jaw assembly 1 . The user slides the sliding jaw assembly against the object and engages the locking assembly. Thus, at this point, the object is loosely held between the jaw assemblies. That is, while the jaws, which have been biased against the object with manual force, may hold the object, the object is not securely clamped between the jaws. When the user actuates the clamp assembly 3 , the stationary jaw assembly 2 shifts toward the sliding jaw assembly thereby securely clamping the object between the jaws with a mechanical force.
The disadvantage to this configuration is that the cam member 5 and the cam actuator 6 pivot about a stationary axis. That is, the cam member 5 and the cam actuator 6 are coupled to the bar 1 by a pivot coupling that is, typically, an opening in the bar 1 and a rod extending therethough. Thus, the cam member 5 and the cam actuator 6 may only pivot about this stationary axis. This is a disadvantage as the cam actuator 6 may not be rotated away from external obstacles or may interfere with work being performed on the clamped object.
SUMMARY OF THE INVENTION
A clamp assembly is provided which includes a cam and cam actuator that are coupled to the bar by a ball-and-socket assembly; that is, rather than a pivot with a fixed axis, the rod has a ball fixed thereto adjacent the stationary jaw assembly. The cam is now a generally cylindrical member having a ball-shaped socket, a slot, a first flat surface, a second flat surface, and an actuator coupling. The ball-shaped socket is sized to correspond to the ball on the rod. The first flat surface is, preferably, a first axial surface. The second flat surface is, preferably, a portion of the cylindrical member sidewall. The first flat surface is closer to the center of the socket than the second flat surface. A transition surface, which is preferably an acute curve, extends between the first flat surface and the second flat surface. The slot bifurcates the first flat surface, the transition surface, and the second flat surface. The cam actuator, which is preferably an elongated handle, is coupled to a second axial surface that is opposite the first axial surface.
In this configuration, the cam member is coupled to the bar by the ball-and-socket coupling. The bar extends through the slot. The cam member is structured to pivot relative to the bar between a first position and a second position. In the first position, the first flat side is adjacent to, and engages, the stationary jaw assembly cam follower. In the second position, the second flat side is adjacent to, and engages, the stationary jaw assembly cam follower. Because the second flat side is disposed further from the pivot than the first flat side, when the cam is in the second position, the stationary jaw assembly is shifted longitudinally along the bar toward the sliding jaw assembly. Further, because the cam flat sides engage a flat surface on the stationary jaw assembly, the cam tends not to rotate without actuation.
Unlike the prior art, the cam member is coupled to the bar via a ball-and-socket coupling; therefore, the cam member and the cam actuator are free to rotate about the ball. Thus, a user may rotate the cam actuator to different orientations that may allow more convenient access to the clamped object.
BRIEF DESCRIPTION OF THE DRAWINGS
A full understanding of the invention can be gained from the following description of the preferred embodiments when read in conjunction with the accompanying drawings in which:
FIG. 1 is a side view of a prior art sliding clamp with a clamp assembly in a first position.
FIG. 2 is a side view of a prior art sliding clamp with a clamp assembly in a second position.
FIG. 3 is a side view of a sliding clamp according to the present invention with a clamp assembly in a first position.
FIG. 4 is a side view of a sliding clamp according to the present invention with a clamp assembly in a second position and the cam actuator in a first orientation.
FIG. 5 is a side view of a sliding clamp according to the present invention with a clamp assembly in a second position and the cam actuator in a second orientation.
FIG. 6 is a side view of a sliding clamp according to the present invention with a clamp assembly in a second position and the cam actuator in a third orientation.
DETAILED DESCRIPTION
As used herein, “coupled” means a link between two or more elements, whether direct or indirect, so long as a link occurs.
As used herein, “directly coupled” means that two elements are directly in contact with each other.
As used herein, “fixedly coupled” or “fixed” means that two components are coupled so as to move as one while maintaining a constant orientation relative to each other.
As used herein, “rotatably fixed” means that two components are coupled so as to move as one and maintain a generally constant position relative to each other, however the components may rotate relative to each other. For example, a bicycle tire is “rotatably fixed” to the bicycle frame; while the tire may rotate, the tire still moves with, and maintains a generally constant position relative to, the frame.
As shown in FIG. 3-6 , a sliding clamp 10 includes an elongated bar 12 , a sliding jaw assembly 14 ( FIG. 3 ), a stationary jaw assembly 16 , and a clamp assembly 30 . The sliding jaw assembly 16 is slidably disposed on the bar 12 and may move longitudinally thereon. As is known in the art, the sliding jaw assembly 16 includes a locking assembly (not shown) structured to limit the direction of travel of the sliding jaw assembly 16 . That is, when the locking assembly is engaged, the sliding jaw assembly 16 may not be moved away from the stationary jaw assembly 16 . The bar has a first end 18 and a first end distal tip 19 . It is noted that the bar first end distal tip 19 is, preferably, an extension from the bar 12 having a smaller cross-sectional area than the bar 12 .
The stationary jaw assembly 16 is coupled to the bar 12 at the bar first end 18 adjacent to the distal tip 19 . The stationary jaw assembly 16 is structured to have a limited longitudinal motion relative to the bar 12 . That is, the word “stationary” is not used in a strict sense, but rather indicates that the stationary jaw assembly 16 has a very limited range of motion relative to the sliding jaw assembly 14 . The stationary jaw assembly 16 moves between a first position, wherein the stationary jaw assembly 16 is closer to the distal tip 19 , and a second position, wherein the stationary jaw assembly 16 is further from the distal tip 19 . The stationary jaw assembly 16 includes a cam follower 20 . The cam follower 20 preferably includes a rigid member 22 and a resilient member 24 . The cam follower rigid member 22 is, preferably, disposed immediately adjacent to the first end distal tip 19 . The stationary jaw assembly 16 moves in response to actuation of the clamp assembly 30 , as described below. Thus, a user may position an object(s) between the sliding jaw assembly 14 and the stationary jaw assembly 16 , then slide the sliding jaw assembly 14 toward the stationary jaw assembly 16 . At this point, the user may apply manual pressure to bias the sliding jaw assembly 14 against the object, thereby loosely holding the object between the jaw assemblies 14 , 16 . However, the object will not be securely clamped until the clamp assembly 30 is actuated.
The clamp assembly 30 includes a ball 32 , a cam member 34 , and a cam actuator 36 . The ball 32 is substantially spherical and is coupled to the bar first end distal tip 19 . The ball 32 may have a flat 33 disposed immediately adjacent to the bar 12 . The cam member 34 has a generally cylindrical body 40 with a first axial surface 42 , a radial sidewall 44 , a second axial surface 46 , and a slot 48 . Within the cam member body 40 is a ball socket 49 . The first axial surface 42 is generally flat and acts as a first flat surface 50 . The radial sidewall 44 also includes a flat portion that is a second flat surface 52 . The second flat surface 52 extends to the cam member first axial surface 42 . Thus, there is an interface of the first flat surface 50 and the second flat surface 52 . Preferably, the interface of the first flat surface 50 and the second flat surface 52 is rounded and acts as a transition surface 54 ( FIG. 5 ) between the first flat surface 50 and the second flat surface 52 . The slot 48 extends over the first flat surface 50 and the second flat surface 52 , as well as the transition surface 54 . That is, the first flat surface 50 , the second flat surface 52 , and the transition surface 54 are bifurcated, or substantially bifurcated, by the slot 48 . The slot 48 extends into the ball socket 49 . That is, the slot has a sufficient depth to be contiguous with the ball socket 49 . The slot 48 is sized to be disposed around the bar first end 18 . The cam actuator 36 is, preferably, an elongated handle 60 . The cam actuator 36 is coupled, and preferably fixed, to the cam member body second axial surface 46 . Further, the cam actuator 36 , preferably, extends in a direction parallel to the longitudinal axis of the cam member 34 .
The clamp assembly 30 is assembled as follows. As noted above, the ball 32 is coupled, and preferably fixed or rotatably fixed, to the bar first end distal tip 19 . Thus, the ball 32 is immediately adjacent to, and may contact, the cam follower rigid member 22 . Preferably, the ball flat 33 is in contact with the cam follower rigid member 22 when the cam member 34 is in the first position, as described below. The ball 32 is further disposed, and trapped within, in the cam member ball socket 49 . The ball 32 partially protrudes into the slot 48 . The ball-and-socket coupling of the ball 32 and the cam member 34 creates a rotatable and pivotal coupling. That is, the cam member 34 may rotate and pivot relative to the ball 32 , but the cam member 34 does not move axially or laterally relative to the ball 32 . The first flat surface 50 is disposed at a first distance from a plane parallel thereto that passes through the center of the ball 32 . The second flat surface 52 is disposed at a second distance from a plane parallel thereto that passes through the center of the ball 32 . That is, in general terms, the first flat surface 50 is closer to the ball 32 than the second flat surface 52 .
The clamp assembly 30 operates as follows. The cam member 34 moves between first and second operational positions. In the first operational position, the first flat surface 50 engages the cam follower rigid member 22 and, preferably, the cam actuator 36 extends in a direction substantially along, or parallel to, the longitudinal axis of the bar 12 . In this position, the cam member 34 does not operatively engage, that is, apply more than an original bias to, the cam follower rigid member 22 . Preferably, there is a slight bias between the cam member 34 and the cam follower rigid member 22 . This slight bias will hold the cam member 34 in the first position. That is, without a slight bias, the weight of the cam actuator 36 may cause the cam member 34 to move into an undesirable transitional position. When the clamp assembly 30 is in the first operational position, the stationary jaw assembly 16 is in the first position.
In the second operation position, the cam member 34 is pivoted so that the second flat surface 52 engages the cam follower rigid member 22 and, preferably, the cam actuator 36 extends in a direction substantially perpendicular to the longitudinal axis of the bar 12 . In this position, the cam member 34 operatively engages, that is, applies more than an original bias to, the cam follower rigid member 22 . The bias created by the cam member 34 causes the stationary jaw assembly 16 to shift away from the bar first end distal tip 19 . That is, when the clamp assembly 30 is in the second operational position, the stationary jaw assembly 16 is in the second position.
During the transition from the first and second operational positions, the transition surface 54 engages the cam follower rigid member 22 . Further, as described above, as the stationary jaw assembly 16 is shifting into the second position, the stationary jaw assembly 16 is moving away from the bar first end distal tip 19 . This action exposes a portion of the bar first end 18 . The exposed portion of the bar first end 18 extends through the slot 48 , as shown in FIG. 5 .
It is noted that the cam member 34 is free to rotate about the ball 32 when the cam member 34 is in either the first or second operational positions. Thus, the cam member 34 may move into an infinite number of positions. This is useful when the cam actuator 36 extends into a space a user needs to occupy or have a tool or other object occupy. For example, if the cam member 34 was only able to pivot in a vertical plane, in a manner similar to the prior art shown in FIG. 1 , and if the bar 12 is disposed close to a workbench (not shown), when the user attempts to move the cam actuator 36 straight down, the cam actuator 36 may contact the workbench, thereby preventing the cam member 34 and stationary jaw assembly 16 from moving into their respective second positions. However, as shown in FIGS. 5 and 6 , with the clamp assembly 30 disclosed herein, a user is able to rotate the cam member 34 and cam actuator 36 about the axis of the bar 12 into a position where the cam actuator 36 would not contact the workbench when moved into the second position. That is, the user could rotate the clamp assembly 30 so that the cam actuator 36 moves in a horizontal plane.
While illustrative embodiments of the invention are disclosed herein, it will be appreciated that numerous modifications and other embodiments may be devised by those skilled in the art. Therefore, it will be understood that the appended claims are intended to cover all such modifications and embodiments that come within the spirit and scope of the present invention.
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A sliding clamp and clamp assembly are provided. The clamp assembly includes a cam member that, when actuated, biases a stationary clamp jaw assembly toward another jaw assembly. The cam member utilizes a ball-and-socket coupling to couple the cam member to the sliding clamp bar. The ball-and-socket coupling allows the cam member, and an extended actuator, to be pivoted and rotated into an infinite number of positions.
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TECHNICAL FIELD
The present invention relates to power converters having power factor correction, such as but not limited to converters of the type suitable for use within a vehicle to facilitate battery charging with energy sourced from a utility power grid.
BACKGROUND
Power factor correction (PFC) defines a consumption ratio of real power to apparent power and is typically reflected with a value between 0-1. PFC can be used to facilitate maximizing real power drawn from an AC power grid or other AC source to power a load by controlling the AC current to match as closely as possible to the shape and phase of the corresponding AC voltage. The load is more efficiently consuming power when the AC current and AC voltage are more closely matched, i.e., the closer the PFC value is to 1.
SUMMARY
One non-limiting aspect of the present invention relates to an efficiency optimized power converter with dual voltage power factor correction (PFC). The converter may include a rectifier circuit operable to rectify an AC input to a first DC output; a boost circuit operable to boost the first DC output to one of a second DC output and a third DC output; and a controller operable to control the boost circuit to output the one of the second DC output and the third DC output with PFC, the controller controlling the boost circuit to output the second DC output when the AC input is less than a threshold and to output the third DC output when the AC input is greater than or equal to the threshold.
The controller may control PFC of the boost circuit at least in part as a function of a voltage sensed at an output node of the boost circuit.
The controller may manipulate the voltage sensed at the output node with control of a voltage divider circuit connected to the output node.
The controller may set the voltage divider circuit to a first resistance in the event the AC input is less than the threshold and to a second resistance in the event the AC input is greater than or equal to the threshold.
The voltage divider circuit may include a first switch connected in series between the output node and a first resistor, the controller closing the first switch to set the voltage divider circuit to the first resistance and opening the first switching to set the voltage divider circuit to the second resistance.
The boost circuit may be configured as a boost converter having: an inductor, diode and capacitor connected in series; second and third resistors connected in parallel with the capacitor; a second switch connected between the inductor and diode and in parallel with the capacitor, the second switch being controlled by the controller to perform switching required to generate the second and third DC outputs with PFC; and wherein the first switch connects the first resistor in parallel with the third resistor.
The rectifier circuit may be a bridge rectifier comprised of four diodes connected to a receptacle used by a cordset that connects to a utility power grid to receive the AC input, and wherein each of the controller, rectifier, and boost circuit are included within a housing secured within a vehicle.
One non-limiting aspect of the present invention relates to a system for dual voltage power conversion comprising: a boost circuit operable to convert a first DC input to one of a second DC output and a third DC output; a voltage scaling circuit connected to the boost circuit and operable to set a power factor correction (PFC) setpoint for use in controlling the boost circuit, the voltage scaling circuit being operable to a first state and a second state, the first state setting the PFC setpoint to a first value and the second state setting the PFC setpoint to a second value; and a controller operable to control the boost circuit to output the one of the second DC output and the third DC output with PFC managed based at least in part on the PFC setpoint, the controller setting the PFC setpoint to the first value when the second DC output is desired and to the second value when the third DC output is desired.
The first DC input may result from conversion of an AC input and wherein the controller is sets the PFC setpoint to the one of the first value when the AC input is less than a threshold and to the second value when the AC input is greater than or equal to the threshold.
The system may include a rectifier operable to perform the conversion of the AC input to the first DC input.
The controller may continuously adjust a duty cycle of a signal used to control the boost circuit based on the AC input and the PFC setpoint.
The system may include a first switch operable between an open position and a closed position in response to a signal from the controller, the open position connecting a first resistor to the voltage scaling circuit and the closed position disconnecting the resistor from the voltage scaling circuit, the voltage scaling circuit having the first state when the switch is in the closed position and the second state when the switch is in the open position.
The boost circuit may be configured as a boost converter having: an inductor, diode and capacitor connected in series; second and third resistors connected in parallel with the capacitor; a second switch connected between the inductor and diode and in parallel with the capacitor, the second switch being controlled by the controller to perform switching required to generate the second and third DC outputs with PFC; and wherein the first switch connects the first resistor in parallel with the third resistor.
The controller may set as duty cycle of the second switch based on an AC input from which the first DC inputs is generated and the PFC setpoint.
One non-limiting aspect of the present invention relates to a method of controlling a dual voltage power conversion system having a boost circuit and a voltage scaling circuit, the boost circuit operable to convert a first DC input to one of a second DC output and a third DC output, and the voltage scaling circuit operable to a first state to set a first voltage scale value and a second state to set a second voltage scale value, the method comprising: setting the voltage scale to the first value when the second DC output is desired and to the second value when the third DC output is desired; and controlling the boost circuit to output the one of the second DC output and the third DC output with PFC managed based at least in part on the set voltage scale.
The method may further include setting the voltage scale based on an AC input being converted to the first DC input.
The method may further include setting a duty cycle of a signal used to control the boost circuit based on the AC input and the voltage scale.
The method may further include setting the voltage scale by issuing a signal to one of open and close a switch used to connected a resistive element to the voltage scaling circuit, connection of the resistive element controlling whether the voltage scaling circuit is in the first state and the second state.
The method may further include closing the switch when an AC input rectified to the first DC input is less than a threshold.
The method may further include opening the switch when an AC input rectified to the first DC input greater than or equal to than the threshold.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention is pointed out with particularity in the appended claims. However, other features of the present invention will become more apparent and the present invention will be best understood by referring to the following detailed description in conjunction with the accompany drawings in which:
FIG. 1 illustrates an efficiency optimized power converter system with dual voltage power factor correction (PFC) in accordance with one non-limiting aspect of the present invention.
FIG. 2 illustrates a PFC circuit contemplated by one non-limiting aspect of the present invention to facilitate dual voltage PFC.
FIG. 3 illustrates a flowchart for a method of dual voltage power conversion with PFC in accordance with one non-limiting aspect of the present invention.
DETAILED DESCRIPTION
As required, detailed embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely exemplary of the invention that may be embodied in various and alternative forms. The figures are not necessarily to scale; some features may be exaggerated or minimized to show details of particular components. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a representative basis for teaching one skilled in the art to variously employ the present invention.
FIG. 1 illustrates an efficiency optimized power converter system 10 with dual voltage power factor correction (PFC) in accordance with one non-limiting aspect of the present invention. The system 10 is described with respect to being a vehicle-mounted type unit having a housing (not shown) secured within a vehicle (not shown) and a receptacle connection (not shown) suitable for operatively connecting to a utility power grid 12 by way of a cordset or suitable connection 14 , such as to facilitate charging of a high voltage battery or other load included within an electric or hybrid electric vehicle with DC energy generated from utility grid supplied AC energy 12 . This exemplary illustration, however, is not intended to unnecessarily limit the scope of the present invention as the present invention fully contemplates its use in other non-vehicle or non-automotive environments where it may be desirable to support PFC for linear or non-linear loads in order to maximize the efficiency at which supplied energy is consumed.
The AC energy received at the receptacle 14 is shown to be rectified with a rectifier circuit 16 . The rectifier circuit 16 may be a diode bridge comprised of four diodes or some other suitable AC-DC inverter. The DC output of the rectifier 16 is shown as a DC input to a PFC circuit 18 , which for exemplary and non-limiting purposes is labeled and described to be a boost circuit as one aspect of the present invention contemplates boosting to the DC output of the rectifier 16 to support high voltage operations, however, the present invention fully contemplates other configuration for providing PFC instead of a boost circuit 18 , such as buck, buck/boost, sepic, or any other DC-DC circuit topology. A bulk capacitor or capacitor bank 20 may be included to smooth the DC output of the PFC circuit 18 prior to a DC-DC converter 24 finally manipulation the DC signals for output to the desired load. The bulk capacitor 20 may be useful in smoothing the output of the PFC circuit 18 and the DC-DC converter 24 may be useful in isolating the load and/or otherwise further processing and controlling the output to the load, which may even include inverting the received DC signal to an AC signal.
The controlling necessary to support the operation of the system 10 may be provided with a controller 26 . The controller 26 may be configured to measure or receive a measurement of the AC signal received at the rectifier 16 and to control the PFC circuit 18 as a function thereof, such as to control switching and/or other operations required of the boost circuit 18 or other circuit being used to process the DC output of the rectifier 16 . The controller 26 may also be configured to utilize a voltage measured at an measurement node 28 (see FIG. 2 ) of the PFC circuit 18 as feedback for use in controlling the PFC and/or boosting provided by the PFC circuit 18 . This voltage measurement, at least with respect to its use in facilitating PFC, may be referred to as a voltage scale or PFC setpoint in that the controller 26 may be configured to adjust the PFC operations used to facilitate aligning the AC current with the AC voltage as function of the PFC setpoint.
One non-limiting aspect of the present invention contemplates controlling the PFC setpoint used by the controller 26 to facilitate dual voltage PFC, i.e., supporting PFC while the system 10 outputs at different voltage levels. This capability may be useful in allowing the system to maximize efficiency at two or more voltage levels (e.g., a unique setpoint may be generated for each desired voltage level).
One non-limiting aspect of the present invention contemplates the system 10 being required to support operations for AC voltage inputs of between 265 VAC and 305 VAC, although these values may vary depending on the particular use of the system 10 . Since the controller 26 may require the PFC setpoint to be set to a voltage level associated with the greatest supported AC voltage input, i.e., 305 VAC. In the absence of the PFC setpoint manipulation contemplated by the present invention, the PFC at lower voltage levels would be less efficient if controlled according to the 305 VAC setpoint (455 VDC), which is undesirable, especially in the event the lower voltage levels are associated with more typical or normal operating conditions, i.e., less than 265 VAC.
The present invention allows one PFC setpoint (400 VDC) to be generated during normal operating conditions of less than 265 VAC and another, different setpoint (455 VDC) to be generated when operating at greater operating conditions of 265 VAC to 305 VAC. This allows the present invention to facilitate dual voltage PFC while maximizing efficiency at both operating conditions. FIG. 2 illustrates the PFC circuit 18 contemplated by one non-limiting aspect of the present invention to facilitate dual voltage PFC. The circuit 18 is shown with respect to the exemplary boost configuration and without intending to unnecessarily limit the scope and contemplation of the present invention.
The PFC circuit 18 may be comprised of a boost portion 30 and a voltage divider or voltage scaling circuit 32 . The PFC circuit 18 may include an inductor 34 , diode 36 and capacitor 38 connected in series, first and second resistors 40 , 42 connected in parallel with the capacitor 38 , and a first switch 44 connected between the inductor 34 and diode 36 and in parallel with the capacitor 38 . The controller 26 may be operable to control the first switch 44 to perform switching required to generate the DC output with PFC. The controller 26 may rely on a voltage sensed at an output node 50 (see FIG. 1 ) to control the switching operations and PFC, which may be set with the voltage divider circuit 32 .
The voltage divider circuit 32 is shown as a resistive configuration where first, second, and third resistors 40 , 42 , 54 are arranged into a dividing configuration where a second switch 56 controls the division of the resistance set by the first and second resistors 40 , 42 with controllable connection of the third resistor 54 . The controller 26 may control opening and closing of the second switch 56 in order to vary the voltage sensed at the measurement node 28 , i.e., the PFC setpoint, in order to adapt PFC according to desired operating conditions.
One non-limiting aspect of the present invention contemplates the controller 26 measuring or otherwise determining the AC input voltage to the rectifier 16 and controlling actuation of the switch 56 as a function thereof, i.e. closing the switch 56 to generate a lower voltage PFC setpoint (e.g., 400 VDC to support less than 265 VAC input) and opening the switch to generate a greater voltage PFC setpoint (e.g., 430 VDC to support 265 VAC to 305 VAC input). While the resistive configuration 32 is shown for exemplary purposes, the present invention fully contemplates the use of other configuration and non-resistive configurations suitable to altering the PFC setpoint as a function of signal received from the controller 26 or signaling otherwise varying depending on one or more operating conditions, such as the above described AC input.
FIG. 3 illustrates a flowchart 60 for a method of dual voltage power conversion with PFC in accordance with one non-limiting aspect of the present invention. The method and/or processes associated therewith may be implemented with instructions or other operations implemented by a processor, such as one within the controller 26 , executing according to instructions or code stored on a computer-readable medium. The method contemplates the controller 26 essentially simultaneously, if possible, processing the present AC input 50 to the system 10 (see block 62 ) with the present DC voltage 28 at the output node (see block 64 ) for use in setting a duty cycle for the first switch (see block 66 ) that then results in the PFC circuit 18 providing one of a second DC voltage (400 VDC) or third DC output (455 VDC) in block 68 . In parallel therewith, the controller 26 may also control the second switch 56 (see block 70 ) between the open and closed state depending on the AC voltage is above a threshold corresponding with the lower PFC setpoint, i.e., the switch is opened when the greater PFC setpoint is needed due to the AC input voltage being greater than 265 VAC.
As supported above, one non-limiting aspect of the present invention contemplates PFC to maximize real power to be drawn from an AC grid by controlling an input AC current to be approximately the same shape and phase as the AC voltage. The contemplated circuit topology may be a boost converter although other converters and circuits may be used. For boost converters, the output voltage must be strictly larger than the input voltage, requiring the PFC output voltage to set at 400 VDC when operating from AC voltages up to 265 VAC (which has instantaneous peak voltage of 375 VDC=265*sqrt(2)). Subsequent power conversion stages may be implemented to provide an isolated, controlled output. In order to support a wider input range, for example 305 VAC, the peak voltage is 430 VDC, which requires more than the normal PFC setpoint of 400 VDC. Rather than permanently set the PFC to 450 VDC to accommodate the occasional use of 305 VAC input and cause the efficiency of the device to suffer due to the increase of power device switching losses at the higher system voltage, this invention provides a nominal PFC setpoint of 400 VDC, which is optimized for operation with AC voltages up to 265 VAC and another mode which switches the PFC setpoint to 455 VAC for use with AC input voltages of between 265 and 305 VAC. This is done by changing the voltage scaling on the AC and DC voltage measurements used by the PFC controller.
The advantages of this invention may include, at least in some aspects, a wider input voltage range, improved efficiency over single PFC setpoint systems, simple and robust implementation of setpoint switching via mosfet transistor and resistor combination
While exemplary embodiments are described above, it is not intended that these embodiments describe all possible forms of the invention. Rather, the words used in the specification are words of description rather than limitation, and it is understood that various changes may be made without departing from the spirit and scope of the invention. Additionally, the features of various implementing embodiments may be combined to form further embodiments of the invention.
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A dual voltage power conversion system with power factor correction (PFC) having a capabilities to adjust a PFC setpoint according to operating conditions. The input signaling levels, for example, may be monitored and used to control adjustments to the PFC setpoint in order to allow the PFC setpoint to dynamically change with any input variation. The PFC setpoint may be adjusted to a PFC setpoint resulting in maximum efficiency.
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FIELD OF THE INVENTION
[0001] The present invention is in the field of telephony communication and pertains more particularly to methods and apparatus for seamless integration in routing of network-based connection-orientated, switched telephony (COST) and Data Network Telephony (DNT) calls, such as Internet-Protocol-Network-Telephony (IPNT) calls, within a call center.
BACKGROUND OF THE INVENTION
[0002] In the field of telephony communication, there have been many improvements in technology over the years that have contributed to more efficient use of telephone communication within hosted call-center environments. Most of these improvements involve integrating the telephones and switching systems in such call centers with computer hardware and software adapted for, among other things, better routing of telephone calls, faster delivery of telephone calls and associated information, and improved service with regards to client satisfaction. Such computer enhanced telephony is known in the art as computer-telephony integration (CTI).
[0003] Generally speaking, CTI implementations of various design and purpose are accomplished both within individual call-centers and, in some cases, at the network level. For example, processors running CTI software applications may be linked to telephone switches, service control points (SCP), and network entry points within a public or private telephone network. At the call-center level, CTI-enhanced processors, data servers, transaction servers, and the like, are linked to telephone switches and, in some cases, to similar CTI hardware at the network level, often by a dedicated digital link. CTI and other hardware within a call-center is commonly referred to as customer premises equipment (CPE). It is the CTI processor and application software at such centers that provides computer enhancement to a call center.
[0004] In a CTI-enhanced call center, telephones at agent stations are connected to a central telephony switching apparatus, such as an automatic call distributor (ACD) switch or a private branch exchange (PBX). The agent stations may also be equipped with computer terminals such as personal computer/video display unit's (PC/VDU's) so that agents manning such stations may have access to stored data as well as being linked to incoming callers by telephone equipment. Such stations may be interconnected through the PC/VDUs by a local area network (LAN). One or more data or transaction servers may also be connected to the LAN that interconnects agent stations. The LAN is, in turn, connected to the CTI processor, which is connected to the call switching apparatus of the call center.
[0005] When a call arrives at a call center, whether or not the call has been pre-processed at an SCP, typically at least the telephone number of the calling line is made available to the receiving switch at the call center by the network provider. This service is available by most networks as caller-ID information in one of several formats such as Automatic Number Identification Service (ANIS). If the call center is computer enhanced (CTI) the phone number of the calling party may be used to access additional information from a customer information system (CIS) database at a server on the network that connects the agent workstations. In this manner information pertinent to a call may be provided to an agent, often as a screen pop.
[0006] In recent years, advances in computer technology, telephony equipment, and infrastructure have provided many opportunities for improving telephone service in publicly-switched and private telephone intelligent networks. Similarly, development of a separate information and data network known as the Internet, together with advances in computer hardware and software have led to a new multi-media telephone system known in the art by several names. In this new systemology, telephone calls are simulated by multi-media computer equipment, and data, such as audio data, is transmitted over data networks as data packets. In this application the broad term used to describe such computer-simulated telephony is Data Network Telephony (DTN).
[0007] For purposes of nomenclature and definition, the inventors wish to distinguish clearly between what might be called conventional telephony, which is the telephone service enjoyed by nearly all citizens through local telephone companies and several long-distance telephone network providers, and what has been described herein as computer-simulated telephony or data-network telephony (DNT). The conventional system is familiar to nearly all, and is often referred to in the art as connection-oriented-switched-telephony (COST). The COST designation will be used extensively herein. The computer-simulated, or DNT systems are familiar to those who use and understand computer systems. Perhaps the best example of DNT is telephone service provided over the Internet, which will be referred to herein as Internet-Protocol-Network-Telephony (IPNT), by far the most extensive, but still a subset of DNT.
[0008] Both systems use signals transmitted over network links. In fact, connection to data networks for DNT such as IPNT is typically accomplished over local telephone lines, used to reach such as an Internet Service Provider (ISP). The definitive difference is that COST telephony may be considered to be connection-oriented telephony. In the COST system, calls are placed and connected by a specific dedicated path, and the connection path is maintained over the time of the call. Bandwidth is thus assured. Other calls and data do not share a connected channel path in a COST system. In a DNT system, on the other hand, the system is not dedicated or connection oriented. That is, data, including audio data, is prepared, sent, and received as data packets. The data packets share network links, and may travel by variable paths, being reassembled into serial order after receipt. Therefore, bandwidth is not guaranteed.
[0009] Under ideal operating circumstances a DNT network, such as the Internet, has all of the audio quality of conventional public and private intelligent telephone-networks, and many advantages accruing from the aspect of direct computer-to-computer linking. However, DNT applications must share the bandwidth available on the network in which they are traveling. As a result, real-time voice communication may at times suffer dropout and delay. This is at least partially due to packet loss experienced during periods of less-than-needed bandwidth which may prevail under certain conditions such as congestion during peak periods of use, and so on.
[0010] Recent improvements to available technologies associated with the transmission and reception of data packets during real-time DNT communication have enabled companies to successfully add DNT, principally IPNT capabilities, to existing CTI-enhanced call centers. Such improvements, as described herein and known to the inventor, include methods for guaranteeing available bandwidth or quality of service (QoS) for a transaction, improved mechanisms for organizing, coding, compressing, and carrying data more efficiently using less bandwidth, and methods and apparatus for intelligently replacing lost data by using voice supplementation methods and enhanced buffering capabilities.
[0011] In typical call centers, DNT is accomplished by Internet connection and IPNT calls. For this reason, IPNT and the Internet will be used almost exclusively in examples to follow. It should be understood, however, that this usage is exemplary, and not limiting.
[0012] In systems known to the inventors, incoming IPNT calls are processed and routed within an IPNT-capable call center in much the same way as COST calls are routed in a CTI-enhanced center, using similar or identical routing rules, waiting queues, and so on, aside from the fact that there are two separate networks involved. Call centers having both CTI and IPNT capability utilize LAN-connected agent-stations with each station having a telephony-switch-connected headset or phone, and a PC connected, in most cases via LAN, to the LAN over which IPNT calls may be routed. Therefore, in most cases, IPNT calls are routed to the agent's PC while conventional telephony calls are routed to the agent's conventional telephone or headset. However, a method known to the inventor allows one headset to be used at an agent's station for handling both IPNT and COST calls. This is accomplished via connecting the agent's telephone to the sound card on the agent's PC/VDU with an I/O cable. In most prior art and current art systems, separate lines and equipment must be implemented for each type of call weather COST or IPNT.
[0013] Due in part to added costs associated with additional equipment, lines, and data ports that are needed to add IPNT capability to a CTI-enhanced call-center, companies are currently experimenting with various forms of integration between the older COST system and the newer IPNT system. For example, by enhancing data servers, interactive voice response units (IVR's), agent-connecting networks, and so on, with the capability of understanding Internet protocol, data arriving from either network may be integrated requiring less equipment and lines to facilitate processing, storage, and transfer of data. However, telephony trunks and IPNT network lines representing the separate networks involved still provide for significant costs and maintenance.
[0014] In some current art implementations, incoming data from the COST network and the Internet is caused to run side by side from the network level to a call center over a telephone connection (T1/E1) acting as a telephone-data bridge, wherein a certain channels are reserved for COST connection, and this portion is dedicated as is necessary in COST protocol (connection oriented), and the remainder is used for DNT such as IPNT calls, and for perhaps other data transmission. Such a service is generally offered by a local phone company. This service eliminates the requirement for leasing numerous telephony trunks and data-network connections. Routing and other equipment, however, must be implemented at both the call center level and network level significantly reducing any realized cost savings.
[0015] A significant disadvantage of such a bridge, having dedicated equipment on each end, is the dedicated nature of individual channels over the bridging link. Efficient use of bandwidth cannot be assured during variable traffic conditions that may prevail at certain times. For example, dedicated channels assigned to IPNT traffic would not be utilized if there were not enough traffic to facilitate their use. Similarly, if there was more COST traffic than the allotted number of COST channels could carry, no additional channels could be made available.
[0016] In a yet more advanced system, known in some call centers, a central switch within the call center is enhanced with IP conversion capability and can communicate via LAN to connected IP phone-sets and PC's eliminating the need for regular telephone wiring within a call center. However, the service is still delivered via a telephone-data bridge as described above. Therefore, additional requirements for equipment and inefficiency regarding use of bandwidth are still factors.
[0017] In still other systems known to the inventor and illustrated as prior art below, IPNT to COST conversion or COST to IPNT conversion is performed within the call center instead of via a network bridge. This is accomplished via a gateway connected to both an IPNT router and a central telephony-switching apparatus. In the first case, all calls are converted to and routed as COST calls over internal telephone wiring to switch-connected headsets. In the second case, all COST calls are converted to and routed as IPNT calls over a LAN to individual PC/VDU's.
[0018] In all of the described prior art systems, the concerted goal has been to integrate COST and IPNT data via converging at the network level or within the call center. The addition of dedicated hardware both at the network level and within the call center adds to the expense of providing such integrated data.
[0019] What is clearly needed is a routing system enabled to route both COST and IPNT calls to available agents sharing a LAN within a call center while maintaining separate delivery and outbound network architectures for the different media. A system such as this would unify all routed events and could be used with COST/IPNT capable headsets (known to the inventor) so an agent can handle both media with the same headset.
SUMMARY OF THE INVENTION
[0020] In a preferred embodiment of the present invention an integrated router (IR) is provided, comprising a first link adapted to connect the IR to a telephony switch capable of receiving and switching connection-oriented, switched telephony (COST) calls to connected telephones at agent stations; a second link adapted to connect the IR to a DNT processor capable of receiving and switching data network telephony (DNT) calls to network-connected DNT interface equipment at the agent stations; and control routines adapted for monitoring and controlling both the telephony switch and the DNT processor. The telephony switch and the DNT processor report incoming calls, whether COST or DNT, to the IR, and the IR controls the telephony switch and the DNT processor to route calls to available agent stations under a single set of rules. In some embodiments IR is connected by the first link to a telephony switch through a CTI processor. To gauge agent status the IR accesses a real-time data base storing agent status.
[0021] In another aspect of the invention a call center is provided, comprising a telephony switch capable of receiving and switching connection-oriented, switched telephony (COST) calls to connected telephones at agent stations; a DNT processor capable of receiving and switching data network telephony (DNT) calls to network-connected DNT interface equipment at the agent stations; and an integrated router adapted to monitor and control both the telephony switch and the DNT processor. In this aspect the telephony switch and the DNT processor report incoming calls, whether COST or DNT, to the IR, and the IR controls the telephony switch and the DNT processor to route calls to available agent stations under a single set of rules. In this embodiment the IR may be connected by the first link to a telephony switch through a CTI processor. Also, the IR accesses a real-time data base storing agent status. In addition, selected agent stations may have both a COST-capable telephone and a personal computer with a video display unit (PC/VDU), with the telephone connected to the PC/VDU through a sound card such that the telephone can be used for both COST and DNT calls. The telephone may be a headset telephone.
[0022] In still another aspect a method for commonly routing COST and DNT calls in a call center is provided, comprising steps of (a) informing an integrated router (IR) of connection-oriented, switched telephony (COST) calls received at a telephony switch connected to telephones at agent stations; (b) informing the IR of Data Network Telephony (DNT) calls received at a DNT-capable call center; (c) consulting an agent-availability data repository; and (d) routing the COST and DNT calls commonly to the agent stations based on agent availability. In this method, in step (c) the agent-availability repository is updated in real time, additional routing rules may be used beyond agent availability.
[0023] The system of the invention, in its various aspects as taught below in enabling detail, a low-cost and easily-implemented solution to the need for common routing of incoming COST and DNT calls is provided
BRIEF DESCRIPTION OF THE DRAWING FIGURES
[0024] [0024]FIG. 1 is a system diagram of a call center connected to a telecommunication network using IPNT to COST conversion according to prior art.
[0025] [0025]FIG. 2 is a system diagram of the call center and telecommunication network of FIG. 1 using IPNT switching at the call center according to prior art.
[0026] [0026]FIG. 3 is a system diagram of the call center and telecommunication network of FIG. 1 enhanced with integrated routing according to an embodiment of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0027] [0027]FIG. 1 is a system diagram of a call center connected to a telecommunication network using IPNT to COST conversion according to prior art. As described briefly with regards to the background section, various prior art telecommunication networks utilize network-bridging techniques for the purpose of causing IPNT and COST incoming calls to run parallel into the call center. In current systems, as was also described, various implementations have been made within the call center for converting IPNT to COST, and conversely, COST to IPNT. FIG. 1 represents one such current art system.
[0028] In FIG. 1 telecommunications network 11 comprises a publicly-switched telephone network (PSTN) 13 , the Internet network 15 , and a call center 17 . PSTN network 13 may be a private network rather than a public network, and Internet 15 may be another public or a private data network as are known in the art.
[0029] In this basic prior art example, call center 17 is equipped to handle both COST calls and IPNT calls. Both COST calls and IPNT calls are delivered to call-center 17 by separate network connections. For example, a telephony switch 19 in the PSTN may receive incoming telephone calls and rout them over a COST network trunk 23 to a central switching apparatus 27 located within call center 17 . IPNT calls from Internet 15 are routed via a data router 21 over a data-network connection 25 to an IPNT router 29 within call center 17 . In this example, network switch 19 is meant to represent a wide variety of processing and switching equipment in a PSTN, and router 21 is exemplary of many routers and IP switches in the Internet, as known in the art.
[0030] Call center 17 further comprises four agent stations 31 , 33 , 35 , and 37 . Each of these agent stations, such as agent station 31 , for example, comprises an agent's telephone 47 adapted for COST telephone communication and an agent's PC/VDU 39 adapted for IPNT communication and additional data processing and viewing. Agent's telephones 47 , 49 , 51 , and 53 along with agent's PC/VDU 39 , 41 , 43 , and 45 are in similar arrangement in agent stations 31 , 33 , 35 , and 37 respectively. Agent's telephones, such as agent's telephone 49 , are connected to COST switching apparatus 27 via telephone wiring 56 .
[0031] A LAN 55 connects agent's PC/VDU's to one another and to a CPE IPNT router 29 . A client-information-system (CIS) server 57 is connected to LAN 55 and provides additional stored information about callers to each LAN-connected agent. Router 29 routes incoming IPNT calls to agent's PC/VDU's that are also LAN connected as previously described. A data network connection 25 connects data router 29 to data router 21 located in Internet 15 . Specific Internet access and connectivity is not shown, as such is well known in the art, and may be accomplished in any one of several ways. The salient feature to be emphasized in this prior art example is that separate connections and equipment are necessary and implemented to be able to handle both COST and IPNT calls at the call center.
[0032] Each agent's PC/VDU, such as PC/VDU 45 has a connection via LAN 55 and data network connection 25 to Internet 15 while the assigned agent is logged on to the system, however, this is not specifically required but rather preferred, so that incoming IPNT calls may be routed efficiently. Dial-up connecting rather than a continuous connection to Internet 15 may sometimes be employed.
[0033] An agent operating at an agent station such as agent station 33 may have COST calls arriving on agent'telephone 49 while IPNT calls are arriving on agent's PC/VDU 41 . In examples prior to this example, router 29 would not have a connection to central switching apparatus 27 . Having no such connection creates a cumbersome situation, requiring agents to distribute their time as best they can between the two types of calls. Thus, agent time is not utilized to maximum efficiency with respect to the total incoming calls possible from both networks.
[0034] In this embodiment however, router 29 is connected to an IPNT-to-COST gateway 59 via data connection 61 . Gateway 59 is connected to central switch 27 via CTI connection 63 . Gateway 59 is adapted to convert all incoming and outgoing IPNT calls to COST calls where they may be routed over wiring 56 to agents (incoming), or over trunk 23 to switch 19 in cloud 13 (outgoing). In this way, agents may use switch-connected telephones, such as telephone 47 to answer both IPNT-to-COST converts and regular incoming COST calls. The agent's time is better utilized, and additional network equipment comprising a network bridge and associated network connections are not required.
[0035] This prior art example, however, presents some problems and limitations. One problem is that traditional COST equipment such as routers, switches, and wiring may have to be significantly expanded to handle more traffic regarding the added call-load received from cloud 15 . Further, the ability to predict possible call overload situations is significantly complicated because of the convergence of IPNT calls into the COST routing system. As IPNT calls are now received by agents as COST calls, certain features inherent to IPNT applications will be lost such as multimedia enhancements, and the like.
[0036] One advantage with this example is that calls originating as IPNT calls within call center 17 may be sent as IPNT calls over data connection 25 , or as converted COST calls over trunk 23 . Another advantage is that LAN 55 is free to carry data other than IPNT audio packets.
[0037] [0037]FIG. 2 is a system diagram of the call center and telecommunication network of FIG. 1 using IPNT switching at the call center according to prior art. This prior art example is essentially reversed from the prior art example described in FIG. 1. For the sake of saving space and avoiding redundancy, elements found in this example that are identical to the example of FIG. 1 will not be re-introduced.
[0038] Call center 17 receives COST calls from cloud 13 over trunk 23 , and IPNT calls from cloud 15 over data connection 25 as described with the prior art example of FIG. 1. However, instead of having a central telephony-switch such as switch 27 of FIG. 1, a COST-to-IPNT gateway 71 is provided and adapted to convert COST calls to IPNT calls.
[0039] After converting incoming COST calls to IPNT calls, these are routed via data connection 73 to an IPNT switch 75 . IPNT switch 75 is adapted to distribute the resulting IPNT calls to selected agent's over LAN 55 . Regular IPNT calls are routed to LAN-connected agents via router 29 .
[0040] Agent's telephones 47 - 53 are, in this example, adapted as IP phones and are each connected to LAN 55 . Internal wiring and other COST related architecture is not required, which is one distinct advantage of this prior art system.
[0041] A disadvantage of this system is that there is no provision to make outbound calls to the PSTN 13 . Only further enhancement to gateway 71 to convert IPNT calls to COST calls enables out-bound dialing to PSTN 13 from within call center 17 . Under heavy call-load situations, a dual gateway such as would be the case with gateway 71 may become congested and cause delay. Additional apparatus may be required to alleviate this problem. In some cases wherein there are concerted outbound campaigns taking place on a frequent basis, it may be more prudent to maintain a COST switch and internal wiring within call center 17 connected to either agent telephones (maintaining dual capability) or, to add a second set of telephones dedicated for outbound campaigns. Moreover, agents are reintroduced with a problem solved in the example of FIG. 1 of having to deal with incoming calls to both IP phones, and PC/VDU's.
[0042] [0042]FIG. 3 is a system diagram of the call center and telecommunication network of FIG. 1 enhanced with integrated routing according to an embodiment of the present invention. As discussed with reference to FIG. 2, common elements introduced with the prior art example of FIG. 1 will not be reintroduced here unless they are altered according to an embodiment of the present invention.
[0043] According to a preferred embodiment of the present invention, call center 17 receives COST and IPNT calls from their respective separate networks comprising telecommunication system 11 . Call center 17 is, in this example, enhanced with an integrated router (IR) 83 capable of routing both COST calls and IPNT calls. Central switch 27 is connected via CTI link to a processor running instances of a CTI application known to the inventors as T-server and Stat-server (TS/STAT). An intelligent peripheral in the form of an IVR 84 is connected to processor 82 via data link 81 . Processors 82 and IVR 84 provide CTI enhancement to switch 27 , as well as an application programming interface (API) to IR 83 via installed software.
[0044] It will be apparent to the skilled artisan that processor 82 , IVR 84 and IR 83 may be implemented in a single computing machine executing all of the necessary software, but the functions have separated here for clarity in description.
[0045] A multimedia data server (MIS) 87 is connected to LAN 55 , and is adapted to store and serve certain multimedia content as known in the art. Switch 27 and Router 29 are maintained as call-arrival points for calls arriving from either PSTN 13 or Internet 15 adhering to the separate network-architecture previously described.
[0046] IR 83 performs in an innovative manner in that it not only controls central switch 27 through interaction with processor 82 , and therefore routing of COST calls, but also controls processor 29 and the routing of IPNT calls. IR 83 controls routing of both COST and IPNT calls whether such calls are incoming or outgoing.
[0047] An agent status-table 86 is a real-time database containing agent availability information, which is continually updated as operation-of the call center proceeds. Table 86 may reside in IR 83 as shown, or may reside on processor 82 as part of the T-Server software. Table 86 keeps track of when agents log on or off to the system, and which agents are busy on calls (either COST or IPNT). It will be appreciated that any combination of rules set by the company hosting center 17 may be in place such as priority routing, routing based on skill, statistical routing, and so on, in various combinations known to the inventors.
[0048] Integrated routing as provided by IR 83 allows calls of both types (COST/IPNT) to be distributed evenly among available agents without adding expensive call conversion equipment, or effecting outbound dialing capabilities.
[0049] Yet another improvement in this example over prior art systems is known to the inventor and implemented at some or all agent stations such as stations 31 - 37 . As briefly described with reference to the background section, agent stations 31 - 37 have PC-connected telephones. An I/O cable completes this interface via connection from a telephone receiver/transceiver apparatus such as on telephone 53 to a sound card installed on an associated PC such as PC/VDU 45 . Individual one's of headsets such as headsets a-d are connected either to each telephone or each PC/VDU and are adapted to allow an agent to engage both COST and IPNT calls using the same headset.
[0050] It will be apparent to one with skill in the art that the integrated routing system of the present invention may be utilized in any call center capable of receiving both COST and IPNT (or other DNT) communication. It will also be apparent to one with skill in the art that the present invention may implemented as part of a CTI software package, or held separately and integrated with such a CTI implementation. The present invention is limited only by the claims that follow.
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An integrated router (IR) in a call center monitors and controls both a telephony switch receiving and forwarding connection-oriented, switched telephony (COST) calls and a Data Network Telephony (DNT) processor receiving and forwarding DNT calls. The one IR consults a common data repository storing status of agents on both types of calls, and routes all calls according to a single set of rules, which can take a variety of forms. In one embodiment telephones at agent stations are adapted to handle both OST and DNT calls.
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CROSS REFERENCE TO RELATED APPLICATIONS
This application is a divisional of Ser. No. 10/799,324, now Pat. No. 7,153,869, filed Mar. 12, 2004, which is a divisional of Ser. No. 09/927,111, now Pat. No. 6,750,369, filed Aug. 10, 2001, which is a divisional of Ser. No. 09/517,976, now Pat. No. 6,310,078, filed Mar. 3, 2000, which is a divisional of Ser. No. 09/294,785, now abandoned, filed Apr. 19, 1999, which claims priority from a Provisional Ser. No. 60/082,392, filed Apr. 20, 1998. The complete disclosures of the aforementioned applications are incorporated herein by reference in their entirety.
This invention relates to a series of small molecules which bind to the erythropoietin receptor and compete with the natural ligand for binding to said receptor. The invention includes pharmaceutical compositions containing these mimetics, their methods of production as well as intermediates used in their synthesis.
Erythropoietin (EPO) is a 34,000 dalton glycoprotein hormone which is produced in the mammalian kidney. Its primary role is stimulation of mitotic cell division and differentiation of erythrocyte precursor cells. As a result this hormone regulates the production of erythrocytes, the hemoglobin contained therein and the blood's ability to carry oxygen. The commercial product Epogen® is used in the treatment of anemia. This drug is produced by recombinant techniques and is formulated in aqueous isotonic sodium chloride/sodium citrate. Even though it has been, used successfully in the treatment of anemia, it is a costly drug that is administered intravenously. This method of administration is both costly and inconvenient for the patient; therefore it would be desirable to find a EPO mimetic which has the potential for oral activity.
A small molecule EPO mimetic has advantages over the natural protein. The immune response associated with large peptides is unlikely to occur with small molecules. In addition, the variety of pharmaceutical formulations that may be used with small molecules are technically unfeasible for proteins. Thus the use of relatively inert formulations for small molecules is possible. The most important advantage of small molecules is their potential for oral activity. Such an agent would ease administration, cost less and facilitate patient compliance.
Although compounds which mimic EPO are useful in stimulating red blood cell synthesis, there are diseases where the overproduction of red blood cells is a problem. Erythroleukemia and polysythemia vera are examples of such diseases. Since EPO is an agent responsible for the maturation of red blood cell precursors, an antagonist of EPO would have utility treating either of those diseases.
SUMMARY OF THE INVENTION
The disclosed invention consists of a series of small molecules which demonstrate competitive binding with the natural ligand for the EPO receptor. As such these compounds are potentially useful in the treatment of diseases or conditions associated with this receptor. In addition, the invention contemplates methods of producing these compounds and intermediates used in their production.
The invention includes compounds of the Formula I:
wherein:
R 1 is the side chain of a natural or unnatural α-amino acids, where if said side chain contains a protectable group, that group may be protected with a member of the group consisting of succinyl, glutaryl, 3,3-dimethylglutaryl, C 1-5 alkyl, C 1-5 alkoxycarbonyl, acetyl, N-(9-fluorenylmethoxycarbonyl), trifluoroacetyl, omega-carboxyC 1-5 alkylcarbonyl, t-butoxycarbonyl, benzyl, benzyloxycarbonyl, 2-chlorobenzyloxycarbonyl, phenylsulfonyl, ureido, t-butyl, cinnamoyl, trityl, 4-methyltrityl, 1-(4,4-dimethyl-2,6-dioxocyclohexylidene)ethyl, tosyl, 4-methoxy-2,3,6-trimethylbenzenesulfonyl, phenylureido, and substituted phenylureido (where the phenyl substituents are phenoxy, halo, C 1-5 alkoxycarbonyl); R 2 and R 3
may be taken together to form a six-membered aromatic ring which is fused to the depicted ring, or are independently selected from the group consisting of hydrogen, C 1-5 alkyl, C 1-5 alkoxy, hydroxy, halo, trifluoromethyl, nitro, amino, phenyl, phenoxy, phenylC 1-5 alkyl, phenyl C 1-5 alkoxy, substituted phenyl (where the substituents are selected from C 1-5 alkyl, C 1-5 alkoxy, hydroxy, halo, trifluoromethyl, nitro, cyano, and is amino), substituted phenoxy (where the substituents are selected from C 1-5 alkyl, C 1-5 alkoxy, hydroxy, halo, trifluoromethyl, nitro, cyano, and amino), substituted phenylC 1-5 alkyl (where the substituents are selected from C 1-5 alkyl, C 1-5 alkoxy, hydroxy, halo, trifluoromethyl, nitro, cyano, and amino), substituted phenylC 1-5 alkoxy (where the substituents are selected from C 1-5 alkyl, C 1-5 alkoxy, hydroxy, halo, trifluoromethyl, nitro, cyano, and amino), and substituted amino (where the substituents are selected from one or more members of the group consisting of C 1-5 alkyl, halosubstitutedC 1-5 alkyl, C 1-5 alknyl, C 1-5 alkenyl, phenyl, phenylC 1-5 alkyl, C 1-5 alkylcarbonyl, halo substituted C 1-5 alkylcarbonyl, carboxyC 1-5 alkyl, C 1-5 alkoxyC 1-5 alkyl, cinnamoyl, naphthylcarbonyl, furylcarbonyl, pyridylcarbonyl, C 1-5 alkylsulfonyl, phenylcarbonyl, phenylC 1-5 alkylcarbonyl, phenylsulfonyl, phenylC 1-5 alkylsulfonyl substituted phenylcarbonyl, substituted phenylC 1-5 alkylcarbonyl, substituted phenylsulfonyl, substituted phenylC 1-5 alkylsulfonyl, substituted phenyl, and substituted phenylC 1-5 alkyl [where the aromatic phenyl, phenylC 1-5 alkyl, phenylcarbonyl, phenylC 1-5 alkylcarbonyl, phenylsulfonyl, and phenylC 1-5 alkylsulfonyl substitutents are independently selected from one to five members of the group consisting of C 1-5 alkyl, C 1-5 alkoxy, hydroxy, halogen, trifluoromethyl, nitro, cyano, and amino]);
R 4 and R 5
may be taken together to form a six-membered aromatic ring which is fused to the depicted ring, or are independently selected from the group consisting of hydrogen, C 1-5 alkyl, C 1-5 alkoxy, hydroxy, halo, trifluoromethyl, nitro, amino, phenyl, phenoxy, phenylC 1-5 alkyl, phenyl C 1-5 alkoxy, substituted phenyl (where the substituents are selected from C 1-5 alkyl, C 1-5 alkoxy, hydroxy, halo, trifluoromethyl, nitro, cyano, and amino), substituted phenoxy (where the substituents are selected from C 1-5 alkyl, C 1-5 alkoxy, hydroxy, halo, trifluoromethyl, nitro, cyano, and amino), substituted phenylC 1-5 alkyl (where the substituents are selected from C 1-5 alkyl, C 1-5 alkoxy, hydroxy, halo, trifluoromethyl, nitro, cyano, and amino), substituted phenylC 1-5 alkoxy (where the substituents are selected from C 1-5 alkyl, C 1-5 alkoxy, hydroxy, halo, trifluoromethyl, nitro, cyano, and amino), and substituted amino (where the substituents are selected from one or more members of the group consisting of C 1-5 alkyl, halosubstitutedC 1-5 alkyl, C 1-5 alknyl, C 1-5 alkenyl, phenyl, phenylC 1-5 alkyl, C 1-5 alkylcarbonyl, halo substituted C 1-5 alkylcarbonyl, carboxyC 1-5 alkyl, C 1-5 alkoxyC 1-5 alkyl, cinnamoyl, naphthylcarbonyl, furylcarbonyl, pyridylcarbonyl, C 1-5 alkylsulfonyl, phenylcarbonyl, phenylC 1-5 alkylcarbonyl, phenylsulfonyl, phenylC 1-5 alkylsulfonyl substituted phenylcarbonyl, substituted phenylC 1-5 alkylcarbonyl, substituted phenylsulfonyl, substituted phenylC 1-5 alkylsulfonyl, substituted phenyl, and substituted phenylC 1-5 alkyl [where the aromatic phenyl, phenylC 1-5 alkyl, phenylcarbonyl, phenylC 1-5 alkylcarbonyl, phenylsulfonyl, and phenylC 1-5 alkylsulfonyl substitutents are independently selected from one to five members of the group consisting of C 1-5 alkyl, C 1-5 alkoxy, hydroxy, halogen, trifluoromethyl, nitro, cyano, and amino]);
W is selected from the group consisting of —CH═CH—, —S—, and —CH═N—; Q is selected from the group consisting of —CH═CH—, —S—, and —CH═N—; X is selected from the group consisting of carbonyl, C 1-5 alkyl, C 1-5 alkenyl, C 1-5 alkenylcarbonyl, and (CH 2 ) m —C(O)— where m is 2-5; Y is selected from the group consisting of carbonyl, C 1-5 alkyl, C 1-5 alkenyl, C 1-5 alkenylcarbonyl, and (CH 2 ) m —C(O)— where m is 2-5; n is 1, 2, or 3; Z is selected from the group consisting of hydroxy, C 1-5 alkoxy, phenoxy, phenylC 1-5 alkoxy, amino, C 1-5 alkylamino, diC 1-5 alkylamino, phenylamino, phenylC 1-5 alkylamino, piperidin-1-yl substituted piperidin-1-yl (where the substituents are selected from the group consisting of C 1-5 alkyl, C 1-5 alkoxy, halo, aminocarbonyl, C 1-5 alkoxycarbonyl, and oxo; substituted phenylC 1-5 alkylamino (where the aromatic substitutents are selected from the group consisting of C 1-5 alkyl, C 1-5 alkoxy, phenylC 1-5 alkenyloxy, hydroxy, halogen, trifluoromethyl, nitro, cyano, and amino), substituted phenoxy (where the aromatic substitutents are selected from the group consisting of C 1-5 alkyl, C 1-5 alkoxy, hydroxy, halogen, trifluoromethyl, nitro, cyano, and amino), substituted phenylC 1-5 alkoxy (where the aromatic substitutents are selected from the group consisting of C 1-5 alkyl, C 1-5 alkoxy, hydroxy, halogen, trifluoromethyl, nitro, cyano, and amino), —OCH 2 CH 2 (OCH 2 CH 2 ) s OCH 2 CH 2 O—, —NHCH 2 CH 2 (OCH 2 CH 2 ) s OCH 2 CH 2 NH—, —NH(CH 2 ) p O(CH 2 ) q O(CH 2 ) p NH—, —NH(CH 2 ) q NCH 3 (CH 2 ) s NH—, —NH(CH 2 ) s NH—, and (NH(CH 2 ) s ) 3 N,
where s, p, and q are independently selected from 1-7
with the proviso that if n is 2, Z is not hydroxy, C 1-5 alkoxy, amino, C 1-5 alkylamino, diC 1-5 alkylamino, phenylamino, phenylC 1-5 alkylamino, or piperidin-1-yl,
with the further proviso that if n is 3, Z is (NH(CH 2 ) s ) 3 N.
and the salts thereof.
DETAILED DESCRIPTION OF THE INVENTION
The terms used in describing the invention are commonly used and known to those skilled in the art. “Independently” means that when there are more than one substituent, the substitutents may be different. The term “alkyl” refers to straight, cyclic and branched-chain alkyl groups and “alkoxy” refers O-alkyl where alkyl is as defined supra. “Cbz” refers to benzyloxycarbonyl. “Boc” refers to t-butoxycarbonyl and “Ts” refers to toluenesulfonyl. “DCC” refers to 1,3-dicyclohexylcarbodiimide, “DMAP” refers to 4-N′,N-dimethylaminopyridine and “HOBT” refers to 1-hydroxybenzotriazole hydrate. “Fmoc” refers to N-(9-fluorenylmethoxycarbonyl), “DABCO” refers to 1,4-Diazabicyclo[2.2.2]octane, “EDCI” refers to 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, “Dde” refers to 1-(4,4-dimethyl-2,6-dioxocyclohexylidene)ethyl, and “TMOF” refers to trimethyl orthoformate. The side chains of α-amino acids refer to the substituents of the stereogenic carbon of an α-amino acid. For example if the amino acid is lysine, the side chain is 1-aminobutan-4-yl. The term natural amino acid refers to the 20 α-amino acids of the L configuration which are found in natural proteins. Unnatural α-amino acids include synthetic amino acids such as, α-aminoadipic acid, 4-aminobutanoic acid, 6-aminohexanoic acid, α-aminosuberic acid, 5-aminopentanoic acid, p-aminophenylalanine, α-aminopimelic acid γ-carboxyglutamic acid, p-carboxyphenylalanine, carnitine, citrulline, α,β-diaminopropionic acid, α,γ-diaminobutyric acid, homocitrulline, homoserine, and statine as well as D-configuration amino acids. The term “protectable group” refers to a hydroxy, amino, carboxy, carboxamide, guanidine, amidine or a thiol groups on an amino acid side. Compounds of the invention may be prepared by following general procedures known to those skilled in the art, and those set forth herein.
The compounds of the invention may be prepared by liquid phase organic synthesis techniques or by using amino acids which are bound to a number of known resins. The underlying chemistry, namely, acylation and alkylation reactions, peptide protection and deprotection reactions as well as peptide coupling reactions use similar conditions and reagents. The main distinction between the two methods is in the starting materials. While the starting materials for the liquid phase syntheses are the N-protected amino acids or the lower alkyl ester derivatives of either the N-protected or N-unprotected amino acids, the starting material for the resin syntheses are N-protected amino acids which are bound to resins by their carboxy termini.
General Procedure for the Solid-Phase Synthesis of Symmetrical Nα,Nα-Disubstituted Amino Acids Scheme 1
An equivalent of an N-Fmoc-protected amino acid which is bound to a resin 1a is suspended in a suitable solvent such as DMF. This solvent is removed and the nitrogen protecting group (Fmoc) is removed by stirring the resin bound amino acid with an organic base, such as piperidine, and an addition portion of the solvent. A solution of about two to three equivalents of an appropriately substituted halide, 1b, and a suitable base such DIEA is added to the resin bound amino acid and this mixture is shaken for 18-36 h. The resulting mixture is washed with several portions of a suitable solvent and is suspended and shaken in an acidic solution, such as 50% TFA/CH 2 Cl 2 , over several hours to cleave the acid from the resin and give the N-disubstituted amino acid 1c.
By varying the resin bound amino acid 1a, one may obtain many of the compounds of the invention. The following resin bound amino acids may be used in Scheme I: alanine, N-g-(4-methoxy-2,3,6-trimethylbenzenesulfonyl)arginine, β-(4-methyltrityl)asparagine, aspartic acid (β-t-butyl ester), S-(trityl)cysteine, γ-(4-methyltrityl)glutamine, glutamic acid (β-t-butyl ester), glycine, N-imidazolyl-(trityl)histidine, isoleucine, leucine, N-ε-(2-chlorobenzyloxycarbonyl)lysine, N-ε-(t-butoxycarbonyl)lysine, methionine, phenylalanine, proline, O-(t-butyl)serine, O-(t-butyl)threonine, N-indolyl-(t-butoxycarbonyl)tryptophan. O-(t-butyl)tyrosine, valine, β-alanine, α-aminoadipic acid, 4-aminobutanoic acid, 6-aminohexanoic acid, α-aminosuberic acid, 5-aminopentanoic acid, p-aminophenylalanine, α-aminopimelic acid γ-carboxyglutamic acid, p-carboxyphenylalanine, carnitine, citrulline, α,β-diaminopropionic acid, α,γ-diaminobutyric acid, homocitrulline, homoserine, and statine. In addition, the choice of “W” and “X” can be varied by using known halide derivatives of 1b. For example using benzylchloride, 2-chloromethylthiophene, or 2-chloromethylpyridine gives compounds of the invention where “W” is —CH═CH—, —S—, or —CH═N—, respectively. For variations in “X”, the use of 2-chloroethylphenyl, 3-chloro-1-propenylbenzene, or benzeneacetyl chloride as 1b, give compounds where Y is (CH 2 ) 2 , —CH═CH—CH 2 —, or —CH 2 C(O)— respectively. Still further, Scheme 1 may be used to produce combinatorial mixtures of products. Using mixtures of resin bound amino acids, 1a, with only one 1b produces said combinatorial mixtures. Alternatively, using one amino acid 1a with a mixture of 1b as well as mixture of 1a with mixtures of 1b gives a large range of combinatorial mixtures.
General Procedure for the Solid-Phase Synthesis of Unsymmetrical Nα,Nα-Disubstituted Amino Acids Scheme 2, Step A
An equivalent of an N-Fmoc-protected amino acid which is bound to a resin 1a is suspended in a suitable solvent such as DMF. This solvent is removed and the nitrogen protecting group (Fmoc) is removed by stirring the resin bound amino acid with an organic base, such as piperidine, and an addition portion of the solvent. Trimethyl orthoformate and an appropriately substituted aldehyde 2a (5 equivalents) is added and the mixture is shaken under N 2 overnight. This mixture is treated with a suspension of NaBH(OAc) 3 (5 equivalents) in CH 2 Cl 2 and shaken under N 2 overnight. After filtration and washing with a suitable solvent, the resulting product, resin bound Nα-monosubstituted amino acid 2b, is rinsed with a suitable solvent and its identity is confirmed by MS and or HPLC analysis after treatmet of a portion of the resin with 50% TFA/CH 2 Cl 2 .
Scheme 2, Step B
The resin 2b is suspended in an appropriate solvent such as DMF and is filtered. The appropriately substituted alkyl or arylkyl halide, 2c, and an appropriate base such as DIEA are added with some additional solvent and the mixture is shaken under N 2 for 18-36 h. The resin bound Nα,Nα-disubstituted amino acid, 2d, is isolated from the suspension and the resin is cleaved with an acidic solution to give the free acid 2e.
Scheme 3, Step C
A resin bound amine, 2d, where R 4 is nitro, is suspended in a suitable solvent, such as DMF, and is filtered. This mixture is treated with SnCl 2 dihydrate in DMF and shaken under N 2 overnight. The solvent is removed and the resin is washed successive portions of a suitable solvent to give the resin bound compound 3a where R 4 is amino. The resin is suspended in a suitable solvent and is combined with an organic base, such as pyridine an appropriately substituted carboxylic acid anhydride, acid chloride, or sulfonyl chloride. The mixture is shaken under N 2 overnight and is filtered to give the resin bound amino acid 3b. This material is treated with an acid and a suitable solvent to give the free amino acid 3b.
Scheme 3, Step D
The resin bound amine 3a is treated with TMOF and an appropriately substituted aldehyde 3c is added and the mixture is shaken under N 2 overnight. The resulting mixture is drained and treated with a suspension of NaBH(OAc) 3 in an appropriate solvent and this mixture is shaken under N 2 overnight. The resin bound 3-aralkylaminophenyl amino acid is identified my spectral techniques after clevage to give the free acid 3d as previously described.
Scheme 3, Step E
Resin bound, 2d, where R 1 is (CH 2 ) 4 NH(Dde) is mixed with a suitable solvent, such as DMF, and shaken with successive portions of 2% solution of hydrazine hydrate in DMF over about 30 min. The resin is filtered and treated with a suitable solvent and a cyclic anhydride derivative 3e, and a base such as DMAP and pyridine. This mixture is shaken under N 2 overnight and filtered to give the resin bound amine, 3f. This material is identified by spectral techniques after clevage to give the free acid 3f as previously described.
Scheme 4, Step F
Resin bound 2b, where R 2 is nitro is suspended in CH 2 Cl 2 and is treated with an organic base, such as pyridine, and 9-fluorenylmethoxy chloride. This mixture is shaken under N 2 overnight, filtered and resuspended in a suitable solvent. This mixture is treated with SnCl 2 dihydrate in DMF and shaken under N 2 overnight. The solvent is removed and the resin is washed successive portions of a suitable solvent and filtered to give the resin bound compound 4a where R 2 is amino. The resin 4a is then suspended in a suitable solvent, such as CH 2 Cl 2 , and is combined with 0.4 mmol of pyridine and 0.25-0.4 mmol of the appropriately substituted carboxylic acid anhydride, acid chloride, or sulfonyl chloride. The mixture is shaken under N 2 overnight, filtered, and washed successively with three portions each of CH 2 Cl 2 and MeOH. This resin is suspended in DMF, filtered, and shaken under N 2 with 5 mL of a 40% solution of piperidine in DMF. After 1 h, the solvent is drained and the resin was washed successively with three portions each of suitable solvents to give the resin bound 4b. The identity of the compound was confirmed by spectral analysis after cleveage as previously described.
Scheme 5
The resin 2b (0.2 mmol) is suspended in CH 2 Cl 2 , filtered, and is resuspended in CH 2 Cl 2 . This suspension is treated with diethyl phosphonoacetic acid and diisopropylcarbodiimide or other suitable carbodiimide reagent, and the mixture is shaken under N 2 overnight. The solvent is drained and the resulting resin 5a was washed successively with three portions each of CH 2 Cl 2 and MeOH. The resin is suspended in DMF and filtered. A solution of the appropriately substituted aldehyde 5b (0.6-1.0 mmol) in 3-5 mL of DMF, lithium bromide (0.6-1.0 mmol), and a suitable base such as DIEA or Et 3 N (0.6-1.0 mmol) is added and the mixture is shaken under N 2 overnight. The solvent is removed and the resin is washed successively with three portions each of DMF, CH 2 Cl 2 , and MeOH. The identity of the resin bound substituted amino acid 5c was confirmed spectral techniques. The resin bound material may be treated with 50% TFA/CH 2 Cl 2 over 1-1.5 h, to give the acid 5c.
Scheme 6
To prepare compounds where n is 2 and Z is NH(CH 2 ) s NH, products of Schemes 1-5 may be used in Scheme 6. Treatment of two equivalents of the substituted amino acid 1c with an equivalent of the diamine 6a, in the presence of HOBT and a peptide coupling agent such as EDCI and a base such as DIEA at room temperature over 16 h gives the dimer 6b.
General Procedure for the Solution-Phase Synthesis of Symmetrical Nα,Nα-Disubstituted Amino Acids Scheme 7, Step A
A solution of of amino acid ester 7a, an appropriately substituted halide derivitive 1b, and an appropriate base such as DIEA, Na 2 CO 3 , or Cs 2 CO 3 in a suitable solvent, such as DMF, is heated at 50-100° C. under N 2 overnight, or until the starting material is exhausted, to give a mixture of the di and mono-substituted amines, 7b and 7c respectively. If the side chains of R 1 contain acid cleavable protecting groups, those groups may be cleaved by treatment with 30-80% TFA/CH 2 Cl 2 . Esters 7b and 7c may be independently converted to the corresponding acids 7d and 7e by hydrolysis with an appropriate base such as aqueous NaOH.
General Procedure for the Solution-Phase Synthesis of Unsymmetrical Nα,Nα-Disubstituted Amino Acids Scheme 8, Step A
A solution of 1 mmol of amino acid ester 8a (or the corresponding HCl salt and 1.1 mmol of DIEA) and 1-1.5 mmol of the appropriately substituted aldehyde 2a in 3-5 mL of trimethyl orthoformate was stirred at room temperature under N 2 overnight. The solution was either concentrated and used directly for the next reaction, or was partitioned between EtOAc and water, washed with brine, dried over Na 2 SO 4 , and concentrated to give crude product, which was purified by MPLC to give mono-substituted product 8b.
Scheme 8, Step B
Amino ester 8b was dissolved in DMF, combined with 1.1-1.5 mmol of the appropriately substituted chloride or bromide 2c, and heated at 50-100° C. overnight. The reaction mixture was cooled and partitioned between water and EtOAc. The organic layer was washed three times with water and once with brine, dried over Na 2 SO 4 , and concentrated. The crude product was purified by MPLC to give pure 8c. For examples of 8c wherein the side chain R 1 contained an acid-cleavable protecting group such as t-butylcarbamate, t-butyl ester, or t-butyl ether, 8c was stirred in 30-80% TFA/CH 2 Cl 2 for 1-3 h. The reaction mixture was concentrated and optionally dissolved in HOAc and freeze-dried to give the deprotected form of 8c. For examples of 8c where R 9 was equal to t-butyl, 8c was stirred in 30-80% TFA/CH 2 Cl 2 for 1-3 h and treated as described above to give acid 8d. For examples of 8c where R 9 was equal to methyl, ethyl, or other primary or secondary alkyl esters, 8c was stirred with with 1-2 mmol of aqueous LiOH, NaOH, or KOH in MeOH, EtOH, or THF at 20-80° C. until TLC indicated the absence of 8c. The solution was acidified to pH 4-5 with aqueous citric acid or HCl and was extracted with CH 2 Cl 2 or EtOAc. The organic solution was washed with brine, dried over Na 2 SO 4 , and concentrated to give 8d.
Scheme 8, Step C
For examples of amino acid ester 8c where R 1 =(CH 2 ) 4 NHBoc, 8c (1 mmol) was stirred in 30-80% TFA/CH 2 Cl 2 for 1-3 h. The reaction mixture was concentrated to provide 8e as the TFA salt. Optionally, the TFA salt was dissolved in CH 2 Cl 2 or EtOAc and washed with aqueous NaOH or Na 2 CO 3 , dried over Na 2 SO 4 , and concentrated to give 8e as the free base.
Scheme 8, Step D
A solution of 1 mmol of 8e, 1-4 mmol of an appropriate base such as DIEA, and 1-2 mmol of the appropriately substituted cyclic anhydride 3e was stirred in CH 2 Cl 2 or DMF under N 2 overnight. The resulting mixture was diluted with CH 2 Cl 2 or EtOAc and washed with aqueous HCl, water, and brine, was dried over Na 2 SO 4 , and concentrated to provide 8f. Alternatively, 1 mmol of 8e, 1-4 mmol of an appropriate base such as DIEA, and 1-2 mmol of the appropriately substituted carboxylic acid anhydride (R 11 CO) 2 O or acid chloride R 11 COCl was stirred in CH 2 Cl 2 or DMF under N 2 overnight and worked up as above to provide 8g. Alternatively, 1 mmol of 8e, 1-4 mmol of an appropriate base such as DIEA, and 1-2 mmol of the appropriately substituted isocyanate R 12 NCO was stirred in CH 2 Cl 2 or DMF under N 2 overnight and worked up as above to provide 8h.
Scheme 9, Step A
For examples of 8c where R 5 ═NO 2 , a solution of 1 mmol of 8c (where R 2 , R 3 , R 4 , or) and 10-12 mmol of SnCl 2 dihydrate was stirred in MeOH, EtOH, or DMF at 20-80° C. for 0.5-24 h under N 2 . The solution was taken to room temperature and poured into aqueous Na 2 CO 3 with rapid stirring. The resulting mixture was extracted with EtOAc or CH 2 Cl 2 and the organic extracts were washed with brine, dried over Na 2 SO 4 , and concentrated to give the aminophenyl product 9a, which was purified by MPLC or used without further purification.
Scheme 9, Step B
A solution of 1 mmol of aminophenyl compound 9a and 1-1.5 mmol of the appropriately substituted aldehyde 2a in 3-5 mL of trimethyl orthoformate was stirred at room temperature under N 2 overnight. The solution was either concentrated and used directly for the next reaction, or was partitioned between EtOAc and water, washed with brine, dried over Na 2 SO 4 , and concentrated to give crude product, which was purified by MPLC to give 9b. For examples of 9b wherein the side chain R 1 or R 9 contained an acid-cleavable protecting group such as t-butylcarbamate, t-butyl ester, or t-butyl ether, 9b was stirred in 30-80% TFA/CH 2 Cl 2 for 1-3 h. The reaction mixture was concentrated and optionally dissolved in HOAc and freeze-dried to give the deprotected form of 9b.
Scheme 9, Step C
A solution of 1 mmol of 3-aminophenyl compound 9a, 1.1-2 mmol of pyridine, and 1-1.5 mmol of the appropriately substituted acid chloride, acid anhydride, or sulfonyl chloride in 3-5 mL of CH 2 Cl 2 or ClCH 2 CH 2 Cl was stirred at room temperature under N 2 overnight. The solution was partitioned between EtOAc and water, washed with water, saturated aqueous NaHCO 3 , and brine, dried over Na 2 SO 4 , and concentrated to give crude product which was optionally purified by MPLC to give amide or sulfonamide 9c. For examples of 9c wherein the side chain R 1 or R 9 contained an acid-cleavable protecting group such as t-butylcarbamate, t-butyl ester, or t-butyl ether, 9c was stirred in 30-80% TFA/CH 2 Cl 2 for 1-3 h. The reaction mixture was concentrated and optionally dissolved in HOAc and freeze-dried to give the deprotected form of 9c.
General Procedure for the Solution-Phase Synthesis of Symmetrical Nα,Nα-Disubstituted Amino Amides and their Dimers and Trimers Scheme 10, Step A
A solution of 1 mmol of N-Cbz-protected amino acid 10a and the appropriate amine (ZH, 1 mmol), diamine (ZH 2 , 0.5 mmol), or triamine (ZH 3 0.33 mmol), was treated with 1.1 mmol of HOBt, 1.1 mmol of DIEA, and 2.1 mmol of EDCI in 3-6 mL of CH 2 Cl 2 or DMF. [Alternatively, 1 mmol of the pentafluorophenyl ester or N-hydroxysuccinimide ester of 10a was mixed with the appropriate portion of amine (ZH), diamine (ZH 2 ), or triamine (ZH 3 ) in 3-6 mL of DMF.] The solution was stirred at room temperature under N 2 for 12-24 h, and EtOAc was added. The organic solution was washed with 5% aqueous citric acid, water, saturated NaHCO 3 , and brine, dried over Na 2 SO 4 , and concentrated. The crude product was optionally purified by MPLC to afford amide 10b. Compound 10b was stirred in 30-80% TFA/CH 2 Cl 2 for 1-3 h. The reaction mixture was concentrated to provide the TFA salt which was dissolved in CH 2 Cl 2 or EtOAc and washed with aqueous NaOH or Na 2 CO 3 , dried over Na 2 SO 4 , and concentrated to give 10c as the free base.
Scheme 10, Step B
A solution of 1 mmol of amino acid ester 10c (n=1), 2.5-3 mmol of the appropriately substituted chloride or bromide 2c, and 2.5-3 mmol of an appropriate base such as DIEA, Na 2 CO 3 , or Cs 2 CO 3 in 3-5 mL of DMF was heated at 50-100° C. under N 2 for 18-24 h. (For examples of 10c where n=2 or 3, the amounts of 2c and base were increased by two- or three-fold, respectively.) The reaction mixture was cooled and partitioned between water and EtOAc. The organic layer was washed three times with water and once with brine, dried over Na 2 SO 4 , and concentrated. The crude product was purified by MPLC to give pure amide 10d.
Alternatively, a solution of 1 mmol of amino acid ester 10c (n=1), 2.5-3 mmol of the appropriately substituted aldehyde 2a, and 2.5-3 mmol of borane-pyridine complex in 3-5 mL of DMF or EtOH was stirred at room temperature under N 2 for 3-5 days. (For examples of 10c where n=2 or 3, the amounts of 2c and borane-pyridine complex were increased by two- or three-fold, respectively.) The mixture was concentrated to dryness and was partitioned between water and CH 2 Cl 2 , washed with brine, dried over Na 2 SO 4 , and concentrated. The crude product was purified by MPLC to give pure amide 10d.
Scheme 10, Step C
For examples of 10d where R 1 =CH 2 CH 2 CO 2 -t-Bu or CH 2 CO 2 -t-Bu, 10d was stirred in 30-80% TFA/CH 2 Cl 2 for 1-24 h. The reaction mixture was concentrated and optionally dissolved in HOAc and freeze-dried to give acid 10e.
Scheme 10, Step D
For examples of 10d where R 1 is equal to (CH 2 ) 4 NHBoc, 10d was stirred in 30-80% TFA/CH 2 Cl 2 for 1-24 h. The reaction mixture was concentrated and optionally dissolved in HOAc and freeze-dried to give amine 10f as the TFA salt which was optionally dissolved in CH 2 Cl 2 or EtOAc, washed with aqueous NaOH or Na 2 CO 3 , dried over Na 2 SO 4 , and concentrated to give 10f as the free base.
Scheme 10, Step E
A solution of 1 mmol of 10f, 1-4 mmol of an appropriate base such as DIEA, and 1-2 mmol of the appropriately substituted cyclic anhydride 3e was stirred in CH 2 Cl 2 or DMF under N 2 overnight. The resulting mixture was diluted with CH 2 Cl 2 or EtOAc and washed with aqueous HCl, water, and brine, was dried over Na 2 SO 4 , and concentrated to provide acid 10g. Alternatively, 1 mmol of 10f, 1-4 mmol of an appropriate base such as DIEA, and 1-2 mmol of the appropriately substituted carboxylic acid anhydride (R 11 CO) 2 O or acid chloride R 11 COCl was stirred in CH 2 Cl 2 or DMF under N 2 overnight and worked up as above to provide 10 h. Alternatively, 1 mmol of 8e, 1-4 mmol of an appropriate base such as DIEA, and 1-2 mmol of the appropriately substituted isocyanate R 12 NCO was stirred in CH 2 Cl 2 or DMF under N 2 overnight and worked up as above to provide 10i.
General Procedure for the Solid-Phase Synthesis Of Nα,Nα-Bis-Cinnamyl Amino Acids and Nα-Cinnamyl Amino Acids Scheme 11
An equivalent of an N-Fmoc-protected amino acid 11a which is bound to a polystyrene resin such as Wang resin is suspended in a suitable solvent such as DMF. This solvent is removed and the nitrogen protecting group (Fmoc) is removed by stirring the resin bound amino acid with an organic base, such as piperidine, and an addition portion of the solvent. After filtration and washing with solvent, the resin is suspended in an appropriate solvent such as DMF. A solution of about 2-3 equivalents of an appropriately substituted halide 11b and a suitable base such DIEA is added to the resin bound amino acid and this mixture is shaken for 18-36 h. The resulting mixture is washed with several portions of a suitable solvent and is suspended and shaken in an acidic solution, such as 50% TFA/CH 2 Cl 2 , over several hours to cleave the acid from the resin to give a mixture of the Nα,Nα-bis-cinnamyl amino acid 11c and the Nα-cinnamyl amino acid 11d.
By varying the resin bound amino acid 11a, one may obtain many of the compounds of the invention. The following resin bound amino acids may be used in Scheme 11: alanine, N-g-(4-methoxy-2,3,6-trimethylbenzenesulfonyl)arginine, β-(4-methyltrityl)asparagine, aspartic acid (β-t-butyl ester), S-(trityl)cysteine, γ-(4-methyltrityl)glutamine, glutamic acid (β-t-butyl ester), glycine, N-imidazolyl-(trityl)histidine, isoleucine, leucine. N-ε-(2-chlorobenzyloxycarbonyl)lysine, N-ε-(t-butoxycarbonyl)lysine, methionine, phenylalanine, proline, O-(t-butyl)serine, O-(t-butyl)threonine, N-indolyl-(t-butoxycarbonyl)tryptophan, O-(t-butyl)tyrosine, valine, β-alanine, α-aminoadipic acid, 4-aminobutanoic acid, 6-aminohexanoic acid, α-aminosuberic acid, 5-aminopentanoic acid, p-aminophenylalanine, α-aminopimelic acid γ-carboxyglutamic acid, p-carboxyphenylalanine, carnitine, citrulline, α,β-diaminopropionic acid, α,γ-diaminobutyric acid, homocitrulline, homoserine, and statine.
Scheme 12, Step A
An equivalent of an N-Fmoc-protected amino acid which is bound to a resin 11a is suspended in a suitable solvent such as DMF. This solvent is removed and the nitrogen protecting group (Fmoc) is removed by stirring the resin bound amino acid with an organic base, such as piperidine, and an addition portion of the solvent. After filtration and washing with solvent, the resin is suspended in an appropriate solvent such as trimethyl orthoformate (TMOF), an appropriately substituted aldehyde 12a (5 equivalents) is added, and the mixture is shaken under N 2 overnight. This mixture is treated with a suspension of NaBH(OAc) 3 (5 equivalents) in CH 2 Cl 2 and shaken under N 2 overnight. After filtration and washing with a suitable solvent, the resulting product, resin bound Nα-monosubstituted amino acid 12b, is suspended and shaken in an acidic solution, such as 50% TFA/CH 2 Cl 2 , over several hours to cleave the acid from the resin to give the Nα-cinnamyl amino acid 11d.
Scheme 12, Step B
The resin 12b is suspended in an appropriate solvent such as DMF and is filtered. The appropriately substituted halide 12c and an appropriate base such as DIEA are added with some additional solvent and the mixture is shaken under N 2 for 18-36 h. The resin bound Nα,Nα-cinnamyl amino acid 12d is isolated from the suspension and the resin is cleaved with an acidic solution as described above to give the free acid 12e.
General Procedure for the Solution-Phase Synthesis of Nα,Nα-Bis-Cinnamyl Amino Acids and Nα-Cinnamyl Amino Acids Scheme 13
A solution of of amino acid ester 13a, an appropriately substituted halide 11b, and an appropriate base such as DIEA, Na 2 CO 3 , or Cs 2 CO 3 in a suitable solvent, such as DMF, is heated at 50-100° C. under N 2 overnight, or until the starting material is exhausted, to give a mixture of the Nα,Nα-bis-cinnamyl amino acid ester 13b and Nα-cinnamyl amino acid ester 13c. If the side chain of R 1 contains an acid-cleavable protecting group such as t-butylcarbamate, t-butyl ester, or t-butyl ether, those groups may be cleaved by, treatment with an acidic solution such as 30-80% TFA/CH 2 Cl 2 or 2-4N HCl in EtOAc. For examples of 13b and 13c where the ester group R 4 is a primary alkyl group such as methyl or ethyl, esters 13b and 13c may be independently converted to the corresponding acids 11c and 11d by hydrolysis with an appropriate base such as aqueous NaOH, KOH, or LiOH. For examples of 13b and 13c where the ester group R 4 is an acid-cleavable group such as t-butyl, esters 13b and 13c may be independently converted to the corresponding acids 11c and 11d by treatment with an acidic solution such as 30-80% TFA/CH 2 Cl 2 or 2-4N HCl in EtOAc.
Scheme 14, Step A
A solution of 1 mmol of amino acid ester and 1-1.5 mmol of the appropriately substituted aldehyde 12a in 3-5 mL of TMOF was stirred at room temperature under N 2 overnight. The solution was concentrated and used directly for the next reaction; optionally, the solution was partitioned between EtOAc and water, washed with brine, dried over Na 2 SO 4 , and concentrated to give crude product, which was purified by MPLC to give mono-substituted product 14a. For examples of 14a wherein the side chain R 1 contained an acid-cleavable protecting group such as t-butylcarbamate, t-butyl ester, or t-butyl ether, 8c was treated with an acidic solution such as 30-80% TFA/CH 2 Cl 2 or 2-4N HCl in EtOAc. The reaction mixture was concentrated and optionally dissolved in HOAc and freeze-dried to give the deprotected form of 14a. For examples of 14a where the ester group R 4 is a primary alkyl group such as methyl or ethyl, esters 14a may be converted to the corresponding acids 11d by hydrolysis with an appropriate base such as aqueous NaOH, KOH, or LiOH. For examples of 14a where the ester group R 4 is an acid-cleavable group such as t-butyl, esters 14a may be converted to the corresponding acids 11d by treatment with an acidic solution such as 30-80% TFA/CH 2 Cl 2 or 2-4N HCl in EtOAc.
Scheme 14, Step B
Amino ester 14a was dissolved in DMF, combined with 1.1-1.5 mmol of the appropriately substituted chloride or bromide 12c, and heated at 50-100° C. overnight. The reaction mixture was cooled and partitioned between water and EtOAc. The organic layer was washed with water and brine, dried over Na 2 SO 4 , and concentrated. The crude product was purified by MPLC to give pure 14b. For examples of 14b wherein the side chain R 1 contained an acid-cleavable protecting group such as t-butylcarbamate, t-butyl ester, or t-butyl ether, 8c was treated with an acidic solution such as 30-80% TFA/CH 2 Cl 2 or 2-4N HCl in EtOAc. The reaction mixture was concentrated and optionally dissolved in HOAc and freeze-dried to give the deprotected form of 14b. For examples of 14b where the ester group R 4 is a primary alkyl group such as methyl or ethyl, esters 14b may be converted to the corresponding acids 12e by hydrolysis with an appropriate base such as aqueous NaOH, KOH, or LiOH. For examples of 14b where the ester group R 4 is an acid-cleavable group such as t-butyl, esters 14b may be converted to the corresponding acids 12e by treatment with an acidic solution such as 30-80% TFA/CH 2 Cl 2 or 2-4N HCl in EtOAc.
Although the claimed compounds are useful as competitive binders to the EPO receptor, some compounds are more active than others and are either preferred or particularly preferred.
The particularly preferred “R 1 ”s are the side chain of lysine, ornithine, arginine, aspartic acid, glutamic acid, glutamine, cysteine, methionine, serine, and threonine.
The particularly preferred “R 2 and R 3 ” s are phenoxy, substituted phenoxy, benzyloxy, and substituted benzyloxy.
The particularly preferred “R 4 and R 5 ” s are phenoxy, substituted phenoxy, benzyloxy, and substituted benzyloxy.
The particularly preferred “W” is —CH═CH—
The particularly preferred “Q” is —CH═CH—
The particularly preferred “X” are C 1-5 alkenyl and CH 2 .
The particularly preferred “Y” are C 1-5 alkenyl and CH 2 .
The particularly preferred “n” are 1 and 2.
The particularly preferred “Z” are hydroxy, methoxy, phenethylamino, substituted phenethylamino, and —NH(CH 2 ) 2 O(CH 2 ) 2 O(CH 2 ) 2 NH—.
Pharmaceutically useful compositions the compounds of the present invention, may be formulated according to known methods such as by the admixture of a pharmaceutically acceptable carrier. Examples of such carriers and methods of formulation may be found in Remington's Pharmaceutical Sciences. To form a pharmaceutically acceptable composition suitable for effective administration, such compositions will contain an effective amount of the compound of the present invention.
Therapeutic or diagnostic compositions of the invention are administered to an individual in amounts sufficient to treat or diagnose disorders in which modulation of EPO receptor-related activity is indicated. The effective amount may vary according to a variety of factors such as the individual's condition, weight, sex and age. Other factors include the mode of administration. The pharmaceutical compositions may be provided to the individual by a variety of routes such as subcutaneous, topical, transdermal, oral and parenteral.
The term “chemical derivative” describes a molecule that contains additional chemical moieties which are not normally a part of the base molecule. Such moieties may improve the solubility, half-life, absorption, etc. of the base molecule. Alternatively the moieties may attenuate undesirable side effects of the base molecule or decrease the toxicity of the base molecule. Examples of such moieties are described in a variety of texts, such as Remington's Pharmaceutical Sciences.
Compounds disclosed herein may be used alone at appropriate dosages defined by routine testing in order to obtain optimal inhibition of the EPO receptor or its activity while minimizing any potential toxicity. In addition, co-administration or sequential administration of other agents may be desirable.
The present invention also has the objective of providing suitable topical, transdermal, oral, systemic and parenteral pharmaceutical formulations for use in the novel methods of treatment of the present invention. The compositions containing compounds according to this invention as the active ingredient for use in the modulation of EPO receptors can be administered in a wide variety of therapeutic dosage forms in conventional vehicles for administration. For example, the compounds or modulators can be administered in such oral dosage forms as tablets, capsules (each including timed release and sustained release formulations), pills, powders, granules, elixirs, tinctures, solutions, suspensions, syrups and emulsions, or by transdermal delivery or injection. Likewise, they may also be administered in intravenous (both bolus and infusion), intraperitoneal, subcutaneous, topical with or without occlusion, transdermal, or intramuscular form, all using forms well known to those of ordinary skill in the pharmaceutical arts. The compounds of the present invention may be delivered by a wide variety of mechanisms, including but not limited to, transdermal delivery, or injection by needle or needle-less injection means. An effective but non-toxic amount of the compound desired can be employed as an EPO receptor modulating agent.
The daily dosage of the products may be varied over a wide range from 0.01 to 1,000 mg per patient, per day. For oral administration, the compositions are preferably provided in the form of scored or unscored tablets containing 0.01, 0.05, 0.1, 0.5, 1.0, 2.5, 5.0, 10.0, 15.0, 25.0, and 50.0 milligrams of the active ingredient for the symptomatic adjustment of the dosage to the patient to be treated. An effective amount of the drug is ordinarily supplied at a dosage level of from about 0.0001 mg/kg to about 100 mg/kg of body weight per day. The range is more particularly from about 0.001 mg/kg to 10 mg/kg of body weight per day. The dosages of the EPO receptor modulators are adjusted when combined to achieve desired effects. On the other hand, dosages of these various agents may be independently optimized and combined to achieve a synergistic result wherein the pathology is reduced more than it would be if either agent were used alone.
Advantageously, compounds or modulators of the present invention may be administered in a single daily dose, or the total daily dosage may be administered in divided doses of two, three or four times daily. Furthermore, compounds or modulators for the present invention can be administered in intranasal form via topical use of suitable intranasal vehicles, or via transdermal routes, using those forms of transdermal skin patches well known to those of ordinary skill in that art. To be administered in the form of a transdermal delivery system, the dosage administration will, of course, be continuous rather than intermittent throughout the dosage regimen.
For combination treatment with more than one active agent, where the active agents are in separate dosage formulations, the active agents can be administered concurrently, or they each can be administered at separately staggered times.
The dosage regimen utilizing the compounds or modulators of the present invention is selected in accordance with a variety of factors including type, species, age, weight, sex and medical condition of the patient; the severity of the condition to be treated; the route of administration; the renal and hepatic function of the patient; and the particular compound thereof employed. A physician or veterinarian of ordinary skill can readily determine and prescribe the effective amount of the drug required to prevent, counter or arrest the progress of the condition. Optimal precision in achieving concentrations of drug within the range that yields efficacy without toxicity requires a regimen based on the kinetics of the drug's availability to target sites. This involves a consideration of the distribution, equilibrium, and elimination of a drug.
In the methods of the present invention, the compounds or modulators herein described in detail can form the active ingredient, and are typically administered in admixture with suitable pharmaceutical diluents, excipients or carriers (collectively referred to herein as “carrier” materials) suitably selected with respect to the intended form of administration, that is, oral tablets, capsules, elixirs, syrups and the like, and consistent with conventional pharmaceutical practices.
For instance, for oral administration in the form of a tablet or capsule, the active drug component can be combined with an oral, non-toxic pharmaceutically acceptable inert carrier such as ethanol, glycerol, water and the like. Moreover, when desired or necessary, suitable binders, lubricants, disintegrating agents and coloring agents can also be incorporated into the mixture. Suitable binders include, without limitation, starch, gelatin, natural sugars such as glucose or beta-lactose, corn sweeteners, natural and synthetic gums such as acacia, tragacanth or sodium alginate, carboxymethylcellulose, polyethylene glycol, waxes and the like. Lubricants used in these dosage forms include, without limitation, sodium oleate, sodium stearate, magnesium stearate, sodium benzoate, sodium acetate, sodium chloride and the like. Disintegrators include, without limitation, starch, methyl cellulose, agar, bentonite, xanthan gum and the like.
For liquid forms the active drug component can be combined in suitably flavored suspending or dispersing agents such as the synthetic and natural gums, for example, tragacanth, acacia, methyl-cellulose and the like. Other dispersing agents which may be employed include glycerin and the like. For parenteral administration, sterile suspensions and solutions are desired. Isotonic preparations which generally contain suitable preservatives are employed when intravenous administration is desired.
Topical preparations containing the active drug component can be admixed with a variety of carrier materials well known in the art, such as, e.g., alcohols, aloe vera gel, allantoin, glycerine, vitamin A and E oils, mineral oil, PPG2 myristyl propionate, and the like, to form, e.g., alcoholic solutions, topical cleansers, cleansing creams, skin gels, skin lotions, and shampoos in cream or gel formulations.
The compounds or modulators of the present invention can also be administered in the form of liposome delivery systems, such as small unilamellar vesicles, large unilamellar vesicles and multilamellar vesicles. Liposomes can be formed from a variety of phospholipids, such as cholesterol, stearylamine or phosphatidylcholines.
Compounds of the present invention may also be delivered by the use of monoclonal antibodies as individual carriers to which the compound molecules are coupled. The compounds or modulators of the present invention may also be coupled with soluble polymers as targetable drug carriers. Such polymers can include polyvinyl-pyrrolidone, pyran copolymer, polyhydroxypropylmethacrylamidephenol, polyhydroxy-ethylaspartamidephenol, or polyethyleneoxidepolylysine substituted with palmitoyl residues. Furthermore, the compounds or modulators of the present invention may be coupled to a class of biodegradable polymers useful in achieving controlled release of a drug, for example, polylactic acid, polyepsilon caprolactone, polyhydroxy butyric acid, polyorthoesters, polyacetals, polydihydro-pyrans, polycyanoacrylates and cross-linked or amphipathic block copolymers of hydrogels, and other suitable polymers known to those skilled in the art.
For oral administration, the compounds or modulators may be administered in capsule, tablet, or bolus form or alternatively they can be mixed in the animals feed. The capsules, tablets, and boluses are comprised of the active ingredient in combination with an appropriate carrier vehicle such as starch, talc, magnesium stearate, or di-calcium phosphate. These unit dosage forms are prepared by intimately mixing the active ingredient with suitable finely-powdered inert ingredients including diluents, fillers, disintegrating agents, and/or binders such that a uniform mixture is obtained. An inert ingredient is one that will not react with the compounds or modulators and which is non-toxic to the animal being treated. Suitable inert ingredients include starch, lactose, talc, magnesium stearate, vegetable gums and oils, and the like. These formulations may contain a widely variable amount of the active and inactive ingredients depending on numerous factors such as the size and type of the animal species to be treated and the type and severity of the infection. The active ingredient may also be administered as an additive to the feed by simply mixing the compound with the feedstuff or by applying the compound to the surface of the feed. Alternatively the active ingredient may be mixed with an inert carrier and the resulting composition may then either be mixed with the feed or fed directly to the animal. Suitable inert carriers include corn meal, citrus meal, fermentation residues, soya grits, dried grains and the like. The active ingredients are intimately mixed with these inert carriers by grinding, stirring, milling, or tumbling such that the final composition contains from 0.001 to 5% by weight of the active ingredient.
The compounds or modulators may alternatively be administered parenterally via injection of a formulation consisting of the active ingredient dissolved in an inert liquid carrier. Injection may be either intramuscular, intraruminal, intratracheal, or subcutaneous, either by needle or needle-less means. The injectable formulation consists of the active ingredient mixed with an appropriate inert liquid carrier. Acceptable liquid carriers include the vegetable oils such as peanut oil, cotton seed oil, sesame oil and the like as well as organic solvents such as solketal, glycerol formal and the like. As an alternative, aqueous parenteral formulations may also be used. The vegetable oils are the preferred liquid carriers. The formulations are prepared by dissolving or suspending the active ingredient in the liquid carrier such that the final formulation contains from 0.005 to 10% by weight of the active ingredient.
Topical application of the compounds or modulators is possible through the use of a liquid drench or a shampoo containing the instant compounds or modulators as an aqueous solution or suspension. These formulations generally contain a suspending agent such as bentonite and normally will also contain an antifoaming agent. Formulations containing from 0.005 to 10% by weight of the active ingredient are acceptable. Preferred formulations are those containing from 0.01 to 5% by weight of the instant compounds or modulators.
The compounds of Formula I may be used in pharmaceutical compositions to treat patients (humans and other mammals) with disorders or conditions associated with the production of erythropoietin or modulated by the EPO receptor. The compounds can be administered in the manner of the commercially available product or by any oral or parenteral route (including but not limited to, intravenous, intraperitoneal, intramuscular, subcutaneous, dermal patch), where the preferred route is by injection. When the method of administration is intravenous infusion, compound of Formula I may be administered in a dose range of about 0.01 to 1 mg/kg/min. For oral administration, the dose range is about 0.1 to 100 mg/kg.
The pharmaceutical compositions can be prepared using conventional pharmaceutical excipients and compounding techniques. Oral dosage forms may be used and are elixirs, syrups, capsules, tablets and the like. Where the typical solid carrier is an inert substance such as lactose, starch, glucose, methyl cellulose, magnesium stearate, dicalcium phosphate, mannitol and the like; and typical liquid oral excipients include ethanol, glycerol, water and the like. All excipients may be mixed as needed with disintegrants, diluents, granulating agents, lubricants, binders and the like using conventional techniques known to those skilled in the art of preparing dosage forms. Parenteral dosage forms may be prepared using water or another sterile carrier.
Typically the compounds of Formula I are isolated as the free base, however when possible pharmaceutically acceptable salts can be prepared. Examples of such salts include hydrobromic, hydroiodic, hydrochloric, perchloric, sulfuric, maleic, fumaric, malic, tartaric, citric, benzoic, mandelic, methanesulfonic, hydroethanesulfonic, benzenesulfonic, oxalic, pamoic, 2-naphthalenesulfonic, p-toluenesulfonic, cyclohexanesulfamic and saccharic.
In order to illustrate the invention the following examples are included. These examples do not limit the invention. They are only meant to suggest a method of practicing the invention. Those knowledgeable in chemical synthesis and the treatment of EPO related disorders may find other methods of practicing the invention. However those methods are deemed to be within the scope of this invention.
BIOLOGICAL EXAMPLES
The compounds of the invention were evaluated for the ability to compete with EPO in the following immobilized EPO receptor preparation (EBP-Ig, EPO binding protein-Ig).
EBP-Ig fusion protein (as disclosed in WO97/27219 which is herein incorporated by reference) was purified by affinity chromatography from the conditioned media of NSO cells engineered to express a recombinant gene construct which functionally joined the N-terminal 225 amino acids of the human EPO receptor and an Ig heavy chain as described herein. The interaction of biotin and streptavidin is frequently employed to capture and effectively immobilize reagents useful in assay protocols and has been employed here as a simple method to capture and immobilize EBP-Ig. EBP-Ig is initially randomly modified with an amine reactive derivative of biotin to produce biotinylated-EBP-Ig. Use of streptavidin coated plates allows the capture of the biotinylated EBP-Ig on the surface of a scintillant impregnated coated well (Flash plates, NEN-DuPont). Upon binding of [ 125 I]EPO to the ligand binding domain, specific distance requirements are satisfied and the scintillant is induced to emit light in response to the energy emitted by the radioligand. Unbound radioligand does not produce a measurable signal because the energy from the radioactive decay is too distant from the scintillant. The amount of light produced was quantified to estimate the amount of ligand binding. The specific assay format was suitable for the multi-well plate capacity of a Packard TopCount Microplate Scintillation counter. Compounds which were capable of reducing the amount of detected signal through competitive binding with the radioligand were identified.
Biotinylated EBP-Ig was prepared as follows. EBP-Ig (3 mL, OD 280 2.9) was exchanged into 50 mM sodium bicarbonate, pH 8.5 using a Centriprep 10 ultrafiltration device. The final volume of the exchanged protein was 1.2 mL (OD 280 2.6, representing about 2 mg total protein). 10 μL of a 4 mg/ml solution of NHS-LC-Biotin (Pierce) was added and the reaction mixture placed on ice in the dark for two hours. Unreacted biotin was removed by exchange of the reaction buffer into PBS in a Centriprep 10 device and the protein reagent aliquoted and stored at −70° C.
Each individual binding well (200 μL) contained final concentrations of 1 μg/mL of biotinylated EBP-Ig, 0.5 nM of [ 125 I]EPO (NEN Research Products, Boston, 100 μCi/μg) and 0-500 μM of test compound (from a 10-50 mM stock in 100% DMSO). All wells were adjusted to a final DMSO concentration of 5%. All assay points were performed in triplicate and with each experiment a standard curve for unlabelled EPO was performed at final concentration of 2000, 62, 15, 8, 4, and 0 nM. After all additions were made, the plate was covered with an adhesive top seal and placed in the dark at room temperature overnight. The next day all liquid was aspirated from the wells to limit analyte dependent quench of the signal, and the plates were counted on a Packard TOPCOUNT Microplate Scintillation Counter. Non-specific binding (NSB) was calculated as the mean CPM of the 2000 nM EPO wells and total binding (TB) as the mean of the wells with no added unlabelled EPO. Corrected total binding (CTB) was calculated as: TB−NSB=CTB. The concentration of test compound which reduced CTB to 50% was reported as the IC 50 . Typically the IC 50 value for unlabelled EPO was ca. 2-7 nM and EMP1 was 0.1 μM. Table 1 lists the average % inhibition, and if determined the IC 50 and IC 30 values for compounds of Formula I, where the compound numbers refer to the compounds in the tables accompanying the preparative examples.
TABLE 1
Inhibition of EPO binding to EBP-Ig
cpd
% inh @ 50 μM
IC 30 μM*
IC 50 , μM*
11
70
nd
nd
12
59
nd
nd
14
30
nd
nd
15
48
nd
nd
77
52
30
40
82
32
nd
nd
86
37
nd
nd
100
34
nd
nd
101
32
nd
nd
104
78
10
30
105
70
25
35
107
78
30
42
108
81
23
36
110
54
6
10
112
59
2
10
114
37
10
nd
115
35
nd
nd
116
32
nd
nd
117
34
nd
nd
118
36
2
10
119
34
nd
nd
120
35
nd
nd
121
45
6
nd
137
60
5
30
139
46
2
10
178
36
nd
nd
179
30
nd
nd
183
36
nd
nd
184
53
10
nd
203
37
50
nd
211
62
20
65
220
45
30
50
221
48
10
80
222
56
5
nd
224
51
25
50
227
48
20
50
230
42
nd
nd
231
36
nd
nd
235
49
20
50
237
55
30
70
238
39
nd
nd
239
46
8
50
243
75
2
18
244
66
1
28
246
79
10
75
247
47
7
18
248
56
7
20
249
72
7
10
250
78
7
20
251
49
10
45
261
51
1.5
2
262
93
1
1.5
263
88
1
1.5
264
89
1.5
8
265
65
1
6
266
82
1
4
267
83
2
6
268
40
nd
nd
269
55
8
85
270
56
7
100
271
77
2
7
272
78
5
10
285
41
nd
nd
286
46
35
65
287
36
nd
nd
300
57
35
145
305
48
35
225
312
45
10
85
321
42
45
nd
363
33
35
220
366
38
65
nd
368
40
90
nd
*nd = not determined
PREPARATIVE EXAMPLES
Unless otherwise noted, materials used in the examples were obtained from commercial supplies and were used without further purification. Melting points were determined on a Thomas Hoover apparatus and are uncorrected. Proton nuclear magnetic resonance ( 1 H NMR) spectra were measured in the indicated solvent with tetramethylsilane (TMS) as the internal standard using a Bruker AC-300 NMR spectrometer. NMR chemical shifts are expressed in parts per million (ppm) downfield from internal TMS using the d scale. 1 H NMR data are tabulated in order; multiplicity, (s, singlet; d, doublet; t, triplet; q, quartet; m, multiplet), number of protons, coupling constant in Hertz). Electrospray (ES) mass spectra (MS) were determined on a Hewlett Packard Series 1090 LCMS Engine. Elemental analyses were performed by Quantitative Technologies, Inc. (QTI), PO Box 470, Salem Industrial Park, Bldg #5, Whitehouse, N.J. 08888-0470. Analytical thin layer chromatography (TLC) was done with Merck Silica Gel 60 F 254 plates (250 micron). Medium pressure liquid chromatography (MPLC) was done with Merck Silica Gel 60 (230-400 mesh).
Example 1
N,N-bis(3-Phenoxycinnamyl)Glu(O-t-Bu)-OMe (cpd 96) and N-(3-phenoxycinnamyl)Glu(O-t-Bu)-OMe (cpd 334)
A solution of 500 mg (1.97 mmol) of H-Glu(O-t-Bu)OMe.HCl, 997 mg (3.45 mmol) of 3-phenoxycinnamyl bromide (Jackson, W. P.; Islip, P. J.; Kneen, G.; Pugh, A.; Wates, P. J. J.Med.Chem. 31 1988; 499-500), and 0.89 mL (5.1 mmol, 660 mg) of DIEA in 5 mL of DMF was stirred under N 2 at room temperature for 40 h. The mixture was partitioned between EtOAc and water and the organic layer was washed with water and brine. After drying over Na 2 SO 4 , the organic solution was concentrated to give 1.24 g of orange oil. The crude residue was purified by MPLC using a solvent gradient ranging from 10-30% EtOAc/hexanes to give two products. The less polar product (cpd 96, 235 mg, 19% based on starting amino acid), was isolated as a pale yellow oil; 1 H NMR (CDCl 3 , 300 MHz) 1.39 (s, 9H), 2.0 (m, 2H), 2.33 (dt, 2H, J=2, 7 Hz), 3.24 (dd, 2H, J=8, 15 Hz), 3.5, (m, 3H), 3.69 (s, 3H), 6.13 (m, 2H), 6.47 (d, 2H, J=16 Hz), 6.86 (dd, 2H, J=1.5, 8 Hz), 7.0-7.4 (complex, 16H); MS (ES+) m/z 634 (MH+).
The more polar product (cpd 334, 422 mg, 50% based on starting amino acid) was isolated as a pale yellow oil; 1 H NMR (CDCl 3 , 300 MHz) 1.42 (s, 9H), 1.9 (m, 2H), 2.35 (t, 2H, J=7.5 Hz), 3.2-3.4 (complex, 3H), 3.71 (s, 3H), 6.17 (dt, 1H, J=16, 6 Hz), 6.46 (d, 1H, J=16 Hz), 6.87 (dd, 1H, J=1.5, 8 Hz), 7.01 (m, 3H), 7.10 (t, 2H, J=7.5 Hz), 7.2-7.4 (complex, 3H); MS (ES+) m/z 426 (MH+). Anal. Calcd for C 25 H 31 NO 5 : C, 70.57; H, 7.34; N, 3.29. Found: C, 70.29; H, 7.14; N, 3.08.
Example 2
N-(3-Phenoxycinnamyl)Glu-OMe (cpd 325)
A solution of 95 mg (0.22 mmol) of N-(3-phenoxycinnamyl)Glu(O-t-Bu)-OMe (cpd 334) in 3 mL of 50% TFA/CH 2 Cl 2 was stirred for 2 h at room temperature. The mixture was concentrated and the residue was dissolve in acetic acid and freeze-dried to give 117 mg of N-(3-phenoxycinnamyl)Glu-OMe (cpd 325) as an off-white solid; 1 H NMR (CD 3 OD, 300 MHz) 2.3-2.7 (complex, 4H), 3.78 (s, 3H), 3.81 (d, 2H, J=7 Hz), 4.09 (t, 1H, J=5 Hz), 6.17 (dt, 1H, J=16, 7 Hz), 6.55 (d, 1H, J=16 Hz), 6.9 (m, 4H), 7.11 (t, 2H, J=7.5 Hz), 7.3 (m, 4H); MS (ES+) m/z 370 (MH+), 209. Anal. Calcd for C 21 H 23 NO 5 .C 2 HF 3 O 2 : C, 57.14; H, 5.00; N, 2.90. Found: C, 57.07; H, 5.02; N, 2.73.
Example 3
N,N-bis(3-Phenoxycinnamyl)Asp(O-t-Bu)-O-t-Bu (cpd 106)
A solution of 1.00 g (3.55 mmol) of Asp(O-t-Bu)-O-t-Bu.HCl, 2.05 g (7.1 mmol) of 3-phenoxycinnamyl bromide, and 1.86 mL (10.7 mmol, 1.38 g) of DIEA in 15 mL of DMF was heated under N 2 at 60° C. overnight. Additional 3-phenoxycinnamyl bromide (1.0 g, 3.4 mmol) and DIEA (0.95 mL, 0.705 g, 5.4 mmol) were added and heating was continued for an additional 14 h. The mixture was cooled and partitioned between EtOAc and water. The organic layer was washed twice with water, once with brine, and was dried over Na 2 SO 4 . The solution was concentrated to give 3.5 g of an amber oil which was purified by MPLC using a solvent gradient ranging from 2.5-3% EtOAc/hexanes to afford 1.21 g of cpd 106 as a pale yellow oil; 1 H NMR (CDCl 3 , 300 MHz) 1.41 (s, 9H), 1.48 (s, 9H), 2.49 (dd, 1H, J=7.5, 15.5 Hz), 2.70 (dd, 1H, J=7.5, 15.5 Hz), 3.26 (dd, 2H, J=7.5, 14.5 Hz), 3.47 (dd, 2H, J=4, 14.5 Hz), 3.88 (t, 1H, J=7.5), 6.13 (m, 2H), 6.48 (d, 2H, J=16 Hz), 6.86 (dd, 2H, J=2, 8 Hz), 7.0 (m, 6H), 7.1 (m, 4H), 7.2-7.4 (complex, 6H); MS (ES+) m/z 662 (MH+).
Example 4
N,N-bis(3-Phenoxycinnamyl)Asp-OH (cpd 107)
A solution of 1.14 g (1.62 mmol) of cpd 106 in 16 mL of 50% TFA/CH 2 Cl 2 was stirred at room temperature for 24 h. The solution was concentrated and pumped to give 1.37 g (˜100%) cpd 107 as an amber oil; 1 H NMR (CD 3 OD, 300 MHz) 3.1 (m, 2H), 4.0 (dd, 2H, J=8, 14 Hz), 4.27 (dd, 2H, J=8, 16 Hz), 4.70 (t, 1H, J=4 Hz), 6.38 (2H, dt, J=16, 8 Hz), 6.7-7.4 (complex, 20H); MS (ES−) m/z 562 ([M-H]+).
Example 5
N,N-bis(4-Benzyloxybenzyl)Lys(Boc)-OMe (cpd 111) and N-(4-Benzyloxybenzyl)Lys(Boc)-OMe
A solution of 594 mg (2.0 mmol) of Lys(Boc)-OMe.HCl, 524 mg (2.25 mmol) of 4-benzyloxybenzyl chloride, 75 mg (0.5 mmol), of NaI, and 0.61 mL (3.5 mol, 452 mg) of DIEA was warmed at 50-70° C. under N 2 overnight. The mixture was cooled and partioned between EtOAc and water. The organic layer was washed twice with water, once with brine, and was dried over Na 2 SO 4 . The organic solution was concentrated to give 0.83 g of amber oil which was purified by MPLC using a solvent gradient ranging from 15-40% EtOAc/hexanes to give two products. The less polar product (296 mg), cpd 111, was isolated as a pale yellow oil; 1 H NMR (CDCl 3 , 300 MHz) 1.28 (m, 4H), 1.43 (s, 9H), 1.70 (m, 2H), 3.03 (m, 2H), 3.28 (t, 1H, J=7 Hz), 3.40 (d, 2H, J=13.5 Hz), 3.74 (s, 3H), 3.81 (d, 2H, J=13.5 Hz), 5.05 (2, 4H), 6.92 (d, 4H, J=8.5), 7.23 (d, 4H, J=8.5), 7.25-7.5 (complex, 10H); MS (ES+) m/z 653 (MH+).
The more polar product (406 mg), N-(4-benzyloxybenzyl)Lys(Boc)-OMe, was isolated as a white solid; 1 H NMR (CDCl 3 , 300 MHz) 1.4 (, 4H), 1.43 (s, 9H), 1.65 (m, 3H), 3.08 (m, 2H), 3.23 (t, 1H, J=6.5 Hz), 3.54 (d, 1H, J=12.5 Hz), 3.71 (s, 3H), 3.73 (d, 1H, J=12.5 Hz), 5.05 (s, 2H), 6.92 (d, 2H, J=8.5 Hz), 7.23 (d, 2H, J=8.5 Hz), 7.25-7.5 (complex, 5H); MS (ES+) m/z 457 (MH+).
Example 6
N-(4-Benzyloxybenzyl)-N-(3-nitrobenzyl)Lys(Boc)-OMe (cpd 113)
A solution of 374 mg (0.82 mmol) of N-(4-Benzyloxybenzyl)Lys(Boc)-OMe, 221 mg (1.03 mmol) of 4-nitrobenzyl bromide, and 197 L (1.13 mmol, 146 mg) of DIEA was warmed at 50-70° C. for 4 h, then at 40-50° C. overnight. After the addition of 0.2 mL of 1N aqueous HCl, the mixture was partioned between EtOAc and water. The organic layer was washed twice with water, once with brine, and was dried over Na 2 SO 4 . The organic solution was concentrated to give 610 mg of an amber oil which was purified by MPLC 1:3 EtOAc/hexanes to afford 436 mg (90%) cpd 113 as a pale yellow oil; 1 H NMR (CDCl 3 , 300 MHz) 1.35 (m, 4H), 1.42 (s, 9H), 1.75 (broad q, 2H, J=8 Hz), 3.06 (broad q, 2H, J=6 Hz), 3.28 (t, 1H, J=7.5 Hz), 3.48 (d, 1H, J=13.5 Hz), 3.66 (d, 1H, J=14.5 Hz), 3.76 (s, 3H), 3.79 (d, 1H, J=13.5 Hz), 3.97 (d, 1H, J=14.5 Hz), 4.47 (broad s, 1H), 5.05 (s, 2H), 6.93 (d, 2H, J=8.5 Hz), 7.22 (d, 2H, J=8.5 Hz), 7.3-7.5 (complex, 6H), 7.65 (d, 1H, J=7.5 Hz), 8.09 (d, 1H, J=8 Hz), 8.22 (s, 1H); MS (ES+) m/z 592 (MH+).
Example 7
N-(3-Aminobenzyl)-N-(4-benzyloxybenzyl)Lys(Boc)-OMe
A solution of 361 mg (0.61 mmol) of cpd 113 and 835 mg (3.7 mmol) of SnCl 2 dihydrate was stirred under N 2 at room temperature for 6 h. The slightly cloudy mixture was poured into 200 mL of 5% aqueous Na 2 CO 3 with rapid stirring. The resulting milky suspension was extracted with three 75 mL portions of CH 2 Cl 2 and the combined organic layers were washed with brine and dried over Na 2 SO 4 . The extracts were concentrated to give 344 mg of colorless oil which was purified by MPLC using 1:2 EtOAc/hexanes to provide 291 mg of N-(3-aminobenzyl)-N-(4-benzyloxybenzyl)Lys(Boc)-OMe as a yellow oil; 1 H NMR (CDCl 3 , 300 MHz) 1.25 (m, 4H), 1.44 (s, 9H), 1.70 (m, 2H), 3.31 (dd, 1H, J=6, 9 Hz), 3.38 (d, 1H, J=14 Hz), 3.40 (d, 1H, J=13.5 Hz), 3.74 (s, 3H), 3.81 (d, 1H, J=14 Hz), 3.83 (d, 1H, J=13.5 Hz), 4.52 (broad s, 1H), 5.05 (s, 2H), 6.50 (broad d, 1H, J=8 Hz), 6.70 (m, 2H), 6.92 (d, 2H, J=8.5 Hz), 7.08 (t, 1H, J=7.5 Hz), 7.2-7.5 (complex, 7H); MS (ES+) m/z 562 (base, MH+), 506.
Example 8
N-(4-Benzyloxybenzyl)-N-(3-((2-furancarbonyl)amino)benzyl)Lys-OMe (cpd 117)
A solution of 42 mg (0.075 mmol) of N-(3-aminobenzyl)-N-(4-benzyloxybenzyl)Lys(Boc)-OMe and 12 μL (12 mg, 0.15 mmol) of pyridine in 0.5 mL of 1,2-dichloroethane was combined with 8.1 μL (11 mg, 0.083 mmol) and stirred under N 2 overnight. EtOAc (3 mL) was added and the solution was washed twice with 2 mL of water and 2 mL of saturated aqueous NaHCO 3 . The EtOAc solution was filtered through a pad of Na 2 SO 4 and concentrated to give 44 mg of N-(4-benzyloxybenzyl)-N-(3-((2-furancarbonyl)amino)benzyl)Lys(Boc)-OMe; MS (ES+) m/z 356 (MH+). The Boc-protected intermediate was stirred in 2 mL of 50% TFA/CH 2 Cl 2 for 2 h and was concentrated and pumped at high vacuum to provide 66 mg of cpd 117 as the bis-TFA salt; 1 H NMR (CD 3 OD, 300 MHz) 1.55 (m, 2H), 1.65 (m, 2H), 2.10 (m, 2H), 2.93 (t, 2H, J=7 Hz), 3.68 (t, 1H, J=7 Hz), 3.78 (s, 3H), 4.20 (m, 4H), 5.09 (s, 2H), 6.66 (dd, 1H, J=1.5, 3.5 Hz), 7.03 (d, 2H, J=8.5 Hz), 7.1-7.6 (complex, 11H), 7.76 (m, H) 8.07 (m, 1H); MS (ES+) m/z 556 (base, MH+), 360, 197.
Example 9
N,N-bis(3-Nitrobenzyl)Asp(O-t-Bu)-O-t-Bu (cpd 62)
A solution of 0.50 mg (1.77 mmol) of Asp(O-t-Bu)-Ot-Bu.HCl, 1.17 g (5.42 mmol) of 3-nitrobenzyl bromide, and 1.25 mL (0.93 g, 7.2 mmol) of DIEA in 6 mL of DMF was stirred at room temperature under N 2 for 24 h and was heated at 70-80° C. overnight. The reaction mixture was partitioned between EtOAc and water and the organic layer was washed twice with water and once with brine. After drying over Na 2 SO 4 , the organic solution was concentrated to give 0.86 g of a yellow oil which was purified by MPLC using 1:9 EtOAc/hexanes to afford 0.849 g (93%) cpd 62 as a pale yellow oil; 1 H NMR (CDCl 3 , 300 MHz) 1.43 (s, 9H), 1.57 (s, 9H), 2.59 (dd, 1H, J=7.5, 16 Hz), 2.76 (dd, 1H, J=7, 16 Hz), 3.72 (t, 1H, J=7.5 Hz), 3.78 (d, 2H, J=14 Hz), 3.92 (d, 2H, J=14 Hz), 7.47 (t, 2H, J=8 Hz), 7.67 (d, 2H, J=7.5 Hz), 8.09 (broad d, 2H J=8 Hz), 8.16 (broad s, 2H); MS (ES+) m/z 538 (MNa+), 516 (base, MH+), 460, 404, 237.
Example 10
N,N-bis(3-Aminobenzyl)Asp(O-t-Bu)-O-t-Bu
A solution of 0.644 g (1.25 mmol) of cpd 62 and 2.82 g (12.5 mmol) of SnCl 2 .2H 2 O in 12 mL of absolute EtOH was refluxed for 1.5 h. The mixture was cooled and poured into 300 mL of 5% aqueous Na 2 CO 3 with rapid stirring. The cloudy mixture was extracted with three 150 mL portions of CH 2 Cl 2 and the organic extracts were washed with brine and dried over Na 2 SO 4 . The CH 2 Cl 2 solution was concentrated to afford 210 mg (37%) of N,N-bis(3-aminobenzyl)Asp(O-t-Bu)-O-t-Bu as a cloudy yellow oil which was used without purification; 1 H NMR (CDCl 3 , 300 MHz) 1.40 (s, 9H), 1.52 (s, 9H), 2.48 (dd, 1H, J=7, 16 Hz), 2.76 (dd, 1H, J=8, 16 Hz), 3.48 (d, 2H, J=14 Hz), 3.55 (m, 1H), 3.73 (d, 2H, J=14 Hz), 6.56 (broad d, 2H J=8 Hz), 6.70 (broad s, 2H), 6.77 (d, 2H, J=7.5 Hz), 7.08 (t, 2H, J=8 Hz); MS (ES+) m/z 478 (MNa+), 456 (base, MH+), 400, 344.
Example 11
N,N-bis(3-(4-Methylbenzoyl)aminobenzyl)Asp(O-t-Bu)-O-t-Bu
To a solution of 109 mg (0.24 mmol) of N,N-bis(3-aminobenzyl)Asp(O-t-Bu)-O-t-Bu, 29 mg (0.24 mmol) of DMAP, 125 μL (93 mg, 0.72 mmol) of DIEA in 1 mL of CH 2 Cl 2 was added 95 μL (111 mg, 0.72 mmol) of 4-methylbenzoyl chloride. The solution was stirred under N 2 overnight and was then partitioned between EtOAc and water. The organic layer was washed with saturated aqueous NaHCO 3 and brine, dried over Na 2 SO 4 , and concentrated to give 177 mg of yellow oil. The crude material was purified by MPLC using a solvent gradient ranging from 20-25% EtOAc/hexanes to provide 87 mg of N,N-bis(3-(4-methylbenzoyl)aminobenzyl)Asp(O-t-Bu)-O-t-Bu as a pale yellow oil; 1 H NMR (CDCl 3 , 300 MHz) 1.36 (s, 9H), 1.55 (s, 9H), 2.35 (s, 6H), 2.53 (dd, 1H, J=6, 16 Hz), 2.76 (dd, 1H, J=9, 16 Hz), 3.69 (d, 2H, J=14), 3.77 (dd, 1H, J=6, 9 Hz), 3.83 (d, 2H, J=14), 7.01 (m, 6H), 7.26 (t, 2H, J=8 Hz), 7.59 (m, 6H), 8.11 (s, 2H), 8.49 (s, 2H); MS (ES+) m/z 714 (MNa+), 692 (base, MH+), 636, 580.
Example 12
N,N-bis(3-(4-Methylbenzoyl)aminobenzyl)Asp-OH (cpd 64)
A solution of 87 mg (0.13 mmol) of N,N-bis(3-(4-methylbenzoyl)amino-benzyl)Asp(O-t-Bu)-O-t-Bu in 1 mL of 50% TFA/CH 2 Cl 2 was stirred overnight. The mixture was concentrated and the residue was dissolved in HOAc and freeze-dried to afford 77 mg cpd 64 as a white solid; 1 H NMR (CD 3 OD, 300 MHz) 2.40 (s, 6H), 2.85 (dd, 1H, J=6, 16.5 Hz), 2.98 (dd, 1H, J=8, 16.5 Hz), 4.02 (d, 2H, J=13.5 Hz), 4.08 (d, 4H, J=13.5 Hz), 4.10 (t, 1H, J=6.5 Hz), 7.22 (m, 6H), 7.34 (t, 2H, J=7.5 Hz), 7.60 (broad d, 2H, J=9 Hz), 7.76 (d, 4H, J=8 Hz), 7.88 (broad s, 2H); MS (ES+) m/z 580 (base, MH+).
Example 13
[N-Cbz-Glu(O-t-Bu)-NHCH 2 CH 2 OCH 2 ] 2
To a solution of 1.69 g (5.0 mmol) of N-Cbz-Glu(O-t-Bu)-OH, 0.365 mL (0.371 g, 2.5 mmol) of 1,8-diamino-3,6-dioxaoctane, 0.743 g (5.5 mmol) of HOBT, and 1.05 mL (0.776 g, 6.0 mmol) of DIEA in 15 mL of CH 2 Cl 2 was added 1.05 g (5.5 mmol) of EDCI in one portion. After stirring at room temperature under N 2 overnight, the mixture was partitioned between EtOAc and 10% aqueous citric acid. The organic layer was washed with water, saturated NaHCO 3 , and brine, dried over Na 2 SO 4 , and concentrated to give 1.87 g of (N-Cbz-Glu(O-t-Bu)-NHCH 2 CH 2 OCH 2 ) 2 as a colorless oil; 1 H NMR (CD 3 OD, 300 MHz) 1.43 (s, 18H), 1.85 (m, 2H), 2.05 (m, 2H), 2.31 (t, 4H, J=8 Hz), 3.37 (t, 4H, J=5 Hz), 3.52 (t, 4H, J=5 Hz), 3.58 (s, 4H), 4.15 (m, 2H), 5.09 (dd, 4H, J=12, 16 Hz), 7.30 (m, 10H); MS (ES+) m/z 809 (base, MNa+), 787 (MH+).
Example 14
[Glu(O-t-Bu)-NHCH 2 CH 2 OCH 2 ] 2
Ammonium formate (0.78 g, 12.4 mmol) and 0.16 g of 10% palladium on carbon were added to a solution of (N-Cbz-Glu(O-t-Bu)-NHCH 2 CH 2 OCH 2 ) 2 in 12 mL of MeOH and the resulting suspension was stirred under N 2 at room temperature overnight. The mixture was diluted with CH 2 Cl 2 and filtered through a Celite pad. The solids were washed thoroughly with CH 2 Cl 2 and the combined organic filtrates were concentrated to dryness. The residue was partitioned between CH 2 Cl 2 and saturated aqueous NaHCO 3 , washed with brine, dried over Na 2 SO 4 , and concentrated to give 1.13 g of (Glu(O-t-Bu)-NHCH 2 CH 2 OCH 2 ) 2 as a colorless oil; 1.44 (s, 18H), 1.81 (m, 2H), 2.08 (m, 2H), 2.35 (m, 4H), 3.39 (dd, 2H, J=5, 7.5 Hz), 3.47 (t, 4H, J=5 Hz), 3.58 (t, 4H, J=5 Hz), 7.53 (m, 2H).
Example 15
[N,N-bis(4-Benzyloxybenzyl)Glu(O-t-Bu)-NHCH 2 CH 2 OCH 2 ] 2 (cpd 245)
A solution of 199 mg (0.384 mmol) of [Glu(O-t-Bu)-NHCH 2 CH 2 OCH 2 ] 2 , 403 mg (1.73 mmol) of 4-benzyloxybenzyl chloride, 30 mg (0.2 mmol) of NaI, and 334 L (248 mg, 1.92 mmol) of DIEA was stirred under N 2 at room temperature for several days. The solution was partitioned between EtOAc and water and the organic layer was washed three times with water and once with brine. After drying over Na 2 SO 4 , the solution was concentrated to give 528 mg of yellow oil which was purified by MPLC using a solvent gradient ranging from 42-50% EtOAc/hexanes to afford 318 mg (64%) of cpd 245 as a white foam; 1 H NMR (CDCl 3 , 300 MHz) 1.42 (s, 18H), 2.01 (m, 4H), 2.38 (m, 2H), 2.55 (m, 2H), 3.03 (dd, 2H, J=5, 8 Hz), 3.31 (m, 2H), 3.4-3.6 (complex, 18H), 4.99 (s, 8H), 6.89 (d, 8H, J=8.5), 7.1-7.4 complex, 30H).
Example 16
[N,N-bis(4-Benzyloxybenzyl)GluNHCH 2 CH 2 OCH 2 ] 2 (cpd 246)
A solution of 219 mg (0.168 mmol) of cpd 245 in 2 mL of 33% TFA/CH 2 Cl 2 was stirred ad room temperature overnight. The mixture was concentrated to give a crude product which was dissolved in HOAc and freeze-dried to afford 251 mg of cpd 246 as an amber oil; 1 H NMR (CD 3 OD, 300 MHz) 2.1-2.6 (complex, 8H), 3.3-3.6 (complex, 8H), 3.57 (s, 4H), 3.78 (m, 2H), 4.25 (broad d, 4H, J=14 Hz), 4.36 (broad d, 4H, J=14 Hz), 5.09 (s, 8H), 7.03 (d, 8H, J=8 Hz), 7.3-7.5 (complex, 28H); MS (ES+) m/z 1192 (MH+), 995, 596, 197 (base).
Example 17
[N-(3-Phenoxybenzyl)Glu(O-t-Bu)-NHCH 2 CH 2 OCH 2 ]2
A solution of 680 mg (0.76 mmol) of [Glu(O-t-Bu)-NHCH 2 CH 2 OCH 2 ] 2 and 278 μL (317 mg, 1.6 mmol) of 3-phenoxybenzaldehyde in 3 mL of TMOF was stirred overnight at room temperature under N 2 . The mixture was concentrated and pumped at high vacuum to give a colorless oil which was dissolved in 3 mL of CH 2 Cl 2 and treated with 678 mg (3.2 mmol) of NaBH(OAc) 3 . After stirring under N 2 for 2 days, 50 mL of saturated aqueous NaHCO 3 was added and the mixture was extracted with CH 2 Cl 2 . The organic layers were combined, dried over Na 2 SO 4 , and concentrated and the crude product (1.01 g) was purified by MPLC using a solvent gradient ranging from 2-4% MeOH/CH 2 Cl 2 to afford 490 mg of [N-(3-phenoxybenzyl)Glu(O-t-Bu)-NHCH 2 CH 2 OCH 2 ] 2 as a colorless oil; 1 H NMR (CDCl 3 , 300 MHz) 1.41 (s, 18H), 1.89 (m, 4H), 2.31 (m, 4H), 3.12 (t, 2H, J=6 Hz), 3.45 (m, 8H), 3.55 (s, 4H), 3.60 (d, 2H, J=13.5 Hz), 3.73 (d, 2H, J=13.5 Hz), 6.86 (dd, 2H, J=1.5, 8 Hz), 7.00 (m, 8H), 7.2-7.4 (complex, 8H); MS (ES+) m/z 883 (MH+), 589, 442, 414, 386 (base), 183.
Example 18
[N-(3-Nitrobenzyl)-N-(3-phenoxybenzyl)-Glu(O-t-Bu)-NHCH 2 CH 2 OCH 2 ] 2
DIEA (269 μL, 199 mg, 1.54 mmol), 3-nitrobenzyl bromide (322 mg, 1.49 mmol), and [N-(3-phenoxybenzyl)Glu(O-t-Bu)-NHCH 2 CH 2 OCH 2 ] 2 (482 mg, 0.546 mmol) were combined in 2 mL of DMF and heated at 60-70° C. under N 2 for 2 days. The reaction mixture was cooled and partitioned between 100 mL of EtOAc and water. The organic layer was washed with three times with water and once with brine, dried over Na 2 SO 4 , and concentrated to give 661 mg (˜100%) of [N-(3-nitrobenzyl)-N-(3-phenoxybenzyl)-Glu(O-t-Bu)-NHCH 2 CH 2 OCH 2 ] 2 which was used without purification; MS (ES+) m/z 1154 (MH+), 577, 130 (base).
Example 19
[N-(3-Aminobenzyl)-N-(3-phenoxybenzyl)-Glu(O-t-Bu)-NHCH 2 CH 2 OCH 2 ] 2
A solution of 661 mg (0.54 mmol) of crude [N-(3-nitrobenzyl)-N-(3-phenoxybenzyl)-Glu(O-t-Bu)-NHCH 2 CH 2 OCH 2 ] 2 and 2.71 g (12.0 mmol) of SnCl 2 . 2H 2 O in 20 mL of absolute EtOH was refluxed under N 2 for 30 min. The cooled solution was poured into 500 mL of 2.5% aqueous Na 2 CO 3 with rapid stirring and the resulting cloudy mixture was extracted thoroughly with EtOAc. The slightly cloudy organic extracts were washed twice with brine, dried over Na 2 SO 4 , anc concentrated to give 604 mg of yellow oil which was purified by MPLC using 3% MeOH/CH 2 Cl 2 to provide 350 mg (59%) of [N-(3-aminobenzyl)-N-(3-phenoxybenzyl)-Glu(O-t-Bu)-NHCH 2 CH 2 OCH 2 ] 2 as a pale yellow oil; 1 H NMR (CDCl 3 , 300 MHz) 1.41 (s, 18H), 1.97 (m, 4H), 2.25 (m, 4H), 2.48 (m, 4H), 3.03 (dd, 2H, J=5, 8 Hz), 3.30 (m, 2H), 3.4-3.8 (complex, 24H), 6.47 (d, 2H, J=7.5 Hz), 6.65 (m, 4H), 6.85 (d, 2H, J=9.5 Hz), 6.9-7.15 (complex, 12H), 7.2-7.4 (complex, 8H); MS (ES+) m/z 1094 (MH+), 547 (base).
Example 20
[N-(3-Phenoxybenzyl)-N-(3-(pentanoylamino)benzyl)-Glu-NHCH 2 CH 2 OCH 2 ] 2 (cpd 247)
Pentanoyl chloride (16 uL, 16 mg, 0.136 mmol) was added dropwise to a solution of 68 mg (0.062 mmol) of [N-(3-aminobenzyl)-N-(3-phenoxybenzyl)-Glu(O-t-Bu)-NHCH 2 CH 2 OCH 2 ] 2 , 20 μL (20 mg, 0.25 mmol) of pyridine in 0.3 mL of 1,2-dichloroethane. The mixture was shaken under N 2 overnight and was then partitioned between EtOAc and water. The organic layer was washed with saturated aqueous NaHCO 3 , dried over Na 2 SO 4 , and concentrated to give 77 mg of [N-(3-phenoxybenzyl)-N-(3-(pentanoylamino)benzyl)-Glu(O-t-Bu)-NHCH 2 CH 2 OCH 2 ] 2 ; MS (ES+) m/z 1073, 575 (base, MH+/2). The crude product was dissolved in 1 mL of 50% TFA/CH 2 Cl 2 and allows to stand overnight. The solution was concentrated and the resulting oil was dissolved in HOAc and freeze-dried to provide 82 mg of cpd 247; 1 H NMR (CD 3 OD, 300 MHz) 3.98 (t, 6H, J=7.5 Hz), 1.39 (sextet, 4H, J=7.5 Hz), 1.66 (quintet, 4H, J=7.5 Hz), 1.65 (m, 2H), 1.78 (m, 2H), 2.35 (t, 4H, J=7.5 Hz), 2.45 (m, 4H), 3.38 (m, 4H), 3.50 (t, 2H, J=5), 3.57 (m, 4H), 4.10 (broad s, 8H), 6.9-7.25 (complex, 14H), 7.25-7.4 (complex, 10H), 7.71 (s, 2H); MS (ES+) m/z 1150 (MH+), 575 (base).
Example 21
[N-Cbz-Lys(Boc)-NHCH 2 CH 2 ] 3 N
A solution of 1.0 g (2.63 mmol) of N-Cbz-Lys(Boc)OH, 0.131 mL (0.128 g, 0.876 mmol) of tris(2-aminoethyl)amine, 0.391 g (2.98 mmol) of HOBt, 0.555 g (2.89 mmol) of EDCI, and 0.55 mL (0.408 g, 3.16 mmol) of DIEA in 5 mL of CH 2 Cl 2 was stirred under N 2 at room temperature overnight. The mixture was diluted with EtOAc and washed with 10% aqueous citric acid, saturated aqueous NaHCO 3 , and brine. The solution was dried over Na 2 SO 4 and concentrated to give 0.872 g of [N-Cbz-Lys(Boc)-NHCH 2 CH 2 ] 3 N as an off-white solid; 1 H NMR (CD 3 OD, 300 MHz) 135 (m, 12H), 1.40 (s, 27H), 1.60 (m, 3H), 1.72 (m, 3H), 2.51 (m, 6H), 2.99 (m, 6H), 3.10 (m, 3H), 3.21 (m, 3H), 4.12 (m, 3H), 5.00 (d, 3H, J=12.5 Hz), 5.08 (d, 3H, J=12.5 Hz), 7.29 (m, 15H); MS (ES+) m/z 1243 (base, MH+), 567, 467.
Example 22
[Lys(Boc)-NHCH 2 CH 2 ] 3 N
A solution of 0.841 g (0.682 mmol) [N-Cbz-Lys(Boc)-NHCH 2 CH 2 ] 3 N, 0.252 g of 10% Pd—C, and 0.774 g (12.3 mmol) of ammonium formate in 10 mL of MeOH was stirred for 5 h at room temperature under N 2 . The mixture was filtered through a Celite pad, the solids were washed with CH 2 Cl 2 , and the reslulting solution was concentrated to dryness. The residue was partitioned between CH 2 Cl 2 and brine; the organic layer was dried over Na 2 SO 4 and concentrated to provide 0.191 g of [Lys(Boc)-NHCH 2 CH 2 ] 3 N as an off-white solid; 1 H NMR (CD 3 OD, 300 MHz) 1.40 (s, 27H), 1.45 (m, 12H), 1.75 (m, 6H), 2.62 (m, 6H), 3.01 (m, 6H), 3.28 (m, 6H), 3.64 (m, 3H); MS (ES+) m/z 853 (MNa+), 831 (MH+), 266 (base).
Example 23
[N,N-bis(3-Phenoxybenzyl)Lys(Boc)-NHCH 2 CH 2 ] 3 N
A solution of 65 mg (0.078 mmol) of [Lys(Boc)-NHCH 2 CH 2 ] 3 N, 120 μL (140 mg, 0.70 mmol) of 3-phenoxybenzaldehyde, and 71 μL (65 mg, 0.70 mmol) of borane-pyridine complexin 3 mL of absolute EtOH was stirred for 4 days at room temperature under N 2 . The mixture was concentrated to dryness and partitioned between water and CH 2 Cl 2 . The organic layer was concentrated to give a yellow oil which was purified by MPLC using 2.5% MeOH/CH 2 Cl 2 to give 78 mg of [N,N-bis(3-phenoxybenzyl)Lys(Boc)-NHCH 2 CH 2 ] 3 N as a yellow oil; MS (ES+) m/z 872 (base, [M—C 13 H 12 O)/2]+), 611, 443.
Example 24
[N,N-bis(3-Phenoxybenzyl)Lys-NHCH 2 CH 2 ] 3 N (cpd 277)
A solution of 78 mg (0.048 mmol) of [N,N-bis(3-phenoxybenzyl)Lys(Boc)-NHCH 2 CH 2 ] 3 N in 2 mL of 50% TFA/CH 2 Cl 2 was stirred for 2 h at room temperature. The mixture was diluted with CH 2 Cl 2 , washed with water and 5% Na 2 CO 3 , and concentrated to give 57 mg of cpd 277 as an off-white foam; 1 H NMR (CD 3 OD, 300 MHz) 1.35 (m, 6H), 1.52 (m, 6H), 1.76 (m, 6H), 2.75 (m, 6H), 3.19 (m, 6H), 3.40 (m, 6H), 3.60 (m, 9H), 3.77 (m, 6H), 6.79 (d, 6H, J=8 Hz), 693 (m, 24H), 7.05 (m, 6H), 7.19 (m, 6H), 7.29 (m, 12H); MS (ES+) m/z 813 ([MH 2 /2]+), 721, 542 (base, [MH/3]+).
Example 25
N,N-bis(3-Phenoxycinnamyl)Ser(t-Bu)-OMe (cpd 290) and N-(3-phenoxycinnamyl)Ser(t-Bu)-OMe (cpd 352)
A solution of 423 mg (2.0 mmol) of H-Ser(t-Bu)OMe.HCl, 1.01 g (3.5 mmol) of 3-phenoxycinnamyl bromide (Jackson, W. P.; Islip, P. J.; Kneen, G.; Pugh, A.; Wates, P. J. J.Med.Chem. 31 1988; 499-500), and 0.87 mL (5.0 mmol, 650 mg) of DIEA in 6 mL of DMF was stirred under N 2 at room temperature for 20 h. The mixture was partitioned between EtOAc and water and the organic layer was washed with water and brine. After drying over Na 2 SO 4 , the organic solution was concentrated to give 0.98 g of yellow oil. The crude residue was purified by MPLC using a solvent gradient ranging from 10-30% EtOAc/hexanes to give two products. The less polar product (168 mg, 14% based on starting amino acid), N,N-bis(3-phenoxycinnamyl)Ser(t-Bu)-OMe (cpd 290), was isolated as a pale yellow oil; 1 H NMR (CDCl 3 , 300 MHz) 1.15 (s, 9H), 3.35 (dd, 2H, J=7, 14.5 Hz), 3.53 (dd, 2H, J=5.5, 14.5 Hz), 3.6-3.8 (complex, 3H), 3.69 (s, 3H), 6.18 (dt, 2H, J=16, 6.5 Hz), 6.49 (d, 2H, J=16 Hz), 6.86 (dd, 2H, J=2, 8 Hz), 6.9-7.4 (complex, 16H); MS (ES+) m/z 614, 592 (MH+, base), 406, 384, 209.
The more polar product (354 mg, 46% based on starting amino acid), N-(3-phenoxycinnamyl)Ser(t-Bu)-OMe (cpd 352), was isolated as a pale yellow oil; 1 H NMR (CDCl 3 , 300 MHz) 1.15 (s, 9H), 1.98 (broad s, 1H), 3.32 (ddd, 1H, J=1.2, 6.5, 14 Hz), 3.4-3.7 (complex, 4H), 3.72 (s, 3H), 6.21 (dt, 1H, J=16, 6.5 Hz), 6.48 (d, 1H, J=16 Hz), 6.88 (dd, 1H, J=1.5, 8 Hz), 7.0-7.4 (complex, 8H); MS (ES+) m/z 789 (2M+Na+), 384 (MH+, base), 209.
Example 26
N,N-Bis(3-phenoxycinnamyl)Ser-OMe (cpd 299)
N,N-Bis(3-phenoxycinnamyl)Ser(t-Bu)-OMe (cpd 290, 168 mg, 0.284 mmol) was stirred in 3 mL of 50% TFA/CH 2 Cl 2 under N 2 overnight. The solvent was removed using a rotary evaporator and the crude residue was partitioned between EtOAc and saturated aqueous NaHCO 3 . After washing with brine and drying over Na 2 SO 4 , the organic layer was concentrated using a rotary evaporator and the crude product (134 mg) was purified by MPLC using 30% EtOAc/hexanes to give 44 mg (29%) of N,N-bis(3-phenoxycinnamyl)Ser-OMe (cpd 299) as a colorless oil; 1 H NMR (CDCl 3 , 300 MHz) 1.6 (broad s, 2H), 3.38 (dd, 2H, J−8, 12 Hz), 3.4-3.9 (complex, 5H), 3.72 (s, 3H), 6.13 (dt, 2H, J=16, 7 Hz), 6.50 (d, 2H, J=16 Hz), 6.8-7.4 (complex, 18H); MS (ES+) m/z 536 (MH+).
Example 27
N,N-Bis(3-phenoxycinnamyl)Ser-OH (cpd 300)
N,N-Bis(3-phenoxycinnamyl)Ser-OMe (cpd 299, 44 mg, 0.082 mmol) was dissolved in 0.2 mL of MeOH and was stirred with 0.090 mL of 1N aqueous NaOH. When TLC analysis revealed that starting material had been consumed, the solvent was removed by rotary evaporation and the residue was lyophilized from acetic acid to give 42 mg (88%) of N,N-bis(3-phenoxycinnamyl)Ser-OH acetate (cpd 300) as a sticky yellow solid; 1 H NMR (methanol-d 4 , 300 M) 1.97 (s, 3H), 3.3-4.2 (complex, 7H), 6.80 (d, 2H, J=16 Hz), 6.9-7.4 (complex, 18H); MS (ES+) m/z 522 (MH+), 209.
Example 28
N-(3-Phenoxycinnamyl)Ser-OMe (cpd 346)
N-(3-Phenoxycinnamyl)Ser(t-Bu)-OMe (cpd 352, 268 mg, 0.699 mmol) was stirred in 3 mL of 50% TFA/CH 2 Cl 2 under N 2 overnight. The solvent was removed using a rotary evaporator and the crude residue (256 mg) was purified by MPLC using EtOAc to give 137 mg (60%) of N-(3-phenoxycinnamyl)Ser-OMe (cpd 346) as a colorless oil; 1 H NMR (CDCl 3 , 300 MHz) 2.2 (broad s, 2H), 3.36 (dd, 1H, J=6, 14 Hz), 3.4-3.5 (complex, 2H), 3.62 (dd, 1H, J=6.5, 11 Hz), 3.74 (s, 3H), 3.80 (dd, 1H, J=4.5, 11 Hz). 6.19 (dt, 1H, J=16, 6.5 Hz), 6.48 (d, 1H, J=6 Hz), 6.88 (dd, 1H, J=1.5, 8 Hz), 7.0-7.4 (complex, 8H); MS (ES+) m/z 677 (2M+Na+), 350 (M+Na+), 328 (MH+), 209 (base).
Example 29
N-(3-phenoxycinnamyl)Ser-OH (cpd 347)
N-(3-Phenoxycinnamyl)Ser-OMe (cpd 346, 110 mg, 0.336 mmol) was dissolved in 1.5 mL of MeOH and was stirred with 0.50 mL of 1N aqueous NaOH. When TLC analysis revealed that starting material had been consumed, the solvent was removed by rotary evaporation. The residue was dissolved in water and acidified to pH 7-8 with 1N aqueous HCl; the resulting solids were filtered, washed with water, and dried to give 71 mg of white powder. The insoluble powder was dissolved in TFA and, after removal of excess TFA by rotary evaporation, lyophilized from acetic acid to give 82 mg (57%) of N-(3-phenoxycinnamyl)Ser-OH trifluoroacetate (cpd 347) as an amber oil; 1 H NMR (methanol-d 4 , 300 MHz) 3.88 (d, 2H, J=7H), 4.0-4.2 (complex, 3H), 6.27 (dt, 1H, J=16, 6.5), 6.83 (d, 1H, J=16 Hz), 6.9-7.4 (complex, 9H); MS (ES+) m/z 314, (MH+), 209.
Example 30
N-(3-Phenoxycinnamyl)Glu(O-t-Bu)-OH (cpd 337)
A mixture of 249 mg (0.585 mmol) of N-(3-phenoxycinnamyl)Glu(O-t-Bu)-OMe (cpd 334) in 3 mL of MeOH was sonicated to speed dissolution, and the resulting solution was treated with 0.585 mL of 1N aqueous NaOH. After stirring overnight, the MeOH was removed using a rotary evaporator and the residue was dissolved in water. Acidification with 0.64 mL of 1N aqueous HCl produced a 250 mg of solid material that was triturated with Et 2 O to give 111 mg (46%) of N-(3-phenoxycinnamyl)Glu(O-t-Bu)-OH (cpd 337) as a white solid; 1 H NMR (300 MHz, methanol-d 4 ) 1.43 (s, 9H), 1.9-2.2 (complex, 2H), 2.46 (t, 2H, J=7 Hz), 3.57 (dd, 1H, J=5, 7 Hz), 3.78 (dd, 1H, J=7, 13.5 Hz), 3.82 (dd, 1H, J=7, 13.5 Hz), 6.28 (dt, 1H, J=16, 7 Hz), 6.81 (d, 1H, J=16 Hz), 6.9-7.5 (complex, 9H); MS (ES+) m/z 412 (MH+, base), 356, 209. Anal. Calcd for C 24 H 29 NO 5 .0.4 H 2 O: C, 68.55; H, 7.04; N, 3.24. Found: C, 68.89; H, 7.04; N, 3.24.
Example 31
N-(3-Phenoxycinnamyl)Glu-OH (cpd 326)
A mixture of 85 mg (0.21 mmol) of N-(3-phenoxycinnamyl)Glu(O-t-Bu)-OH (cpd 337) in was stirred in 1 mL of 50% TFA/CH 2 Cl 2 for 1 h. After solvent removal using a rotary evaporator, the residue was dissolved in acetic acid and freeze-dried to give 75 mg (76%) of N-(3-phenoxycinnamyl)Glu-OH tifluoroacetate (cpd 326) as a fluffy white solid; 1 H NMR (300 MHz, methanol- 4 ) 2.0-2.4 (complex, 2H), 2.55 (m, 2H), 3.84 (d, 2H, J=7 Hz), 3.96 (dd, 1H, J=5, 7 Hz, 6.24 (dt, 1H, J=16, 7 Hz), 6.84 (d, 1H, J=16 Hz), 6.9-7.4 (complex, 9H); MS (ES+) m/z 356 (MH+), 209 (base).
TABLE 2
R 1 (amino
cpd
% inh
acid side chain)
R 2
R 3
W, Q
11
70
Asn, Asp, Gln, Glu
3-PhO
CH═CH
12
59
Cys, Met, Ser, Thr
3-PhO
CH═CH
13
nd
Arg, Gly, His, Pro
3-PhO
CH═CH
14
30
Lys(2-Cl—Cbz),
3-PhO
CH═CH
Phe, Trp, Tyr
15
48
Ala, Ile, Leu, Val
3-PhO
CH═CH
16
nd
Glu, Asp
2,3-benzo
CH═CH
17
nd
Cys, Met
2,3-benzo
CH═CH
18
nd
Ser, Thr
2,3-benzo
CH═CH
19
nd
His, Arg(Mtr)
2,3-benzo
CH═CH
20
nd
Pro, Gly
2,3-benzo
CH═CH
21
nd
Phe, Tyr
2,3-benzo
CH═CH
22
nd
Trp,
2,3-benzo
CH═CH
Lys(2-Cl—Cbz)
23
nd
Ile, Ala
2,3-benzo
CH═CH
24
nd
Val, Leu
2,3-benzo
CH═CH
25
nd
Asn, Lys
2,3-benzo
CH═CH
26
nd
Ala, Ile
3,4-benzo
CH═CH
27
nd
Arg(Mtr),
3,4-benzo
CH═CH
Lys(2-Cl—Cbz)
28
nd
Asp, Glu
3,4-benzo
CH═CH
29
nd
Cys, Met
3,4-benzo
CH═CH
30
nd
Gly, Pro
3,4-benzo
CH═CH
31
nd
His, Lys
3,4-benzo
CH═CH
32
nd
Leu, Val
3,4-benzo
CH═CH
33
nd
Lys(2-Cl—Cbz),
3,4-benzo
CH═CH
Phe
34
nd
Ser, Thr
3,4-benzo
CH═CH
35
nd
Trp, Tyr
3,4-benzo
CH═CH
TABLE 3
EPO/EBP-Ig
cpd
% inh @ 50 μM
R 1
R 2
R 9
W, Q
MS MH+
36
nd
CH 3
4-CF 3
H
CH═CH
458
37
19
H
4-CF 3
H
CH═CH
430
38
nd
(CH 2 ) 4 NH(2-Cl—Cbz)
4-F
H
CH═CH
448
40
nd
CH 3
4-F
H
CH═CH
223
41
nd
CH 2 CO 2 H
4-F
H
CH═CH
266
42
nd
CH 2 CH 2 CO 2 H
4-F
H
CH═CH
281
43
nd
(CH 2 ) 3 NHC(═NH)NH 2
4-F
H
CH═CH
308
45
nd
PhCH 2
4-F
H
CH═CH
299
46
nd
4-HO—PhCH 2
4-F
H
CH═CH
315
47
nd
CH 2 OH
4-F
H
CH═CH
238
48
nd
CH(OH)CH 3
4-F
H
CH═CH
253
49
1
(CH 2 ) 3 NHC(═NH)NH 2
H
H
S
419
50
−6
(CH 2 ) 4 NH 2
H
H
S
391
51
nd
CH(CH 3 )CH 2 CH 3
H
H
S
376
52
21
CH 2 CH 2 CO 2 H
H
H
S
392
53
14
CH 2 CO 2 H
H
H
S
378
54
18
CH 3
H
H
S
334
55
4
CH 2 CH 2 CONH 2
H
H
S
391
56
nd
(CH 2 ) 4 NHCbz
H
Me
S
539
57
0
(CH 2 ) 4 NHCbz
H
CH 2 Ph
S
615
58
nd
CH 2 (indol-3-yl)
H
Me
S
463
59
26
CH 2 CH 2 CO 2 -t-Bu
H
Me
S
462
60
9
CH 2 CH 2 CO 2 Et
H
Me
S
434
61
14
CH 2 CH 2 CO 2 H
H
Me
S
406
TABLE 4
EPO/EBP-Ig
cpd
% inh @ 50 μM
R a
R 2
R 4
R 9
MS, MH+
62
nd
t-Bu
NO 2
NO 2
t-Bu
516
63
20
H
PhCH 2 NH
PhO
H
511
64
−4
H
4-MePhCONH
4-MePhCONH
H
580
65
−7
H
4-MePhSO 2 NH
4-MePhSO 2 NH
H
652
66
−16
H
3-ClPhCH 2 NH
PhO
H
546
67
−8
H
3-BrPhCH 2 NH
PhO
H
590
68
−13
H
2-FPhCH 2 NH
PhO
H
529
69
−13
H
2-MePhCH 2 NH
PhO
H
525
70
−8
H
4-FPhCH 2 NH
PhO
H
529
71
−6
H
3-ClPhCH 2 NH
4-Me—PhO
H
560
72
−14
H
F 5 —PhCH 2 NH
4-Me—PhO
H
615
73
−13
H
2-FPhCH 2 NH
4-Me—PhO
H
543
74
−7
H
3-CNPhCH 2 NH
4-Me—PhO
H
550
75
−2
H
PhCH 2 NH
4-Me—PhO
H
525
TABLE 5
EPO/EBP-Ig
MS,
cpd
% inh @ 50 μM
R a
R 2
R 3
R 4
R 5
R 9
n
MH+
76
25
t-Bu
PhO
H
PhO
H
t-Bu
1
636
77
52
H
PhO
H
PhO
H
H
1
524
78
nd
H
H
4-MePhCONH
H
BnO
H
2
593
79
nd
H
H
n-BuCONH
H
BnO
H
2
559
80
nd
H
H
2-naphthyl CONH
H
BnO
H
2
629
81
nd
H
H
2-furyl CONH
H
BnO
H
2
569
82
32
H
H
4-MeO—PhCONH
H
BnO
H
2
609
83
18
H
H
HO 2 C(CH 2 ) 3 CONH
H
BnO
H
2
589
84
14
H
H
C 2 F 5 CONH
H
BnO
H
2
621
85
20
H
H
CF 3 CONH
H
BnO
H
2
571
86
37
H
H
4-pyridyl-CONH
H
BnO
H
2
580
87
23
H
H
4-MePhSO 2 NH
H
BnO
H
2
629
88
10.3
H
H
HO 2 CCH 2 (1,1-
H
BnO
H
2
643
cyclopentyl)
CH 2 CONH
89
22
H
H
PhOCONH
H
BnO
H
2
595
90
29
H
H
4-Ph—PhCONH
H
BnO
H
2
655
91
19
H
H
4-NO 2 —PhCONH
H
BnO
H
2
624
TABLE 6
EPO/EBP-Ig
MS,
cpd
% inh @ 50 μM
R a
R 2
R 3
R 4
R 5
R 6
R 9
MH+
92
20
H
H
H
H
H
2
Me
394
93
20
t-Bu
H
H
H
H
2
Me
450
94
25
Et
H
H
H
H
2
Me
422
95
15
t-Bu
2,3-benzo
2,3-benzo
2
Me
550
96
−5
t-Bu
PhO
H
PhO
H
2
Me
634
97
14
t-Bu
3,4-benzo
3,4-benzo
2
H
536
98
12
t-Bu
H
Ph
H
Ph
2
Me
602
99
13
t-Bu
3,4-di-Cl—PhO
H
3,4-di-Cl—PhO
H
2
Me
772
100
34
H
H
Ph
H
Ph
2
Me
546
101
32
H
3,4-di-Cl—PhO
H
3,4-di-Cl—PhO
H
2
Me
716
102
5
t-Bu
4-t-Bu—PhO
H
4-t-Bu—PhO
H
2
t-Bu
789
103
17
t-Bu
3-CF3—PhO
H
3-CF3—PhO
H
2
t-Bu
812
104
78
H
4-t-Bu—PhO
H
4-t-Bu—PhO
H
2
H
676
105
70
H
3-CF3—PhO
H
3-CF3—PhO
H
2
H
700
106
20
t-Bu
PhO
H
PhO
H
1
t-Bu
662
107
78
H
PhO
H
PhO
H
2
H
562*
108
81
H
PhO
H
PhO
H
1
H
550
*[M − H] −
TABLE 7
EPO/
EBP-Ig
% inh
@ 50
MS,
cpd
μM
R a
R 2
R 3
R 4
R 5
R 9
MH+
109
7
Boc
BnO
H
BnO
H
Me
653
110
54
H
H
BnO
H
BnO
Me
553
111
5
Boc
H
BnO
H
BnO
Me
653
112
59
H
BnO
H
BnO
H
Me
553
113
24
Boc
H
BnO
NO 2
H
Me
592
114
37
H
H
BnO
NO 2
H
Me
492
115
35
H
H
BnO
NH 2
H
Me
462
116
32
H
H
BnO
n-BuCONH
H
Me
546
117
34
H
H
BnO
2-furylCONH
H
Me
556
118
36
H
H
BnO
4-MePhCONH
H
Me
580
119
34
H
H
BnO
i-Pr—CONH
H
Me
532
120
35
H
H
BnO
4-pyridyl-
H
Me
567
CONH
121
45
H
H
BnO
2-naphthyl-
H
Me
616
CONH
122
nd
Boc
PhCH 2 NH
H
PhCH 2 NH
H
Me
651
123
nd
Boc
2-MePhCH 2 NH
H
2-MePhCH 2 NH
H
Me
679
124
nd
Boc
4-MeO—PhCH 2 NH
H
4-MeO—PhCH 2 NH
H
Me
711
125
nd
Boc
3,4-di-MeO—PhCH 2 NH
H
3,4-di-MeO—PhCH 2 NH
H
Me
771
126
nd
Boc
—NH 2
H
—NH 2
H
Me
417
127
nd
H
PhCH 2 NH
H
PhCH 2 NH
H
Me
551
128
nd
H
2-MePhCH 2 NH
H
2-MePhCH 2 NH
H
Me
579
129
nd
H
4-MeO—PhCH 2 NH
H
4-MeO—PhCH 2 NH
H
Me
611
130
nd
H
3,4-di-MeO—PhCH 2 NH
H
3,4-di-MeO—PhCH 2 NH
H
Me
671
131
nd
H
PhCH 2 CH 2 NH
H
PhCH 2 CH 2 NH
H
Me
579
132
nd
HO 2 CCH 2 CH 2 CO
PhCH 2 NH
H
PhCH 2 NH
H
Me
651
133
nd
HO 2 CCH 2 CH 2 CO
2-MePhCH 2 NH
H
2-MePhCH 2 NH
H
Me
679
134
nd
HO 2 CCH 2 CH 2 CO
4-MeO—PhCH 2 NH
H
4-MeO—PhCH 2 NH
H
Me
711
135
nd
HO 2 CCH 2 CH 2 CO
3,4-di-MeO—PhCH 2 NH
H
3,4-di-MeO—PhCH 2 NH
H
Me
771
136
nd
HO 2 CCH 2 CH 2 CO
PhCH 2 CH 2 NH
H
PhCH 2 CH 2 NH
H
Me
679
TABLE 8
EPO/EBP-Ig
MS,
cpd
% inh @ 50 μM
R a
R 2
R 4
R 5
R 9
MH+
137
nd
H
PhO
PhO
H
Me
551
138
nd
Boc
4-t-Bu—PhO
BnO
H
Me
721
139
nd
H
4-t-Bu—PhO
BnO
H
Me
621
140
nd
H
(CF 3 CO) 2 N
BnO
H
H
666
141
nd
H
PhCONH
BnO
H
H
578
142
nd
H
4-pyridyl-CONH
BnO
H
H
579
143
nd
H
(CF 3 CO) 2 N
PhO
H
H
652
144
nd
H
PhCONH
PhO
H
H
564
145
nd
H
4-pyridyl-CONH
PhO
H
H
565
146
nd
H
(CF 3 CO) 2 N
MeO
MeO
H
620
147
nd
H
PhCONH
MeO
MeO
H
532
148
nd
H
4-pyridyl-CONH
MeO
MeO
H
533
149
nd
H
(CF 3 CO) 2 N
H
PhO
H
652
150
nd
H
PhCONH
H
PhO
H
564
151
nd
H
4-pyridyl-CONH
H
PhO
H
565
152
nd
H
PhCONH
H
BnO
H
578
153
nd
H
4-pyridyl-CONH
H
BnO
H
579
154
nd
H
(CF 3 CO) 2 N
H
BnO
H
666
155
nd
HO 2 CCH 2 CH 2 CO
4-MeO—PhCONH
PhO
H
H
694
156
nd
HO 2 CCH 2 CH 2 CO
PhCONH
PhO
H
H
664
157
nd
HO 2 CCH 2 CH 2 CO
2-naphthyl-
PhO
H
H
714
CONH
158
nd
HO 2 CCH 2 CH 2 CO
4-Me—PhSO 2 NH
PhO
H
H
714
159
nd
HO 2 CCH 2 CH 2 CO
4-MeO—PhCONH
2,3-
H
652
benzo
160
nd
HO 2 CCH 2 CH 2 CO
PhCONH
2,3-
H
622
benzo
161
nd
HO 2 CCH 2 CH 2 CO
2-naphthyl-
2,3-
H
672
CONH
benzo
162
nd
HO 2 CCH 2 CH 2 CO
4-Me—PhSO 2 NH
2,3-
H
672
benzo
163
nd
HO 2 CCH 2 CH 2 CO
4-MeO—PhCONH
H
F
H
620
164
nd
HO 2 CCH 2 CH 2 CO
PhCONH
H
F
H
590
165
nd
HO 2 CCH 2 CH 2 CO
2-naphthyl-
H
F
H
640
CONH
166
nd
HO 2 CCH 2 CH 2 CO
4-Me—PhSO 2 NH
H
F
H
640
167
nd
HO 2 CCH 2 CH 2 CO
4-MeO—PhCONH
BnO
H
H
708
168
nd
HO 2 CCH 2 CH 2 CO
PhCONH
BnO
H
H
678
169
nd
HO 2 CCH 2 CH 2 CO
2-naphthyl-
BnO
H
H
728
CONH
170
nd
HO 2 CCH 2 CH 2 CO
4-Me—PhSO 2 NH
BnO
H
H
728
TABLE 9
EPO/
EBP-Ig
% inh
@ 50
MS,
cpd
μM
R a
R 2
R 3
R 4
R 5
R 9
MH+
171
nb
Cbz
H
H
H
H
Me
527
172
15
Cbz
H
H
H
H
H
513
173
5
Cbz
H
H
H
H
t-Bu
569
174
23
Cbz
H
MeO
H
MeO
Me
587
175
1
Cbz
3,4-
3,4-
Me
627
benzo
benzo
176
−4
Cbz
PhO
H
PhO
H
Me
711
177
nd
Cbz
2,3-benzo
2,3-benzo
Me
627
178
36
Boc
H
NO 2
H
NO 2
Me
583
179
30
Boc
H
NO 2
H
NO 2
H
569
180
−4
Boc
PhO
H
PhO
H
Me
677
181
−9
Boc
4-t-Bu—PhO
H
4-t-Bu—PhO
H
Me
790
182
18
H
4-t-Bu—PhO
H
4-t-Bu—PhO
H
Me
689
183
36
Boc
NO 2
H
NO 2
H
Me
583
184
53
H
NO 2
H
NO 2
H
Me
483
185
29
H
NH 2
H
NH 2
H
Me
423
186
nd
H
n-Bu—CONH
H
n-Bu—CONH
H
Me
591
187
nd
H
2-furyl-CONH
H
2-furyl-CONH
H
Me
611
188
nd
H
PhCONH
H
PhCONH
H
Me
631
189
nd
H
4-Me—PhCONH
H
4-Me—PhCONH
H
Me
659
190
nd
H
4-NO 2 —PHCONH
H
4-NO 2 —PHCONH
H
Me
721
191
nd
H
4-Me—PHSO 2 NH
H
4-Me—PHSO 2 NH
H
Me
731
192
nd
H
Cbz—NH
H
Cbz—NH
H
Me
691
193
nd
H
4-Br—PhCONH
H
4-Br—PhCO
H
Me
789
194
nd
H
2-MeO—PhCONH
H
2-MeO—PhCONH
H
Me
691
195
nd
H
3-MeO—PhCONH
H
3-MeO—PhCONH
H
Me
691
196
nd
H
4-MeO—PhCONH
H
4-MeO—PhCONH
H
Me
691
197
nd
H
CH 3 CH═CHCONH
H
CH 3 CH═CHCONH
H
Me
559
198
nd
H
C 2 F 5 CONH
H
C 2 F 5 CONH
H
Me
715
199
nd
H
2-naphthyl-
H
2-naphthyl-
H
Me
731
CONH
CONH
200
nd
H
EtO 2 CCH 2 CH 2 CONH
H
EtO 2 CCH 2 CH 2 CONH
H
Me
679
201
nd
H
CF 3 CONH
H
CF 3 CONH
H
Me
615
202
nd
H
MeSO 2 NH
H
MeSO 2 NH
H
Me
579
TABLE 10
EPO/
EBP-Ig
% inh @
MS,
cpd
50 μM
R a
R 2
R 3
R 4
R 5
Z
MH+
203
37
Boc
H
H
H
H
4-(MeCOCH 2 CH 2 )—PhNH
640
204
−6
H
H
H
H
H
4-(MeCOCH 2 CH 2 )—PhNH
540
205
26
H
H
H
H
H
n-Bu-NH
434
206
17
2-MeO—PhCO
H
H
H
H
n-Bu—NH
568
207
20
4-MeO—PhCO
H
H
H
H
n-Bu—NH
568
208
22
PhCO
H
H
H
H
n-Bu—NH
538
209
25
2-MeO—PhCO
H
H
H
H
n-Bu—NH
568
210
nd
Boc
H
H
H
H
4-MeO—PhCH 2 CH 2 NH
612
211
62
H
H
H
H
H
4-MeO—PhCH 2 CH 2 NH
512
212
−10
H
H
H
H
H
n-Pr—NH
420
214
nd
Boc
H
H
H
H
3,4-di-MeO—PhCH 2 CH 2 NH
642
215
nd
Boc
H
H
H
H
3-MeO—PhCH 2 CH 2 NH
612
216
10
Boc
H
H
H
H
4-(PhCH═CHCH 2 O)—PhCH 2 NH
700
217
nd
Boc
H
H
H
H
4-HO—PhCH 2 NH
584
218
nd
Boc
H
H
H
H
EtNH
506
219
nd
Boc
H
H
H
H
MeNH
492
220
45
H
H
H
H
H
4-(PhCH═CHCH 2 O)—PhCH 2 NH
600
221
48
H
H
H
H
H
3,4-di-MeO—PhCH 2 CH 2 NH
542
222
56
H
H
H
H
H
3-MeO—PhCH 2 CH 2 NH
512
223
nd
Boc
H
H
H
H
2-MeO—PhCH 2 CH 2 NH
612
224
51
H
H
H
H
H
2-MeO—PhCH 2 CH 2 NH
512
225
10
Boc
PhO
H
PhO
H
4-MeO—PhCH 2 CH 2 NH
797
226
nd
Boc
H
H
H
H
PhCH 2 CH 2 NH
582
227
48
H
H
H
H
H
PhCH 2 CH 2 NH
482
228
21
PhNHCO
PhO
H
PhO
H
4-MeO—PhCH 2 CH 2 NH
816
229
22
4-PhO—PhNHCO
H
H
H
H
4-MeO—PhCH 2 CH 2 NH
723
230
42
3,4-di-Cl—PhNHCO
H
H
H
H
4-MeO—PhCH 2 CH 2 NH
700
231
36
4-EtO2C—PhNHCO
H
H
H
H
4-MeO—PhCH 2 CH 2 NH
703
232
14
4-PhO—PhNHCO
PhO
H
PhO
H
4-MeO—PhCH 2 CH 2 NH
908
233
18
H
H
NO2
H
NO2
4-MeO—PhCH 2 CH 2 NH
602
234
nd
Boc
H
H
H
H
PhCH 2 NH
568
235
49
H
H
H
H
H
PhCH 2 NH
468
236
nd
Boc
H
Ph
H
Ph
4-MeO—PhCH 2 CH 2 NH
765
237
55
HO 2 CCH 2 CH 2 CO
H
H
H
H
3-MeO—PhCH 2 CH 2 NH
612
238
39
H
H
Ph
H
Ph
4-MeO—PhCH 2 CH 2 NH
664
239
46
H
PhO
H
PhO
H
PhCH 2 CH 2 NH
666
240
nd
HO 2 CCH 2 CH 2 CH 2 CO
PhO
H
PhO
H
PhCH 2 CH 2 NH
780
285
40
H
H
H
H
H
4-(NH 2 CO)piperidin-1-yl
489
TABLE 11
EPO/
EBP-Ig
% inh @
MS,
cpd
50 μM
R a
R 2
R 3
R 4
R 5
Z
r
[MH 2 /2]+
241
2
t-Bu
H
BnO
H
BnO
NH(CH 2 ) 3 O(CH 2 ) 4 O(CH 2 ) 3 NH
1
666
242
1
t-Bu
H
BnO
H
BnO
NH(CH 2 ) 3 O(CH 2 CH 2 O) 2 (CH 2 ) 3 NH
1
674
243
75
H
H
BnO
H
BnO
NH(CH 2 ) 3 O(CH 2 ) 4 O(CH 2 ) 3 NH
1
610
244
66
H
H
BnO
H
BnO
NH(CH 2 ) 3 O(CH 2 CH 2 O) 2 (CH 2 ) 3 NH
1
618
245
0
t-Bu
H
BnO
H
BnO
NH(CH 2 ) 2 O(CH 2 ) 2 O(CH 2 ) 2 NH
2
652
246
79
H
H
BnO
H
BnO
NH(CH 2 ) 2 O(CH 2 ) 2 O(CH 2 ) 2 NH
2
596
247
47
H
n-Bu—CONH
H
PhO
H
NH(CH 2 ) 2 O(CH 2 ) 2 O(CH 2 ) 2 NH
2
575
248
56
H
2-furyl-
H
PhO
H
NH(CH 2 ) 2 O(CH 2 ) 2 O(CH 2 ) 2 NH
2
585
CONH
249
72
H
4-Me—PhCONH
H
PhO
H
NH(CH 2 ) 2 O(CH 2 ) 2 O(CH 2 ) 2 NH
2
609
250
78
H
4-Me—PhSO 2 NH
H
PhO
H
NH(CH 2 ) 2 O(CH 2 ) 2 O(CH 2 ) 2 NH
2
645
TABLE 12
EPO/EBP-Ig
% inh @
MS,
cpd
50 μM
R a
R 2
R 4
Z
r
[MH 2 /2]+
251
49
H
H
H
NH(CH 2 ) 2 O(CH 2 ) 2 O(CH 2 ) 2 NH
2
436
252
−4
t-Bu
4-t-Bu—PhO
4-t-Bu—PhO
NH(CH 2 ) 3 O(CH 2 ) 4 O(CH 2 ) 3 NH
1
803
253
−5
t-Bu
4-t-Bu—PhO
4-t-Bu—PhO
NH(CH 2 ) 3 O(CH 2 CH 2 O) 2 (CH 2 ) 3 NH
1
811
254
−9
t-Bu
4-t-Bu—PhO
4-t-Bu—PhO
NH(CH 2 ) 10 NH
1
787
255
0
t-Bu
4-t-Bu—PhO
4-t-Bu—PhO
NH(CH 2 ) 12 NH
1
801
256
10
t-Bu
4-t-Bu—PhO
4-t-Bu—PhO
NH(CH 2 ) 2 O(CH 2 ) 2 O(CH 2 ) 2 NH
1
789
TABLE 13
EPO/EBP-Ig
% inh @
MS,
cpd
50 μM
R a
Z
[MH 2 /2]+
257
−26
Boc
NH(CH 2 ) 3 O(CH 2 CH 2 O) 2 (CH 2 ) 3 NH
731
258
−24
Boc
NH(CH 2 ) 3 O(CH 2 ) 4 O(CH 2 ) 3 NH
723
259
−13
Boc
NH(CH 2 ) 12 NH
721
260
−12
Boc
NH(CH 2 ) 2 O(CH 2 ) 2 O(CH 2 ) 2 NH
695
261
51
H
NH(CH 2 ) 2 O(CH 2 ) 2 O(CH 2 ) 2 NH
595
262
93
HO 2 CCH 2 CH 2 CO
NH(CH 2 ) 2 O(CH 2 ) 2 O(CH 2 ) 2 NH
695
263
88
HO 2 C(CH 2 ) 3 CO
NH(CH 2 ) 2 O(CH 2 ) 2 O(CH 2 ) 2 NH
709
264
89
HO 2 CCH 2 CMe 2 CH 2 CO
NH(CH 2 ) 2 O(CH 2 ) 2 O(CH 2 ) 2 NH
737
265
65
HO 2 CCH 2 CH 2 CO
NH(CH 2 ) 3 O(CH 2 ) 4 O(CH 2 ) 3 NH
723
266
82
HO 2 C(CH 2 ) 3 CO
NH(CH 2 ) 3 O(CH 2 ) 4 O(CH 2 ) 3 NH
737
267
83
HO 2 CCH 2 CMe 2 CH 2 CO
NH(CH 2 ) 3 O(CH 2 ) 4 O(CH 2 ) 3 NH
765
268
40
HO 2 CCH 2 CMe2CH 2 CO
NH(CH 2 ) 12 NH
764
269
55
HO 2 CCH 2 CH 2 CH 2 CO
NH(CH 2 ) 12 NH
735
270
56
HO 2 CCH 2 CH 2 CO
NH(CH 2 ) 12 NH
721
271
77
HO 2 CCH 2 CH 2 CO
NH(CH 2 ) 3 O(CH 2 CH 2 O) 2 (CH 2 ) 3 NH
731
272
78
HO 2 CCH 2 CH 2 CH 2 CO
NH(CH 2 ) 3 O(CH 2 CH 2 O) 2 (CH 2 ) 3 NH
745
TABLE 14
EPO/
EBP-Ig
% inh @
MS,
cpd
50 μM
R a
R 2
R 4
Z
n
[MH 2 /2]+
273
nd
HO 2 CCH 2 CH 2 CO
4-Me—PhO
4-Me—PhO
NH(CH 2 ) 2 O(CH 2 ) 2 O(CH 2 ) 2 NH
2
695
274
nd
HO 2 CCH 2 CH 2 CO
PhO
PhO
NH(CH 2 ) 2 O(CH 2 ) 2 O(CH 2 ) 2 NH
2
667
275
nd
HO 2 CCH 2 CH 2 CO
4-Me—PhO
4-Me—PhO
NH(CH 2 ) 2 O(CH 2 ) 2 O(CH 2 ) 2 NH
2
727
276
nd
HO 2 CCH 2 CH 2 CO
4-t-Bu—PhO
4-t-Bu—PhO
NH(CH 2 ) 2 O(CH 2 ) 2 O(CH 2 ) 2 NH
2
780
277
nd
H
PhO
PhO
(NHCH 2 CH 2 ) 3 N
3
813
278
nd
H
4-Me—PhO
4-Me—PhO
(NHCH 2 CH 2 ) 3 N
3
855
279
nd
H
4-Me—PhO
4-Me—PhO
(NHCH 2 CH 2 ) 3 N
3
903
280
nd
HO 2 CCH 2 CH 2 CO
4-Me—PhO
4-Me—PhO
(NHCH 2 CH 2 ) 3 N
3
1053
281
nd
HO 2 CCH 2 CH 2 CO
4-Me—PhO
4-Me—PhO
(NHCH 2 CH 2 ) 3 N
3
1005
282
nd
HO 2 CCH 2 CH 2 CO
PhO
PhO
(NHCH 2 CH 2 ) 3 N
3
963
283
nd
Boc
PhO
PhO
NH(CH 2 ) 3 NMe(CH 2 ) 3 NH
2
666
284
nd
Boc
4-Me—PhO
4-Me—PhO
NH(CH 2 ) 3 NMe(CH 2 ) 3 NH
2
694
TABLE 15
EPO/EBP-Ig
% inh @
cpd
50 μM
R 1
R 2
R 3
MS, MH+
285
−28
Me
H
H
473
286
46
H
BnO
H
565
287
36
H
4-Me—PhO
H
565
288
27
H
4-tBu—PhO
H
607
289
20
H
H
PhO
551
TABLE 16A
EPO/EBP-Ig
% inh @
cpd
50 μM
R 1
R 2
R 3
R 4
290
0
Me
PhO
H
t-Bu
291
17
Me
H
Ph
t-Bu
292
11
Me
3-CF3—C6H4O
H
t-Bu
293
14
Me
3,4-Cl2—C6H3O
H
t-Bu
294
9
Me
4-t-Bu—C6H4O
H
t-Bu
295
10
Me
H
Ph
H
296
0
Me
3,4-Cl2—C6H3O
H
H
297
0
Me
3-CF3—C6H4O
H
H
298
1
Me
4-t-Bu—C6H4O
H
H
299
nd
Me
PhO
H
H
300
57
H
PhO
H
H
301
25
H
H
Ph
t-Bu
302
30
H
3,4-Cl2—C6H3O
H
t-Bu
303
21
H
3-CF3—C6H4O
H
t-Bu
304
19
H
4-t-Bu—C6H4O
H
t-Bu
305
48
H
H
Ph
H
306
21
Me
H
H
t-Bu
307
25
H
3,4-Cl2—C6H3O
H
H
308
25
H
3-CF3—C6H4O
H
H
309
13
H
4-t-Bu—C6H4O
H
H
310
34
Me
H
H
H
TABLE 16B
MS,
cpd
MPLC solvent
appearance
empirical formula
MH+
290
10-30%
pale yellow oil
C38H41NO5
592
EtOAc/hex
291
1:5 EtOAc/hex
yellow oil
C38H41NO3
560
292
1:5 EtOAc/hex
yellow oil
C40H39F6NO5
728
293
1:5 EtOAc/hex
yellow oil
C38H37C14NO5
728
294
1:5 EtOAc/hex
yellow oil
C46H57NO5
704
295
off-white solid
C34H33NO3/1
504
C2H4O2
296
amber solid
C34H29C14NO5/1
672
C2H4O2
297
amber oil
C36H31F6NO5/1
672
C2H4O2
298
off-white solid
C42H49NO5/1
648
C2H4O2
299
30%
colorless oil
C34H33NO5
536
EtOAc/hex
300
sticky yellow solid
C33H31NO5/1
522
C2H4O2
301
yellow solid
C37H39NO3
546
302
amber oil
C37H35C14NO5
714
303
amber oil
C39H37F6NO5
714
304
amber oil
C45H55NO5
690
305
amber solid
C33H31NO2/1
490
C2HF3O2
306
light-yellow oil
C26H33NO3/0.25
408
H2O
307
amber solid
C33H27C14NO5/1
658
C2HF3O2
308
amber oil
C35H29F6NO5/1
658
C2HF3O2
309
off-white solid
C41H47NO5/1
634
C2HF3O2
310
light yellow oil
C22H25NO3/1
352
C2H4O2
TABLE 17A
EPO/EBP-Ig
% inh @
cpd
50 μM
R 1
R 2
R 3
311
5.3
t-Bu
PhO
H
312
45
H
PhO
H
TABLE 17B
cpd
MPLC solvent
appearance
empirical formula
MS, MH+
311
10% EtOAc/hex
pale yellow oil
C36H37NO4
548
312
sticky brown
C32H29NO4/1
492
solid
C2HF3O2
TABLE 18A
EPO/
EBP-Ig
% inh
@
cpd
50 μM
R 1
R 2
R 3
R 4
313
28
H
H
CF3
(CH2)4NH(2-Cl—Cbz)
314
12
Me
H
CO2H
(CH2)4NH2
315
nd
Me
H
NO2
(CH2)4NHBoc
316
20
Me
OPh
H
(CH2)4NHBoc
317
13
Me
4-
H
(CH2)4NHBoc
t-Bu—C6H4O
318
14
Me
H
H
(CH2)4NHCbz
319
nd
Me
H
H
(CH2)4NHCbz
320
17
Me
H
OMe
(CH2)4NHCbz
321
42
Me
CO2Me
H
(CH2)4NHCbz
322
nd
Me
H
2,3-
(CH2)4NHCbz
benzo
323
6
Me
H
CO2H
(CH2)4NHCbz
324
nd
Me
H
CO2Me
nd
TABLE 18B
cpd
MPLC solvent
appearance
empirical formula
MS, MH+
313
yellow oil
C25H28ClF3N2O4\1
499
C2HF3O2
314
yellow oil
C17H24N2O4
321
315
30%
EtOAc/hex
dark yellow gum
C21H31N3O6
422
316
20-50%
EtOAc/hex
pale yellow oil
C27H36N2O5
469
317
pale yellow oil
C31H44N2O5
525
318
gum
C24H30N2O4
411
319
pale yellow oil
C24H30N2O4
411
320
2%
MeOH/CH2Cl2
yellow oil
C25H32N2O5
441
321
yellow oil
C26H32N2O6\1
469
C2H4O2
322
25-50%
EtOAc/hex
clear residue
C28H32N2O4
461
323
yellow oil
C25H30N2O6
455
324
yellow oil
C26H32N2O6
469
TABLE 19A
EPO/EBP-Ig
% inh @
cpd
50 μM
R 1
R 2
R 3
R 4
325
6
Me
OPh
H
CH2CH2CO2H
326
0
H
OPh
H
CH2CH2CO2H
327
11
Me
H
Ph
CH2CH2CO2H
328
33
Me
3,4-Cl2—C6H3O
H
CH2CH2CO2H
329
13
H
H
Ph
CH2CH2CO2H
330
12
H
3-CF3—C6H4O
H
CH2CH2CO2H
331
18
H
4-t-Bu—C6H4O
H
CH2CH2CO2H
332
17
H
3,4-Cl2—C6H3O
H
CH2CH2CO2H
333
16
Me
3,4-benzo
CH2CH2CO2-t-Bu
334
6
Me
OPh
H
CH2CH2CO2-t-Bu
335
25
Me
H
Ph
CH2CH2CO2-t-Bu
336
32
Me
3,4-Cl2—C6H3O
H
CH2CH2CO2-t-Bu
337
0
H
OPh
H
CH2CH2CO2-t-Bu
338
23
t-Bu
3-CF3—C6H4O
H
CH2CH2CO2-t-Bu
339
10
t-Bu
4-t-Bu—C6H4O
H
CH2CH2CO2-t-Bu
340
14
H
H
Ph
CH2CH2CO2-t-Bu
341
19
H
3,4-Cl2—C6H3O
H
CH2CH2CO2-t-Bu
TABLE 19B
cpd
MPLC solvent
appearance
empirical formula
MS, MH+
325
off-white solid
C21H23NO5\1
370
C2F3HO2
326
fluffy white
C20H21NO5\1
356
solid
C2HF3O2
327
off-white solid
C21H23NO4\1
354
C2F3HO2
328
amber oil
C21H21Cl2NO5\1
438
C2F3HO2
329
amber solid
C20H21NO4\1
340
C2HF3O2
330
amber oil
C21H20F3NO5\1
424
C2HF3O2
331
amber oil
C24H29NO5\1
412
C2HF3O2
332
amber oil
C20H19CL2NO5\1
424
C2HF3O2
333
10-25%
EtOAc/hex
yellow oil
C23H29NO4
384
334
10-30%
EtOAc/hex
pale yellow oil
C25H31NO5
426
335
1:5
EtOAc/hex
yellow oil
C25H31NO4
410
336
1:5
EtOAc/hex
yellow oil
C25H29Cl2NO5
494
337
white powder
C24H29NO5\0.4
412
H2O
338
1:5
EtOAc/hex
yellow oil
C29H36F3NO5
536
339
1:5
EtOAc/hex
yellow oil
C32H45NO5
524
340
yellow solid
C24H29NO4
396
341
white solid
C24H27Cl2NO5
480
TABLE 20A
EPO/EBP-Ig
% inh @
cpd
50 μM
R 1
R 2
R 3
R 4
342
0
Me
H
Ph
CH2OH
343
37
Me
4-t-Bu—C6H4O
H
CH2OH
344
4
Me
3-CF3—C6H4O
H
CH2OH
345
40
Me
3,4-Cl2—C6H3O
H
CH2OH
346
28
Me
OPh
H
CH2OH
347
23
H
OPh
H
CH2OH
348
21
H
H
Ph
CH2OH
349
23
H
3,4-Cl2—C6H3O
H
CH2OH
350
23
H
3-CF3—C6H4O
H
CH2OH
351
29
H
4-t-Bu—C6H4O
H
CH2OH
352
8
Me
OPh
H
CH2O-t-Bu
353
24
Me
H
Ph
CH2O-t-Bu
354
31
Me
3,4-Cl2—C6H3O
H
CH2O-t-Bu
355
22
Me
3-CF3—C6H4O
H
CH2O-t-Bu
356
23
Me
4-t-Bu—C6H4O
H
CH2O-t-Bu
357
12
H
3-CF3—C6H4O
H
CH2O-t-Bu
TABLE 20B
cpd
MPLC solvent
appearance
empirical formula
MS, MH+
342
off-white solid
C19H21NO3\1
312
C2F3HO2
343
amber oil
C23H29NO4\1
384
C2F3HO2
344
amber oil
C20H20F3NO4\1
396
C2F3HO2
345
amber oil
C19H19Cl2NO4\1
396
C2F3HO2
346
EtOAc
pale yellow oil
C19H21NO4
328
347
amber oil
C18H19NO4\1
314
C2HF3O2
348
yellow solid
C18H19NO3\1
298
C2HF3O2
349
amber oil
C18H17Cl2NO4\1
382
C2HF3O2
350
amber oil
C19H18F3NO4\1
382
C2HF3O2
351
amber oil
C22H27NO4\1
370
C2HF3O2
352
10-30%
EtOAc/hex
pale yellow oil
C23H29NO4
384
353
20%
EtOAc/hex
off-white solid
C23H29NO3
368
354
20%
EtOAc/hex
yellow oil
C23H27Cl2NO4
452
355
20%
EtOAc/hex
yellow oil
C24H28F3NO4
452
356
20%
EtOAc/hex
yellow oil
C27H37NO4
440
357
white solid
C23H26F3NO4
438
TABLE 21A
EPO/EBP-Ig
% inh @
cpd
50 μM
R 1
R 2
R 3
R 4
358
0
H
H
CF3
(s)-CH(OH)CH3
359
25
Me
CO2Me
H
(s)-CH(OMe)CH3
360
18
Me
H
H
Bn
361
24
Me
CO2Me
H
Bn
362
0
H
H
CF3
CH2(4-HOC6H4)
363
33
Me
CO2Me
H
CH2(4-MeOC6H4)
364
16
Me
H
H
CH2(indol-3-yl)
365
0
H
H
CF3
CH2CH2SMe
366
38
Me
CO2Me
H
CH2CO2Me
367
0
H
H
CF3
CH2CONH2
368
40
Me
CO2Me
H
CH2SBn
369
12
H
H
CF3
i-Bu
370
0
H
H
CF3
i-Pr
371
16
Me
CO2Me
H
i-Pr
372
0
Me
H
H
Me
TABLE 21B
cpd
MPLC solvent
appearance
empirical formula
MS, MH+
358
amber oil
C14H16F3NO3\1
304
C2HF3O2
359
amber oil
C17H23NO5\1
322
C2H4O2
360
20% EtOAc/hex
light-yellow
C19H21NO2
296
oil
361
amber oil
C22H25NO5\1
354
C2H4O2
362
amber oil
C19H18F3NO3\1
366
C2HF3O2
363
amber oil
C22H25NO5\1
384
C2H4O2
364
1:2 EtOAc/hex
tan solid
C21H22N2O2
335
365
amber oil
C15H18F3NO2S\1
334
C2HF3O2
366
amber oil
C17H21NO6\1
336
C2H4O2
367
amber oil
C14H15F3N2O3\1
317
C2HF3O2
368
amber oil
C22H25NO4S\1
400
C2H4O2
369
amber oil
C17H22F3NO2\1
316
C2HF3O2
370
amber oil
C15H18F3NO2\1
302
C2HF3O2
371
amber oil
C17H23NO4\1
306
C2H4O2
372
20% EtOAc/hex
yellow oil
C13H17NO2\0.10
220
C4H8O2
|
This invention relates to a series of substitituted amino acids of Formula I
pharmaceutical compositions containing them and intermediates used in their manufacture. The compounds of the invention are small molecules which bind to the erythropoietin receptor and compete with the natural ligand for binding to this receptor.
| 2
|
FIELD OF THE INVENTION
The present invention relates to machines for producing chenille yarns.
SUMMARY OF THE INVENTION
According to the present invention, there is provided in a machine for producing chenille yarn, at least one yarn-forming assembly including means for feeding at least one pair of binding yarns and at least one effect yarn, a winding member, means for forming turns of the effect yarn on the winding member, cutter means, and means for moving the cutter means towards and away from said winding member in order to cut the turns of effect yarn when the cutter is moved towards the winding member, and to leave them intact when it is moved away from the winding member to provide respectively for the formation of yarn comprising normal chenille portions or boucle portions.
Preferably, the winding member comprises a longitudinal slot in which the cutter means is located in its operative position.
This machine may have a plurality of aligned yarn-forming assemblies with cutter means which are movable cyclically under the control of a cylinder-piston servo motor or the like. Each cutter means comprises a disc-shaped blade with means for rotating it and which is moved towards and away from the respective winding member.
BRIEF DESCRIPTION OF THE DRAWINGS
An embodiment of the invention will now be described, by way of example only, with reference to the accompanying diagrammatic drawings, in which:
FIG. 1 is a fragmentary front elevation of a yarn-forming assembly in a machine for producing chenille yarn;
FIG. 2 is a section to an enlarged scale of a detail of FIG. 1;
FIG. 3 is a section taken on line III--III of FIG. 2;
FIGS. 4 and 5 are, respectively, an enlarged detail of FIG. 2, and a section of line V--V of FIG. 4, illustrating the operation when a cutting blade is in its active position;
FIG. 6 is a view similar to FIG. 4, but showing the operation when the blade has been moved out of its active position;
FIGS. 7 and 8 are sections taken respectively on lines VII--VII and VIII--VIII of FIG. 6; and
FIG. 9 shows a length of fancy yarn produced by the machine.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The machine shown in the accompanying drawings comprises a support structure 1 on which are mounted two assemblies 3 and 5 which are disposed in mutually offset relation. The assembly 3 (FIG. 2) comprises an external casing 7 supported by the structure 1 and containing bearings 9 which mount a rotor 10 which can rotate about the axis of the assembly. A core 14 is mounted inside the rotor 10 by bearings 12. The core 14 has an upper extension which projects from the upper end of the casing 7 to carry an upper head 14A and a lower extension 14B, to which a winding member 16 is fitted. An effect yarn E is wound around a triangular part of the winding member 16 as will be described later and this determines the size of individual lengths of effect yarn or of boucle loops. The winding member 16 is preferably replaceable to permit changes in size.
The assembly 5 is similar to the assembly 3 and comprises a rotor equivalent to the rotor 10, carrying at its upper end 18A a yarn guide 36 and at its lower end 18B a pulley 19. Inside the rotor 18 there is mounted a core 20 corresponding to the core 14, and having projecting lower and upper end portions 20A and 20B, respectively, which can be seen in FIG. 1. The core is mounted so that it can rotate about an axis which is offset relative to the axis of the core 14. The two cores are connected rigidly together by a pair of profiled bars 22.
Although each core is rotatably mounted within the assembly 3 or 5, the connection provided by the bars 22 between the two cores prevents their rotation due to the interaction between the cores. In contrast, the two rotors 10 and 18 can rotate, and are in fact rotated synchronously. For this purpose, the rotor 10 comprises a toothed pulley 10C, about which is wound a toothed belt 24 driven from a shaft which also drives a second toothed belt 30 wound about the pulley 19 fixed to the rotor 18. The two rotors 10 and 18 therefore rotate at the same speed, and support the two cores 14 and 20 but without causing rotation of the cores. The two cores 14 and 20 are therefore prevented from rotating without having any external connection to a fixed part.
On the upper end portion 20B of the core 20 there is disposed a platform 20C which carries spools 34 of binding or core yarn A. The core yarns which are unwound from the spools 34 pass through longitudinal bores in the cores 20 and 14 to reach the winding member 16 mounted at the lower end of the core 14. The platform 20C also carries a ring 20E, along which slides a free span of effect yarn E fed from an overlying fixed spool. After passing through a ring yarn guide 36, the effect yarn E passes through a guide tube 38 contained in the rotor 18, to emerge below this rotor and then pass into a tube 39 mounted on the rotor 10. The tube 39 opens into an annular cage 40, having a lower ring 40A which forms a yarn guide rotatable around the winding member 16 to wind the effect yarn E. The effect yarn E describes a circular trajectory outside the assemblies 3 and 5, inside the tubes 38 and 39, inside the cage 40 and around the winding member 16 without any interference with the stationary cores 14, 20, which are located within the trajectory described by the effect yarn.
There may be only a single effect yarn E, or several effect yarns fed in an analogous manner simultaneously via the same tube.
The winding member 16 mounted at the lower end of the stationary core 14 comprises a base 41 traversed by two bores 43, one of which receives a core yarn A from one of the spools 34. The yarn A emerges from the base 41 and is fed to a yarn guide 45 fitted against a triangular winding plate 47, connected to the base 41, which has an extension plate 49 having a portion centrally extending through the winding plate and a portion extending therefrom provided with a longitudinal slot 49B to receive a cutting blade when the chenille portion is to be formed, as will be described hereinafter.
The winding member 16 is associated with means for feeding an external core yarn A2, which passes round a roller 51 to the side of the extension 49 of the triangular plate 47.
To provide improved guiding and entrainment of the effect yarn E which may be sheared into individual lengths, a backing roller 53 lies against the roller 51, and is driven thereby.
The core yarn A from a spool 34 is drawn through the axial bores in the two cores 20 and 14, and then through the bore 43 in the winding member 16, to reach the yarn guide 45 and thus pass on to the roller 51. The effect yarn E is fed around the triangular plate 47 of the winding member 16 from the yarn guide formed by the ring 40A, so as to form turns as the rotor 10 rotates, with consequent rotation of the cage and ring 40,40A. These turns become gradually tightened and slide along the edges of the plate 47 to form tight turns on its extension 49. In this manner, turns or coils of effect yarn are formed, as indicated at E1.
This arrangement gives a fancy yarn of the so-called boucle or flocked chenille type CF, i.e. with uncut coils of effect yarn, as shown in FIGS. 6, 7, and 8. The turns leave the winding member 16 below the end of the extension 49.
The machine is also equipped to produce a special fancy yarn as shown in FIG. 9. This yarn comprises portions X of flocked chenille (boucle), produced in the aforesaid manner, interspaced with portions Y of normal chenille CN, i.e. with individual sheared lengths of effect yarn. This is obtained by providing a cutting blade with is made periodically active and inactive. For this purpose a rotatable disc-shaped blade 60 mounted on a movable support 62 on which there is also mounted a motor 64 for driving the blade 60. The support 62 is preferably mounted for rectilinear sliding movement and is controlled by a cylinder 66, which can displace the support 62 between an inactive position in which the blade 60 is remote from the member 16 (FIGS. 6 and 8) and an active position in which the blade 60 enters the narrow slot 49b provided longitudinally in the surface of the extension 49 opposite the feed roller 51 for the core yarn A2 (FIGS. 4 and 5). This position can be determined by an adjustable stop 67. In its active position the blade 60 cuts a plurality of successive turns E1, so that instead of forming successive loops of flocked chenille CF, cut lengths of effect yarn are formed, to constitute the portions Y of normal chenille CN (FIG. 9). Each blade 60 is advantageously protected by a suitable guard. The operation of the blade 60 can be program controlled to provide any required alternation between the portions X and Y. In practice the machine will be provided with several yarn-forming assemblies as described above, with the blades of the respective assemblies being controlled by the same program so that identical yarn will be produced by each assembly.
|
A machine for producing chenille yarn has a winding member on which turns of effect yarn are formed. A rotating disc-shaped cutter can be moved into an operative position to cut the turns on the winding member into individual lengths of effect yarn for forming conventional chenille yarn. The cutter can also be moved to a non-operative position remote from the winding member whereby the turns of effect yarn are uncut and the chenille yarn then produced is of the boucle type. The cutter may be moved between its operative and inoperative positions during operation of the machine so that the yarn produced has alternate chenille portions and boucle portions.
| 3
|
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application claims priority to U.S. Provisional Patent Application No. 60/758,718, filed Jan. 13, 2006 and incorporated herein by reference in its entirety.
FIELD OF THE INVENTION
[0002] The present invention relates generally to tilt systems. More particularly, the present invention relates to audio and/or video tilt systems that enable a user to position an attached device in a variety of orientations.
BACKGROUND OF THE INVENTION
[0003] In recent years, flat-panel television units have become enormously popular in both the commercial and the residential sectors. As the prices for plasma and liquid crystal display (LCD) flat panel displays have continued to fall, and as the quality for the same devices have improved, more and more businesses and individuals have purchased such devices both for business and home entertainment purposes.
[0004] One of the advantages of flat-panel television units that customers have found particularly appealing is their relatively low thickness. Because conventional “tube” televisions have a relatively large depth, the display options for such devices are quite limited. In the residential setting, most users require a television stand or large entertainment center to store the television. Such stands or entertainment centers can take up significant floor space, which is often undesirable. In the commercial or educational setting, users will often install large overhead tilt systems that can contain the television. However, these systems usually require professional installation and, once the television is secured in the mount, it is often very difficult to access and adjust due to its height.
[0005] With flat-panel televisions, on the other hand, users are presented with a relatively new option: tilt the television directly to a wall or similar surface. By tilting the television relative to a wall, a person can eliminate the need to take up potentially valuable floor space with a television stand or entertainment unit. Furthermore, individuals and entities can mount the television at a sufficiently low height to be able to adjust the television's orientation with little difficulty.
[0006] Although the introduction of flat-panel televisions on a wide scale has presented new opportunities to both residential and commercial customers, it has also presented new challenges. Over the past few years, a number of wall tilt systems have been developed for use with flat panel televisions, but each has their own drawbacks. For example, U.S. Pat. No. 6,905,101 discloses a wall tilt system that permits a flat panel television to have a limited range of motion once it is mounted to the wall. The products described in these disclosures rely upon the use of a set of curved slots to form a rotatable connection between a tilt bracket and a support bracket, with rolling pins being used to create a rolling connection between the two brackets. Similarly, U.S. application Publication No. 2004/0245420 discloses a tilt system where a plurality of arc-shaped glides are used instead of rolling pins.
[0007] Although such systems are moderately useful, they suffer from a number of important drawbacks. Such systems often rely upon friction knobs or other friction-based mechanisms both to control the amount of resistance during the adjustment process, as well as to maintain a particular angular orientation once the positioning process has been completed. However, these friction-based mechanisms do not definitely “lock” the respective brackets in place, and these mechanisms can be forced from their set positions. As a result, even a slight bump of the flat screen unit can cause the orientation of the mount to be altered. In many settings, once the mount has been correctly positioned, it will not be (or will only infrequently be) readjusted. In such situations, accidental movement of the mount is especially undesirable.
[0008] It would therefore be desirable to provide an adjustable tilt system that enables a user to more securely fix the orientation of the mount once a desired orientation has been attained.
SUMMARY OF THE INVENTION
[0009] The present invention provides an improved tilt system including an incremental angular position and locking system. According to various embodiments of the present invention, an adapter bracket is slidably and/or rollingly engaged with a tilt bracket. One of the adapter bracket and the tilt bracket includes a plurality of angular positioning portions along at least one side wall thereof. The other of the adapter bracket and the tilt bracket includes a locator portion on at least one side wall thereof. The locator portion is positioned to selectively align with the various angular positioning portions depending upon the particular orientation of the adapter bracket relative to the tilt bracket. When a locator portion is aligned with one of the angular positioning portions, the user can use a locking member to fix the position of the tilt bracket relative to the adapter bracket.
[0010] With the present invention, a user is capable of effectively fixing the angular orientation of the tilt system, and therefore an attached device, once a desired angular orientation has been achieved, while still providing a user with a large degree of autonomy in selecting the desired orientation. Additionally, when these systems are used in an “array” format, the present invention allows for all of the individual mounting systems in the array to be positioned and locked at the same angular orientation from one unit to the next. This allows the array of mounted audio/visual products to be oriented in a highly organized, professional and orderly manner, making the use of the mounting systems more efficient.
[0011] These and other objects, advantages and features of the invention, together with the organization and manner of operation thereof, will become apparent from the following detailed description when taken in conjunction with the accompanying drawings, wherein like elements have like numerals throughout the several drawings described below.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] FIG. 1 is a perspective view of an adjustable tilt system with an angular position and locking mechanism constructed according to a first embodiment of the present invention;
[0013] FIG. 2 is a side view of the tilt bracket of FIG. 1 ;
[0014] FIG. 3 is a side view of the adapter bracket of FIG. 1 ;
[0015] FIG. 4 is a magnified view of an adapter bracket with various components attached thereto;
[0016] FIG. 5 is a perspective view of an adjustable tilt system with an angular position and locking mechanism constructed according to a second embodiment of the present invention;
[0017] FIG. 6 is a side view of the adapter bracket of FIG. 5 ; and
[0018] FIG. 7 is a side view of the tilt bracket of FIG. 5 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0019] FIG. 1 shows an adjustable mounting system 10 constructed in accordance with a first embodiment of the present invention. The adjustable mounting system 10 of FIG. 1 comprises a tilt bracket 12 which is configured to engage a retaining member (not shown) which can be affixed to a wall, floor pedestal, ceiling mount, or other surface. The tilt bracket 12 includes a tilt bracket engagement portion 11 and a pair of tilt bracket flanges 13 on each side thereof. It should also be noted, however, that the tilt bracket 12 can be directly secured to a wall, floor pedestal, ceiling mount, or other surface instead of engaging one or more retaining members. The tilt bracket 12 can also be connected to the wall, floor pedestal, ceiling mount, or other surface via several intermediate components, such as an articulating arm (not shown) or other brackets or plates. These various components can be used to translate an attached electronic device away from or towards the wall, floor pedestal, ceiling mount, or other surface, to tilt the electronic device to the left or right, or for other purposes.
[0020] In the embodiments shown in FIG. 1 , an adapter bracket 14 is rotatably coupled to the tilt bracket 12 . The adapter bracket 14 includes an adapter bracket contact portion 15 bounded by a pair of adapter bracket flanges 17 on each side thereof in one embodiment of the invention. In this particular embodiment, the adapter bracket 14 is attached directly to the respective electronic device (not shown). However, it should also be noted that, in other embodiments of the invention, a display bracket (not shown) can be secured to the adapter bracket contact portion 15 , with the display bracket being configured to attach to a flat panel display or other electronic device.
[0021] As shown in FIG. 1 , the tilt bracket 12 includes a plurality of tilt bracket guide paths 24 , and the adapter bracket 14 includes a plurality of adapter bracket guide paths 26 . FIG. 1 shows the tilt bracket guide paths 24 and adapter bracket guide paths 26 as slots that are formed completely within the tilt bracket 12 and adapter bracket 14 , respectively. However, it should be understood that the present invention is not strictly limited to the use of slots. Instead, guide paths for the tilt bracket 12 and the adapter bracket 14 can comprise items such as rails and outer surfaces that define a path of travel, as well as other structures that provide guide paths. The present invention should therefore not be strictly limited to the use of slots.
[0022] Both the tilt bracket guide paths 24 and the adapter bracket guide paths 26 are sized to accept a carrier 22 therethrough. In one embodiment, the carriers 22 comprise rolling pins. However, other types of carriers, such as gliders or other items, could also be used. In one particular embodiment of the invention, two rolling pins are used, with one rolling pin passing through the uppermost tilt bracket guide paths 24 and adapter bracket guide paths 26 on each of the respective flanges, and another rolling pin passing through the lowermost tilt bracket guide paths 24 and adapter bracket guide paths 26 on each of the respective flanges.
[0023] In the embodiment of the invention shown in FIG. 1 , each guide path is substantially straight in nature. While the tilt bracket guide paths 24 and the adapter bracket guide paths 26 can also be curved, the use of straight guide paths creates a “scissoring” action which diminishes sliding and promotes the smooth movement of the carrier mechanisms with the guide paths. The substantially straight guide paths also aid in ensuring that the carrier mechanisms do not slip when a user or installer lifts and removes the electronic device from the remainder of the adjustable mounting system 10 .
[0024] The tilt bracket guide paths 24 are located on the tilt bracket flanges 13 , and the adapter bracket guide paths 26 are located on the adapter bracket flanges 17 . In one embodiment of the invention, each tilt bracket flange 13 includes two tilt bracket guide paths 24 , and each adapter bracket flange 17 includes two adapter bracket guide paths 26 , each of which are configured to align with a respective tilt bracket guide slot 24 .
[0025] The embodiment of the invention shown in FIG. 1 also includes a friction member 30 for adjusting the level of resistance that is met during the adjustment process. In one particular embodiment, the friction member 30 includes an adjustment screw that passes through both a friction slot 28 in the adapter bracket flange 17 , shown in FIG. 3 and a friction hole 29 in the corresponding tilt bracket flange 13 , shown in FIG. 2 . It should be noted that the friction hole 29 and friction slot 28 can also be reversed, such that the friction slot 28 appears on the tilt bracket 12 . It is also possible to include two friction slots instead of one friction slot and one friction hole. A plurality of washers 31 may also be used along with the adjustment screw. In this embodiment of the invention, a clockwise rotation of the adjustment screw causes the respective adapter bracket flange 17 and tilt bracket flange 13 to come into closer contact with each other, which results in an increased level of friction when the user moves the electronic device (and therefore the adapter bracket 14 ) relative to the tilt bracket 12 . A counterclockwise rotation of the adjustment screw correspondingly reduces the friction level between the tilt bracket 12 and the adapter bracket 14 . It should be understood that other types of friction devices may also be used, and that these friction devices may or may not include an adjustment screw of the type described herein.
[0026] As shown in FIG. 2 , the tilt bracket 12 also includes a plurality of angular position features 40 on at least one of the tilt bracket flanges 13 . In the embodiment depicted in FIG. 2 , the angular position features 40 comprise holes in the tilt bracket flange(s) 13 . However, it should be noted that other features, such as slots, could also be used. The angular position features 40 are strategically placed to track the tilting motion of the adjustable mounting system 10 for the purposes described below.
[0027] FIG. 3 is a side view of the adapter bracket 14 of FIG. 1 . The adapter bracket 14 includes an angular positioning element 42 that passes through a locking feature (shown at 43 in FIG. 7 ) within the adapter bracket flanges 17 . The angular positioning element can comprise a screw or similar item. The locking feature 43 can comprise a hole, slot, or other item which is capable of cooperating with the angular positioning element 42 .
[0028] The operation of the present invention is generally as follows. As discussed above, the tilt bracket 12 is directly or indirectly attached to a surface such as a wall, while the adapter bracket 14 is directly or indirectly attached to an object to be mounted. As discussed previously, the object may comprise an audio/visual device such as a flat screen television. However, a wide variety of other objects can also be mounted using the adjustable mounting system 10 of the present invention. Once the object is mounted, the user can adjust the angular tilt of the object by simply rotating the object, which causes the adapter bracket 14 to rotate relative to the tilt bracket 12 .
[0029] In the embodiments shown in FIGS. 1-4 , the adapter bracket 14 rotates about an axis that runs substantially parallel to adapter bracket flanges 17 and tilt bracket flanges 13 , as well as about an axis substantially parallel to the wall or other surface to which the adjustable mounting system 10 is attached. This rotation is also about an axis substantially parallel to the tilt bracket engagement portion 1 . However, it is also possible for some or all of these orientations to be altered. For example, if the tilt bracket 12 is coupled to an articulating arm with different degrees of movement, then the axis of rotation of the adjustable mounting system 10 may be different than substantially parallel to the wall or other surface. During the rotation process, adjusting the friction member 30 allows the user to control the amount of resistance that is encountered while rotating the adapter bracket 14 .
[0030] When the user has positioned the adapter bracket 14 relative to the tilt bracket 12 to his her own satisfaction, he or she uses the angular positioning element 42 to secure the position of the adapter bracket 14 . In the situation where the angular positioning element 42 comprises a screw, pin, spring loaded pin, locking pin, clevis pin, clevis pin with lanyard, pin with ball detent, or similar fastener, this is accomplished by passing the angular positioning element 42 through the locking feature 43 and the angular position features 40 which most closely aligns with the angular positioning element 42 . Because there is a certain amount of space between the angular position features 40 , it is possible that a very slight adjustment of the adapter bracket 14 may be necessary in order to create the proper alignment. Once the angular positioning element 42 has been secured with the proper angular position features 40 , the adapter bracket 14 is prevented from further rotation. If a user later wants to readjust the orientation of the object about the axis created by the sliding or rolling connection depicted in FIG. 1 , he or she simply has to disengage the angular positioning element 42 from the respective angular position feature 40 .
[0031] The engagement and disengagement of the angular positioning element 42 can take a variety of forms. For example, in a case where the angular positioning element 42 comprises a simple screw, then the screw may, when not engaged with an angular position features 40 , may not be engaged with the locking feature 43 either. Alternatively, the screw or other angular positioning element 42 may, in the default position, be nested within the locking feature 43 such that it only needs to be “pushed into” the appropriate angular position feature for locking to occur. This provides the benefit of not having to worry about losing the angular positioning element 42 during the adjustment process.
[0032] As shown in FIG. 3 , one embodiment of the adjustable mounting system 10 also includes an alignment feature 44 strategically positioned relative to the locking feature 43 and the angular positioning element 42 . The alignment feature 44 is utilized by the user to quickly and easily align the tilt bracket 12 and the adapter bracket 14 so that the locking system can be used. In particular, the angular position features 40 are positioned such that, if one of the angular position features 40 is aligned with the locking feature 43 , then the alignment feature 44 will indicate the presence of such an alignment. In the embodiment shown in FIGS. 1-4 , the alignment feature 44 comprises a visual alignment feature in the form of a hole. Therefore, when one of the angular position features 40 is aligned with the locking feature 43 , the user will be able to see another of the angular position features 40 through the alignment feature 44 .
[0033] In the embodiment shown in FIGS. 1-4 , the alignment feature 44 is shown as being positioned substantially above the locking feature 43 . In such a case, it is possible that, if a user wants to use the upper most angular position features 40 for alignment and locking, the user may not observe the alignment through the alignment feature 44 . To resolve this issue, one could use a “dummy” angular position feature (not shown), solely for the purpose of using the alignment feature 44 . For example, the tilt bracket flanges 13 could include a colored marking where the next angular position features 40 would otherwise have been located, or a “dummy” hole that is too small for locking purposes could be used instead of a marking. Other types of “dummy” features could also be used in such a situation, and the location of this feature can be positioned to strategically correlate to the requirements set by the location of the alignment feature 44 . Other systems to demarcate angular position include but are not limited to angular scales and/or numbered readouts that are visible through the alignment feature 44 .
[0034] It should be noted that, although the alignment feature 44 comprises a hole in the embodiment shown in FIGS. 1-4 , it is also possible for the alignment feature to comprise a slot or similar visual indicator. Additionally, it is also possible for the alignment feature 44 to not be visual in nature in other embodiments. For example, the alignment feature can comprise a structure that creates an audible “click” or similar sound when a proper alignment has been attained. Other types of alignment features would also be understood to be applicable by those skilled in the art.
[0035] Additionally, it should also be noted that many of the components depicted and described herein can essentially be reversed while still achieving the intended results of the present invention. For example, in the embodiments shown in FIGS. 1-4 , the tilt bracket flanges 13 are positioned outside of the respective corresponding adapter bracket flanges 17 . However, it is possible that the tilt bracket flanges 13 can be positioned inside of the corresponding adapter bracket flanges 17 . In such a scenario, the angular positioning features 40 can be located on the adapter bracket 14 , and the tilt bracket 12 can include the locking feature 43 and the alignment feature 44 can be located on the adapter bracket 14 . FIGS. 5-7 show such an embodiment of the present invention. Although FIGS. 5-7 show a structure that is similar to the structure depicted in FIGS. 1-4 , these figures show that the various components are capable of being formed in a variety of shapes and sizes. For this reason, it should be understood that the various components used in the present invention should not be interpreted as being limited to the shapes and sizes depicted herein. Other arrangements and combinations would also be understood by those in the art.
[0036] The foregoing description of embodiments of the present invention have been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the present invention to the precise form disclosed, and modifications and variations are possible in light of the above teachings or may be acquired from practice of the present invention. The embodiments were chosen and described in order to explain the principles of the present invention and its practical application to enable one skilled in the art to utilize the present invention in various embodiments and with various modifications as are suited to the particular use contemplated.
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A mounting system comprising an incremental angular position and locking system. A tilt bracket is configured to operatively connect to a surface, and an adapter bracket is operatively and movably connected to the tilt bracket, with the adapter bracket being configured to operatively connect to an object such as an audio/video device. A plurality of angular position features are associated with one of the tilt bracket and the adapter bracket, and an angular positioning element is configured to selectively engage at least one of the plurality of angular position features. When the angular positioning element is in engaged with at least one angular position feature, the adapter bracket is impeded from moving relative to the tilt bracket. When the angular positioning element is not in engagement with at least one angular position feature, the adapter bracket is substantially free to move relative to the tilt bracket.
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FIELD OF INVENTION
The present invention generally relates to structural reinforcement devices and more particularly to an improved system for protecting buildings against shear stress and uplifting.
BACKGROUND OF THE INVENTION
A large portion of the United States periodically suffers from earthquakes, tornados, or hurricanes. Low-level wooden buildings, including virtually all residential structures, are particularly susceptible to damage from these events. Consequently, even one such event can damage or destroy large numbers of wood-framed structures and their contents, causing billions of dollars of damage, displacing thousands of people from their homes, and seriously injuring or killing their occupants.
Earthquakes, tornados, and hurricanes destroy low-level wood-framed structures in two primary ways: creating high shear forces in the walls and uplifting the structure from its foundation. Lateral forces created by wind pressure or by seismic activity create substantial shear forces in the walls of the building which it would not normally experience. Further, the walls of a wood-framed building are generally weakest against shear loads. Consequently, violent shear forces can tear a standard wood-framed building apart. Uplifting of the building from its foundation also results from the abnormal atmospheric pressures and wind forces associated with tornados and hurricanes, and from the seismic motion of the ground during an earthquake.
Because of the significant damage and loss of life than can result from a tornado, hurricane, or earthquake, the Uniform Building Code (UBC) began to impose requirements in the 1970s for providing additional shear strength in the walls of low-level wood-framed structures. Originally, plywood shear panels nailed onto a wooden wall frame and attached to the building's base with hold-downs were used to provide the extra shear strength needed to meet the UBC requirements.
Plywood shear panels have several disadvantages. They take up a great amount of space and restrict the height to width ratio and design flexibility of buildings. This problem occurs because the plywood shear panels must be a certain size in order to comply with the strict strength requirements of the UBC. Additionally, the end vertical studs to which the plywood shear walls attach must be bulky 3×5 or 4×4 studs instead of the customary 2×4 studs in order to accommodate the nailing schedule used to attach the plywood shear wall to the skeletal frame. Builders using plywood shear panels must follow a complex nailing schedule and utilize a specific type of nail to meet those requirements. A large amount of time and skilled labor is required to hammer in all of the nails that are required by the prior art, adding to construction time and expense. In addition, significant inspection time is required to ensure that the proper nailing schedule and nail type were used, adding to construction time and placing a burden on city building inspectors.
Hold-downs were used along with plywood shear panels to provide the necessary shear strength and address the problem of uplifting. Two primary types of hold-down were used. The first consisted of a bolt that attached the plywood shear wall to a bottom plate, which is then attached to the foundation. L-shaped braces were also used to attach the end vertical studs to the bottom plates; those braces were then attached in turn to the foundation. Neither of these methods directly attaches the shear wall to the foundation. Rather, a bottom plate intermediates between the two, creating a failure point. As the structure ages, a wooden bottom plate may deteriorate for several reasons. The constant pressure of the structure on the wooden bottom plate for year after year can crush or compress it. Insects such as termites can attack and destroy the wooden bottom plate. As the wood dries out, it can shrink or become brittle. Consequently, as the wooden bottom plate ages and deteriorates, the hold-down nut remains stationary on the hold-down bolt, forming a gap between the nut and the wooden bottom plate. Such a loosened hold-down loses much of its effectiveness for uplift resistance. Further, because these hold-downs were not attached in line with the uplift forces, they were subject to significant moment forces during uplift, creating extra strain on the hold-downs and increasing the likelihood of failure.
SUMMARY OF THE INVENTION
The present invention provides an reinforcing brace frame in a stud wall.
In a first, separate aspect of the present invention, a frame structure is contemplated including a stud wall, a foundation, and a reinforcing brace frame. The reinforcing brace frame includes two horizontally-extending frame members, two vertically-extending frame members, a diagonal frame member, and at least two slots bolted to the foundation. The reinforcing brace frame satisfies the requirements of the UBC, and of building codes in high-risk areas like Los Angeles, for shear resistance in wood-framed buildings. The installation of several reinforcing brace frames in a wood-framed structure obviates the need for expensive plywood shear panels that require significant time to construct and inspect. The reinforcing brace frame provides a unitary solution to the problems of shear stress and uplift. At the same time that it reinforces a structure against severe shear stress, the reinforcing brace frame protects it from uplift through its direct integration with the structure's concrete foundation by means of shear bolts and hold down bolts.
In a second, separate aspect of the present invention, a unitary vertically-extending member with an upper frame member and a lower frame member on either end thereof. The unitary member is an open section forming a semi-enclosed rectangular space. This structural device is of particular utility in small wall areas such as to either side of a garage door.
Accordingly, it is an object of the present invention to provide an improved reinforcing brace frame structure. Other and further objects and advantages will appear hereinafter.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is a front elevation of a preferred embodiment of the reinforcing brace frame of the present invention, shown secured in a building wall to studs, top and bottom plates.
FIG. 1A is a cross-sectional view of a horizontal support member.
FIG. 1B is a cross-sectional view of a vertical support member.
FIG. 1C is a cross-sectional view of an additional vertical member.
FIG. 1D is a cross-sectional view of the diagonal support member.
FIG. 1E is a top view of the washer.
FIG. 1F is a detail of a corner of the reinforcing brace frame.
FIG. 2 is a front view of an second embodiment of the reinforcing brace frame.
FIG. 2A is a cross-sectional view of the unitary vertical support member in the second embodiment of the reinforcing brace frame.
FIG. 3 is a front elevation of two reinforcing brace frames stacked and connected together top to bottom with bolts.
FIG. 3A is a front elevation of two reinforcing brace frames stacked and connected together top to bottom with metal straps.
FIG. 4 is a front elevation of two reinforcing brace frames staggered and connected together top to bottom with a bolt.
FIG. 4A is a front elevation of two reinforcing brace frames staggered and connected together top to bottom with a metal strap.
FIG. 5 is a reinforcing brace frame in a stud wall.
DETAILED DESCRIPTION
Now referring more particularly to FIG. 1 of the accompanying drawings, a first preferred embodiment of the reinforcing brace frame of the present invention is schematically depicted therein.
Thus, a first preferred embodiment of an reinforcing brace frame 10 is shown which includes a vertically spaced pair of horizontal frame members, the top member 12 and the bottom member 14. The opposite ends of both the top member 12 and the bottom member 14 are rigidly connected, preferably by welding, to a laterally spaced pair of vertical frame members, the left member 16 and the right member 18, to form therewith an open rectangular box 20. While the rigid connection between members is preferably accomplished by welding, any method of rigid connection may beused, such as, e.g., brazing or bolting. Preferably, the top member 12 and the bottom member 14 possess a "U"-shaped cross-section, as shown in FIG. 1A, but any other cross-section that provides adequate strength may be used. Preferably, the top member 12 is oriented such that the open portion of the "U"-shaped cross-section is directed downward. Preferably, the bottom member 14 is oriented such that the open portion of the "U"-shaped cross-section is directed upward. Preferably, the left member 16 and the right member 18 possess a "C"-shaped cross-section, as shown in FIG. 1B, where the opening in each "C" section has been welded closed to form an enclosed hollow member, but any other cross-section that provides adequate strength may be used. The left member 16 and the right member 18 are oriented such that the open portion of the "C"-shaped cross section that has been welded shut is facing away from the center of the reinforcing brace frame 10.
The reinforcing brace frame 10 also includes a diagonal support member 26, the opposite ends 28 and 30 of which are rigidly connected, preferably by welding, to the top member 12 and the bottom member 14, and to the left member 16 and the right member 18, at opposite corners of rectangular box 20. While the rigid connection between members is preferably accomplished by welding, any method of rigid connection may be used, such as, e.g., brazing or bolting. Preferably, diagonal support member 26 possesses a "C"-shaped cross-section, as shown in FIG. 1C, but any other cross-section that provides adequate strength may be used.
Preferably, the reinforcing brace frame 10 includes two additional vertical support members, the first additional vertical member comprising a first upper member 22 and a first lower member 42, and the second additional vertical member comprising a second upper member 24 and a second lower member 44. More than two such additional vertical members may be used as needed. The first upper member 22 is rigidly connected at one end to top member 12 and rigidly connected at the opposite end to diagonal member 26. The first lower member 42 is located directly below and in line with the first upper member 22. The first lower member is rigidly connected at one end to the diagonal member 28 and rigidly connected at the opposite end to the bottom member 14. The second upper member 24 is rigidly connected at one end to the top member 12 and rigidly connected at the opposite end to the diagonal member 26. The second lower member 44 is located directly below and in line with the second upper member 24. The second lower member 44 is rigidly connected at one end to the diagonal member 28 and rigidly connected at the opposite end to the bottom member 14. Preferably, these rigid connections are accomplished by welding, but any rigid connection may be used, such as, e.g., bolting or brazing. Preferably, the first upper member 22, the first lower member 42, the second upper member 24, and the second lower member 44 possess a "U"-shaped cross-section, as shown in FIG. 1D, but any other cross-section that provides adequate strength may be used. Preferably, the first upper member 22 and the first lower member 42 are oriented such that the open portion of the first upper member 22 is directed in the opposite direction as the open portion of the first lower member 42 such that the first upper member 22 and the first lower member 42 cooperatively resist shear loading. Preferably, the second upper member 24 and the second lower member 44 are oriented such that the open portion of the second upper member 24 is directed in the opposite direction as the open portion of the second lower member 44 such that the second upper member 22 and the second lower member 42 cooperatively resist shear loading.
Preferably, the reinforcing brace frame 10 is composed of steel, but wood or other metal, or a combination, of sufficient strength may be used. Thus, the reinforcing brace frame 10 forms a self-contained strong, rigid unit resistant to shear stress which can be directly incorporated into a framed wall to substantially increase the resistance of the wall to collapse during tornados, hurricanes and earthquakes.
FIG. 1 shows the reinforcing brace frame 10 secured in place in the framing of a stud wall 32 comprising vertical studs 34, a sill 36 and a base 38 above a concrete foundation 40. FIG. 5 shows an alternate view of the reinforcing brace frame 10 secured in place in a stud wall 32 comprising vertical studs 34, a sill 36 and a base 38 above a concrete foundation 40, showing a typical installation of the reinforcing brace frame 10. Preferably, the reinforcing brace frame 10 is secured to the foundation by shear bolts 48 and hold down bolts 50. The hold down bolts 50 pass through a washer 70, then through slots 56 in the bottom member 14 through a base 38 directly into a concrete foundation 40. The washer 70 is positioned within the open channel of the bottom member 14, within the semi-enclosed space defined by either left member 16 or right member 18. The washer 70 is rectangular in shape, and is made from steel.
FIG. 1E shows a top view of the washer 70. The washer 70 contains a slot 72 oriented such that its longer dimension runs perpendicular to the plane defined by the reinforcing brace frame 10. The slot 72 preferably possesses semicircular ends and a substantially rectilinear portion therebetween. The slots 56 in the bottom member 14 possess the same size and shape. The washers 70 are positioned such that the slot 72 in each washer is located directly above a corresponding slot 56 in the bottom member 14. Further, each washer 70 is oriented such that each slot 72 and each slot 56 are directionally aligned. The orientation and shape of the slot 72 and the slots 56 allow construction personnel to adjust the alignment of the reinforcing brace frame 10 to ensure it is substantially parallel to the wood frame wall it is located within.
The shear bolts 48 pass through the base 38 and penetrate a sufficient distance into the concrete foundation 40 to prevent the reinforcing brace frame 10, and the stud wall 32 to which it is secured, from sliding during severe shear stress. Preferably, three shear bolts 48 are used, but additional shear bolts 48 may be used in a specific installation if needed. The hold down bolts 50 pass through the base 38 and penetrate a sufficient distance into the concrete foundation 40 to prevent uplifting of the reinforcing brace frame 10 and consequently of the building itself. Preferably, two hold down bolts 50 are used, with one hold down bolt 50 centered in line with the left member 16 and another hold down bolt 50 centered in line with the right member 18, but additional slots 56 and hold down bolts 50 may be used in a specific installation if needed. Centering the hold down bolts 50 with respect to the longitudinal centerline of both the left member 16 and the right member 18 places the hold down bolts 50 in line with uplift forces, thereby minimizing the moment force experienced by the hold down bolts 50 during uplift.
The reinforcing brace frame 10 is also secured to the sill 36. Preferably, the reinforcing brace frame 10 is secured to the sill 36 by screws 46, but any other connectors or connection methods possessing the required strength may be used. The number of screws 46 used is dependent on the specific installation of the reinforcing brace frame 10.
FIG. 1A shows the preferred "U"-shaped cross-sectional structure of the top member 12 and the bottom member 14.
FIG. 1B shows the preferred closed "C"-shaped cross-sectional structure of the left member 16 and the right member 18.
FIG. 1C shows the preferred "C"-shaped cross-sectional structure of the first upper member 22, the first lower member 42, the second upper member 24, and the second lower member 44.
FIG. 1D shows the preferred "C"-shaped cross-sectional structure of the diagonal member 26.
FIG. 1F shows a corner of the reinforcing brace frame in detail.
A second preferred embodiment of the reinforcing brace frame 10 is shown in FIG. 2. This embodiment is advantageously used in smaller and narrower spaces in a wall to be reinforced, such as, e.g., a short wall on either side of a garage door. This second embodiment includes a vertically spaced pair of horizontal frame members, the top member 12 and the bottom member 14. Preferably, the top member 12 and the bottom member 14 each possess a "U"-shaped cross-section. The top member 12 is oriented such that the open portion of the "U"-shaped cross-section is directed downward, and the bottom member 14 is oriented such that the open portion of the "U"-shaped cross-section is directed upward.
A vertical member 58 is formed from a single sheet of metal bent twice along both its left edge and its right edge such that the left and right sides of the vertical member 58 each form an open rectangular semi-closed space as shown in FIG. 2 with inwardly extending flanges 58A and B, end panels 58C and D and an interconnecting flat web 58E. The vertical member 58 is sized such that it fits into the open portion of both the top member 12 and the bottom member 14. The vertical member 58 is rigidly connected to the top member 12 and the bottom member 14, preferably by welding. Two washers 70 are rigidly connected to the bottom member 14, preferably by tack welding. These washers are sized such that they fit atop the bottom member 14 within the space defined by the open rectangular semi-closed portions of the vertical member 58. As with the first preferred embodiment, the washers 70 are oriented such that the slot 72 in each washer 70 is aligned with its corresponding slot 56 on the bottom member 14.
By disposing the top and bottom ends of the vertical member 58 within the open portion of the top member 12 and the bottom member 14, and rigidly connecting the vertical member 58 to the top member 12 and the bottom number 14, the vertical member 58 gains significant rigidity. The top member 12 and the bottom member 14 constrain the ends of the vertical member 58 and thereby increase the resistance of the vertical member 58 to shear and torsion. Due to this interaction among the vertical member 58, the top member 12, and the bottom member 14, the second embodiment of the reinforcing brace frame 10 can withstand shear loads at least as great as the requirements imposed by the UBC, without the need for a diagonal member 26.
FIG. 2 shows the second embodiment of the reinforcing brace frame 10 secured in place in the framing of a stud wall 32 comprising vertical studs 34, a sill 36 and a base 38 above a concrete foundation 40. Preferably, the reinforcing brace frame 10 is secured to the foundation by hold down bolts 50. The hold down bolts 50 pass through a washer 70, then through slots 56 in the bottom member 14 through a base 38 directly into a concrete foundation 40. The washer 70 is positioned within the open channel of the bottom member 14, within the semi-enclosed space defined by either left member 16 or right member 18.
The hold down bolts 50 penetrate a sufficient distance into the concrete foundation 40 to prevent uplifting of the reinforcing brace frame 10 and consequently of the building itself. Preferably, two hold down bolts 50 are used, with one hold down bolt 50 centered in line with the open rectangular space on the left edge of the vertical member 58 and another hold down bolt 50 centered in line with the open rectangular space on the right edge of the vertical member 58, but additional slots 56 and hold down bolts 50 may be used in a specific installation if needed. Centering the hold down bolts 50 with respect to the longitudinal centerlines of the open rectangular spaces at the left and right edges of vertical member 58 places the hold down bolts 50 in line with uplift forces, thereby minimizing the moment force experienced by the hold down bolts 50 during uplift. In this embodiment, the hold down bolts 50 also act as shear bolts, resisting shear forces as well as uplift.
The reinforcing brace frame 10 is also secured to the sill 36. Preferably, the reinforcing brace frame 10 is secured to the sill 36 by screws 46, but any other connectors or connection methods possessing the required strength may be used. The number of screws 46 used is dependent on the specific installation of the reinforcing brace frame 10.
As shown in FIG. 3, a plurality of brace frames 10, if desired, can be stacked on top of one another, and can be welded, bolted or otherwise permanently connected together to reinforce a multi-story building. For such purposes, the top member 12 of the lower reinforcing brace frame 10 and the bottom member 14 of the upper reinforcing brace frame 10 can be aligned for placing bolts 60 through both vertically stacked reinforcing brace frames. The two reinforcing brace frames 10 are aligned such that the bolts 60 are in line with the hold down bolts 50 which secure the lower reinforcing brace frame 10 to the foundation 40. Preferably, the lower reinforcing brace frame 10 and the upper reinforcing brace frame 10 are separated by a sill 36 through which the bolts 60 pass. The direct connection between the reinforcing brace frames 10 enables the connected reinforcing brace frames 10 to resist shear and uplift forces as a single unit.
In an alternate embodiment shown in FIG. 3A, metal straps 80 are used to directly connect the stacked reinforcing brace frames 10. Preferably, the strap 80 is welded to both reinforcing brace frames 10, but any rigid connection may be used, such as, e.g., bolting.
The stacked reinforcing brace frames 10 may be separated by other types of structural member so long as they are directly connected; for example, by bolts 60 passing through a joist from one reinforcing brace frame 10 to the other. Further, more than two reinforcing brace frames 10 may be stacked together.
As shown in FIG. 4, a plurality of brace frames 10 may be stacked together in a staggered fashion. The top member 12 of the lower reinforcing brace frame 10 is aligned with the bottom member 14 of the upper reinforcing brace frame 10 such that a bolt 66 can be placed downward from a bottom corner of the upper reinforcing brace frame 10 to the opposite top corner of the lower reinforcing brace frame 10. The two reinforcing brace frames 10 are aligned such that the bolt 66 is in line with one of the hold down bolts 50 which secure the lower reinforcing brace frame 10 to the foundation 40. Preferably, the lower reinforcing brace frame 10 and the upper reinforcing brace frame 10 are separated by a sill 36 through which the bolt 66 passes.
In an alternate embodiment shown in FIG. 4A, a metal strap 80 is used to directly connect the staggered reinforcing brace frames 10. Preferably, the strap 80 is welded to both reinforcing brace frames 10, but any rigid connection may be used, such as, e.g., bolting.
The staggered reinforcing brace frames 10 may be separated by other types of structural member so long as they are directly connected; for example, by a bolt 66 passing through a joist from one reinforcing brace frame 10 to the other. The other lower corner of the upper reinforcing brace frame 10 is connected by a bolt 68 to a wall framing member 82. The wall framing member 82 is directly connected to the foundation 40 by hold down bolt 52. The wall framing member 82 is aligned with the upper reinforcing brace frame 10 such that the bolt 68 is in line with the hold down bolt 52. More than two reinforcing brace frames 10 may be staggered in this manner.
An reinforcing brace frame and many of its attendant advantages have thus been disclosed. It will be apparent, however, that various changes may be made in the form, construction, and arrangement of the parts without departing from the spirit and scope of the invention, the form hereinbefore described being merely a preferred or exemplary embodiment thereof. Therefore, the invention is not to be restricted or limited except in accordance with the following claims.
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The reinforcing brace frame is utilized in building walls as a complete system of protection against both the severe shear stress and uplifting encountered during tornados, hurricanes and earthquakes. The reinforcing brace frame includes two vertically-spaced horizontally extending frame members joined at their opposite ends to two horizontally-spaced vertically extending frame members, and a diagonal member rigidly connected to opposite ends of the horizontally extending frame members. The reinforcing brace frame can also include spaced vertical support members between the vertical frame members. The reinforcing brace frame is directly attached to a concrete foundation by shear bolts and hold down bolts. Consequently, the reinforcing brace frame provides increased resistance against simultaneous shear stress and uplifting, eliminating the need for plywood shear panels.
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FIELD OF THE INVENTION
This invention relates to an information holding device. The device is referred to below as a memory, though it is to be understood that the information may be held only briefly, in which case the device may function, for example, as a delay line, or the information may be held for a longer time, in which case the device may function as a normal memory.
BACKGROUND OF THE INVENTION
In recent years, memories have been developed, for example for computers, which have been increasingly compact, but there is, nevertheless, a demand for still more compact memories. An object of the present invention is to provide such a memory, and in particular a memory employing a Langmuir-Blodgett film (hereinafter referred to as an L-B film).
Before the invention is described in detail an outline will be given of the nature and properties of L-B films.
Many molecules having a hydrophilic and hydrophobic end, for example long chain fatty acids, form insoluble monolayers at an air-water interface. The packing in the monolayer may be controlled by the application of surface pressure through barriers and the equation of state of the film is given by the surface pressure-area isotherm. When an appropriate substrate, for example glass, silicon or indium phosphide, is dipped through the air-water interface then one monolayer may be transferred to the substrate each time the interface is traversed. A film of great perfection can thus be built up a single monolayer at a time. It has been demonstrated that it is possible to build up extremely precise supermolecular structures consisting of fatty acids, long-chain dyes and similar molecules for the study of electron and exciton transport. More recently it has been demonstrated that fatty acids with certain substitutes, for example a diacetylene group, may be polymerized either at the air-water interface or after the film has been prepared.
Charge and energy transport in L-B films will now be summarized.
(a) Electron tunneling.
Monolayers of fatty acids with varying chain lengths, and hence varying thickness, have been prepared as a sandwich between conducting aluminium layers. The electrical conductivity of such films has been demonstrated to decrease logarithmically with increasing monolayer thickness. This is the result which would be expected if the currents were due to electrons tunneling through the dielectric monolayers. With some reservations this view is generally accepted as is the conclusion that these experiments demonstrate the remarkably perfect quality of the monolayers.
(b) Exciton transfer.
Monolayers of dye substituted fatty acids commonly exhibit the characteristic absorption and fluorescence spectra of the isolated dye. Detailed investigations have been made of energy transfer from one type of dye in one monolayer to a second type of dye in neighbouring or more distant monolayers. If for example a sensitizer dye S which absorbs in the UV and emits in the blue is incorporated in an L-B film assembly with an acceptor dye A which absorbs in the blue and emits in the yellow then considerable energy transfer can occur. Under UV illumination the blue fluoresence is partially quenched by the presence of dye A and yellow fluorescence appears. The relative quenching of dye A fluorescence depends upon the proximity of dye S in a manner predicted by the classical electric dipole model.
(c) Photoinduced electron transfer.
Electron as well as exciton transfer has been observed between different chromophores in multilayer assemblies. In this case when the photon is absorbed an electron is transferred from one molecule acting as the donor D to the second acting as acceptor A. Quenching of fluorescence is observed in monolayer assemplies if donor and acceptor are in the same monolayer or at the hydrophilic interface between adjacent monolayers. When D and A layers are separated by a single fatty acid monolayer it has been possible to observe this transfer as a photocurrent.
(d) Compensated photoinduced electron transfer.
In general the photoinduced electron transfer D - A is reversible and in the dark the electron will return A - D. The reverse process can be inhibited if an electron source molecule ES can supply an electron to the photo-oxidized donor. This possibility has been demonstrated by a monolayer sandwich: ES (leucostearylenblue), D (ω-pyrenestearate), fatty acid, A (dioctadecyl-bipyridinium). Under illumination the system acted as an inefficient electron pump.
(e) Photoinduced electron release.
Photocurrents can be generated from a layer of an absorbing molecule located in a film of fatty acid layers if the excited state energy level of the absorber lies close to the potential barrier of the fatty acid layers. It is known that this is possible for the linear conjugated molecule quinquethienyl for which the excited state lies 0.4eV below the potential barrier of arachidate layers.
The potential of the L-B multilayer technique for the fabrication of supramolecular structures has been amply demonstrated, as described above. However, the practical application of structures with photo-excited energy and charge transfer has been inhibited by the poor stability of L-B multilayers primarily composed of fatty acids. This arises from the low melting points of the long-chain fatty acids and the large amplitude molecular motions, which give rise to solid-state phase transitions below the melting points of paraffinic crystals. Thus, the ceiling temperature of fatty-acid L-B multilayers is close to room temperature and they exhibit pronounced ageing, with consequent changes in physical properties, due to molecular re-arrangement within the L-B layers.
One solution to this problem, which has been extensively studied over a number of years, is the inclusion in the monolayer-forming molecules of reactive units capable of producing polymer chains within the layer. Such reactions can occur in L-B layers since the molecular packing within each layer brings the reactive units into close contact. Molecules containing double bonds were studied first, e.g vinyl stearate and octadecyl methacrylate. polymerization was observed with UV and electron beam irradiation but the materials were found to oxidise readily, so that all film preparation has to be carried out in an inert atmosphere, and the dimensional changes on polymerization gave a rather imperfect product.
The solid-state topochemical polymerization of certain di-substituted diacetylenes has been known for some time. This polymerization is insensitive to normal atmosphere and there followed development to investigate the properties of L-B films made from fatty-acids containing diacetylinic units. The topochemical polymerization was found to occur under UV in irradiation in air and the dimensional changes were sufficiently small that the final films were as perfect as the initial monomer films.
The stability and quality of polydiacetylene L-B multilayers has been shown by their inclusion in MIS devices. Although the conditions for the formation of pin-hole free L-B monolayers are more stringent than those for the unsubstituted fatty acids they are now well documented in the literature so that routine fabrication is possible. The ceiling temperature of polydiacetylene L-B films has not been critically determined. Values in excess of 200° C. are to be expected since this is the regime in which polydiacetylene crystals are observed to decompose. In one case the first stage of this decomposition has been identified as cleavage of the bulky, reactive sidegroups, probably initiated by absorbed oxygen. This suggests that diacetylenes with less reactive paraffinic sidegroups are likely to decompose at higher temperatures. Ageing of the polymerized films should be negligible since on polymerization the paraffinic side chains are locked in place by the polymer chains, which prevents any translational motion either in or out of the plane of the film. This is revealed most dramatically by the disappearance of phase transitions in both the pure acids and their salts. It should be emphasised that the incorporation of polydiacetylene chains into L-B multilayers offers benefits in addition to providing more durable films. These derive from the properties of the PDA chain, which is a wide band-gap wide band semiconductor with strong electron-hole interaction. Thus the PDA chains can play an active role in the photo-excitation of energy and charge transfer through L-B multilayer structures.
The electronic and vibrational excitations of the conjugated polydiacetylene backbone are now very well understood. Optical absorption and reflection spectroscopy have demonstrated the existence of an exciton state on the backbone at approximately 2eV while photoconduction measurements have shown that the conduction band lies 2.4eV above the valence band. Resonance Raman spectroscopy has revealed that only a few phonons on the backbone are strongly coupled to the exciton. The most prominent of these are at 2100cm -1 and 1500cm -1 ; lattice dynamical analysis of the backbone has shown that the former mode primarily involves distortion of the triple bond while the latter involves the double bond.
BRIEF SUMMARY OF THE INVENTION
According to the present invention there is provided a memory for carrying information comprising a multilayer Langmuir-Blodgett film in which each layer is capable of carrying a charge; means located adjacent one face of the film for introducing charges into the film in a time sequence which corresponds to the information to be carried, means for applying a voltage between the faces of the film to cause the charge carried by any layer to be transferred to the adjacent layer, and means for reading out the sequence of charges carried by the film.
Preferably the layers of the Langmuir-Blodgett film (hereinafter referred to as an L-B film) are polymeric, and they may, for example, be formed of a polydiacetylene (PDA).
Materials for the film which are particularly suitable are ones, like polydiacetylene, which have a conjugated bond structure, as such structures have a low energy gap.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows diagramatically a first embodiment of the invention;
FIG. 2 shows diagramatically a second embodiment of the invention;
FIGS. 3a to 3f illustrate the detection of charge and current in the devices of the invention;
FIGS. 4a and 4b show the energy levels for a multilayer composed of two different materials, for small applied field and large applied field respectively;
FIGS. 5 to 7 show the energy levels for three arrangements of the photo-injector which can be used; and
FIGS. 8 to 10 show the energy levels for three arrangements of electron arrival detector which can be used.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The embodiment shown in FIG. 1 comprises an L-B film 1 formed of a plurality of n layers 2 (eight are illustrated) of PDA. The layers are spaced a distance a apart from one another and the overall film thickness is d. Adjacent one face of the film 1 is a layer D of electron donor molecules which require a photon energy above ω D to donate. ω D is the energy needed to take an electron from the donor layer D and put it in the conductance band of the PDA. A source 3 of photon energy is provided, and the drawing also shows a means 4 for modulating the output of the source 3 in a manner described. below. Adjacent the other face of the file 1 is a layer F of molecules which fluoresce on receiving an electron. An optical loop O feeds the output of the layer F back to the layer D. Since the quantum efficiency of the layer D and the layer F is less than unity the loop O must have gain.
For the purposes of amplification the optical signal produced by the layer F could be converted into an electrical signal which could then be amplified, or amplification of the optical signal could take place directly without such conversion. A voltage source 6 applies a d.c. voltage across the film 1 via electrodes 7. In some cases, as will be apparent from what is said below the layers D and F could themselves function as electrodes. An amplifier 5 is diagramatically shown.
To understand the behaviour of the embodiment described above, consider the fate of an extra electron resident in the conduction band of one chain. It diffuses rapidly in the plane. It has a long jump time τ to the next plane, estimated by Mott type argument as
1/τ=νexp (-2ka) (1)
where ν is a phonon frequency. An estimate of k is given by
k.sup.2 =2mA/ .sup.2 (2)
where A is the electron affinity, and m is the electron mass.
So the diffusion coefficient D and mobility μ in a perpendicular direction are
D=a.sup.2 /τ,
μ=(e/k.sub.B T)d (3)
where e is the electron charge, k B is the Boltzmann constant, and T is the absolute temperature.
There are three regimes of possible applied voltage V across the film:
(A) For 0<V<k B T/e=V(1) diffusion dominates drift in the perpendicular transport.
(B) For V(1)<V<n 2 k B T/e=V(h) drift dominates diffusion over the film thickness d but not over the layer separation a.
(C) For V(h)<V drift dominates diffusion even over the layer separation. In this regime the energy difference between an electron in adjacent layers is greater than k B T and back jumping against the field is rare. The mobility also becomes field dependent.
The transit time across the film due to drift, at velocity v is t=d/v=d/μE=d 2 /μV. Using equation 3 then
t=n.sup.2 τ,v=a/nτ, at V=V(1)
t=nτ,v=a/τ, at V=V(h)
An approximate estimate of the actual magnitude of the figures involved is as follows.
At room temperature k B T/e=25mV which is also V(1).
So for a film of 8 layers V(h)=0.2 volt.
The values of D, μ, τ and t are exponentially sensitive to a (and A). Taking a=1nm and A=4eV(and ν=10 14 Hz) than τ=8.8 μs. So, with 0.2 volts applied, an electron put on the first layer will jump to adjacent layers every 8.8 μs and emerge out of layer 8 after 70 μs.
Because of the above mentioned exponential dependence different devices with small differences of a or A can have large differences of t and τ.
In operation of the above described device the photon energy, for example light, emitted by the source 3 is pulse-code modulated by the modulation means 4, the pulses having a width <t and a period t/n, while the voltage V>V(h) is applied across the film. Because of the synchronism between the period of the pulse train and the jump time for an electron to jump from one plane to the next the pulse train is translated into a corresponding spatial charge distribution across the film. Thus, for example, if the pulse train emitted by the source 3 is 10011010 then after a time equal to t has elapsed there will be a corresponding charge distribution 10011010 across the width of the film, 0 and 1 corresponding respectively to the absence and presence of charge on an individual layer of the film. This charge pattern is continuously cycled through the device by the action of optical loop O.
It is to be understood that although the description of the drawing refers only to a single electron on a particular layer there could in practice be a group of electrons. Thus, consider a device of area A c containing a charge Q. There is an upper limit to Q at a given applied electric field E, denoted Q m , set by space charge considerations, and given by
Q.sub.m =εε.sub.o A.sub.C E.
Here ε and ε o are the dielectric constant of the medium and permittivity of free space respectively. So in a device of n layers the upper limit to q, the charge on one layer, is q m , and
q.sub.m =εε.sub.o A.sub.C E/n.
Suppose the arrival of an electron at F leads to the fluorescence of a photon of energy V L electron volts with quantum efficiency η. Then the arrival of one bit at F, over a time duration τ which is the hop time, gives a maximum fluoresced power P given by
P=ηq.sub.m V.sub.L /τ
It may be noted at this stage that the above described device uses electron arrival detection (abbreviated herein as EAD) and an alternative detection method, namely current differentiation (abbreviated herein as CD) is described later on in this description.
The above description refers to the storage of one bit per layer. However, an alternative possibility is to use n layers to store n/M bits, so that the bits are M layers apart. This has the advantage that diffusion, destroying the spatial coherence of the store, is less significant. Using the previous equations, then the criterion for adjacent bits not to diffuse together after N cycles round the device is V/V(h)>N/M 2 .
FIG. 2 shows an embodiment employing current differentiation (CD). This comprises a pair of devices 1 and 1' each comprising n layers 2,2' of PDA. Each device has a layer D of electron donor molecules but no layer F as in FIG. 1. Each device is provided with a source 3,3' of photon energy, in the form of a light-emitting diode (LED). Each device is further provided with a current differentiation detector 8,8' for detecting, in a manner described below, the current in the device. The current detector of each device is coupled to the LED of the other device so that information is continuously cycled around the arrangement consisting of the pair of devices. Each device is further provided, as in FIG. 1, with a device (not shown) for modulating the output of the source 3,3' and a voltage source 6 (not shown) for applying a d.c. voltage across the electrodes 7.
Reference will now be made to FIGS. 3a to 3f which illustrate the operations of electron arrival detection and current differentiation for a bit pattern 0011100. FIG. 3a represents the charge density ρ as a function of position, the double-headed arrow denoting the direction of travel of the bits. The maximum charge in any one bit is q m . FIG. 3b represents the fluoresced power P from the layer F as a function of time t, the maximum power being ηq m V L /τ. This is what is detected by electron arrival detection, as in FIG. 1. FIG. 3c shows the current I due to exit only of the bit pattern, as a function of time. The maximum change in this current over a duration τ due to the arrival of one bit at F is
ΔI=q.sub.m /nτ.
and the maximum change in the current due to the injection of one bit at D over a duration τ (FIG. 3d) is
ΔI=q.sub.m /nτ.
If this current is differentiated with respect to time then dI/dt due to the arrival of one bit F is a negative peak of duration and height ΔI/τ (FIG. 3e), and dI/dt due to the injection of one bit at D is a positive peak of duration τ and height ΔI/τ (FIG. 3f). This current differentiation (CD) method, in contrast to EAD, records entry of bits as well as exit of bits. Moreover they are recorded with different sign. If bits are entering simultaneously with their leaving then CD records no change; in contrast EAD records the exiting bits correctly whether bits are entering or not. The device of FIG. 2 is so arranged so that writing in of bits never overlaps in time the reading out of bits; in addition the signs of connections are chosen so that exiting bits only, and not entering bits, cause entry of bits of the next stage.
Another device using CD is described further on in this description.
The signal to noise ratio of given detectors of fluorescence (EAD) or differentiated current (CD) is determined by the products Pτ and τΔI respectively. The maximum value of these is:
Pτ=ηq.sub.m V.sub.L =εε.sub.o A.sub.C EV.sub.L η/n Joules, EAD,
τΔI=q.sub.m /n=εε.sub.o A.sub.C E/n.sup.2 Coulombs, CD.
Even if η is small EAD is more sensitive than CD at sufficiently large n. Increasing the device area and operating field increase the signal strength.
With the numerical example already used i.e. n=8, a=1nm, V(h)=0.2 volts, A=4eV,ν=10 14 Hz, τ=8.8 μs, and taking in addition ε=3, A C =10 -11 m 2 (corresponding to 10 5 such devices per mm 2 ), V=2 volts, then
ΔI=6×10.sup.-11 A,
P=8ηV.sub.L ΔI Watts.
FIG. 4 illustrates diagramatically a film composed of alternate layers of two different materials, for example two types of PDA, which have different values of electron affinity A, differing by ΔA. Different PDA's of different side groups, have energy gaps differing by up to 0.25 eV and corresponding differences occur also in A. Thus ΔA can be as large as 10 times the thermal energy k B T (at room temperature). The jump times denoted in FIGS. 4a and 4b are then
1/τ.sub.12 (S)=νexp (-2ka) exp (-εA/k.sub.B T)
small or zero field, E<ΔA/ea
1/τ.sub.12 (1)=νexp (-2ka)
large field, E≧ΔA/ea
1/τ11=νexp (-4ka).
where τ 12 is the jump time from a layer of type 1 to an adjacent layer of type 2, and τ 11 is the jump time from one layer of the type 1 to the nearest layer of type 1. Thus
τ.sub.12 (1)<<τ.sub.12 (s)<<τ.sub.11.
Suppose these alternating layers are used to store one bit per 2 layers, so that M=2. (It is to be noted that this need not be the case and that there may be a plurality of layers of type 1 between adjacent layers of type 2 and/or a plurality of layers of type 2 between adjacent layers of type (1). Then for the large field the jump time is as before and the device behaviour is essentially unchanged (from the previous M=2 case). For the small field however, the bits are essentially frozen in the bilayers in the highest A chains for the time τ 12 (s). Thus the hold time before diffusion destroys the static bit pattern is τ 12 (s).
With the previous numerical example, and ΔA=10k B T at room temperature:
τ.sub.12 (1)=8.8μs, τ.sub.12 (s)=0.19s,
and
τ.sub.11 =2.17 hours.
Thus, with such PDA alternating layers bits can be written into the device with the high field applied, stored for a time up to τ 12 (s) with the field small or zero, and read out of the device with the high field re-applied. This alternating layer device is more complicated than the original device because the applied field now has to be controlled, i.e. it must be turned on and off in synchronism with the bits entering and leaving, but the information holding time is longer.
The read and write field, E=ΔA/ea, is very large. In the numerical example it is 10k B T per layer separation a i.e. 250 mV per 1nm, i.e., 2.5=10 8 V/m. However, the application of such fields is quite feasible with existing technology.
If the read and write fields are of opposite sign to one another the bits can be written and read at the same side of the multilayer using EAD, since the bits will move in opposite directions under the influence of the two fields.
The last bit in will be the first bit out. If reading and writing are to be done at separate times, using the long hold time of the alternating layer device, it is possible to abandon EAD and use CD instead.
The hold time can be increased by lowering the temperature and so lengthening τ 12 (s) until it equals τ 11 . In the numerical example this equality occurs at T=140K, below which the hold time would be 2.17 hours. Further lowering of the temperature leaves the hold time unaffected.
As will be apparent, there are two hold times to consider. The first is the hold time before diffusion destroys the bit pattern when the field is on and the bits are being written in or read out. This is the hold time considered in relation to FIG. 1. This time sets the maximum write-read time; i.e. it sets the maximum byte length as limited by diffusion. The second hold time is the time the bit pattern is retained statically in small or zero field before diffusion destroys the bit pattern. These hold times may be referred to respectively as the dynamic hold time and the static hold time. The dynamic hold time can be lengthened by using the previously described technique of storing one bit in M layers of which one has high A and (M-1) have low A. This exponentially lengthens τ 11 which is the upper limit to the static hold time which can be reached on lowering the temperature.
With the present numerical example then for M=3 (i.e. where there are 2 layers of type 2 between each layer of type 1) τ 11 becomes 200,000 years. At liquid nitrogen temperature, T=77K, τ 12 (s) is 6,000 years.
Some materials suitable for forming the various components of the device according to the invention will now be discussed.
The electrodes both apply the electric field across the device and also supply the transit electrons from the D layer and collect the transit electrons at the F layer. They can be metals or doped semiconductors. They can be substrates onto which LB layers are deposited; or they can be evaporated or sputtered onto such LB layers. For semiconductor electrodes with photon energies below the semiconductor band-gap the electrode is transparent; otherwise the electrode is semi-transparent (and opaque if thick).
The layer D forming the electron photo-injector can be a metal, in which case D is also the electrode. FIG. 5 shows that the minimum photon energy ω D to photo-inject an electron is given by ω D =W-A. The metal electrode is denoted M and the LB layer as LB. v is the reference energy of an unbound electron at rest, cb is the conduction band edge of the material of the LB layer (e.g. PDA) at an energy A below V, vb is the valence band edge of PDA or an energy I below V, and w is the Fermi level of the metal at an energy W below v. The available range of W is large so ω D can virtually be chosen at will.
Suitable metals for use as metal electrodes on PDA crystals include Ag, Al, Au, Cd, Cu, Ga, Hg, In, Mg, Pb, Zn, Sn.
Alternatively D can be a p-type semiconductor, in which case it is also the electrode. FIG. 6 shows that the minimum energy to photo-inject using a semiconductor S is ω D =E G (provided A>W-E g ). W is the valence band edge of the semiconductor at energy W below v, E G is the energy gap of the semiconductor, and the other symbols have the same meaning as in FIG. 5. Suitable semiconductors include Ge, Si, GaAs, GaSb, InP, InAs, InSb, HgTe.
Another possibility is for D to be a dye molecule DM, shown in FIG. 7. The dye is a strong adsorber of photons of energy (G-E), creating an exciton at energy level e. The exciton can auto-ionise to create an electron at level cb and a hole at level w if (G-E)<W-A. The net result of the photon adsorbtion is electron injection. The auto-ionisation will only be efficient if DM is a monolayer. LB monolayers of dye molecules can be produced, as is mentioned below in reference to the layer F. In FIG. 7 w is the Fermi level of a metal or the valence band edge of a semiconductor, depending on whether the electrode is a metal M or a semiconductor S, g is the electronic ground slate of the dye DM at energy G below V, e is the first singlet exciton state of the dye at energy E below v, and the other symbols have the same meaning as in FIGS. 5 and 6.
If (G-E)<2eV the dye exciton will not propagate in the PDA. If the electrode is a semiconductor of E G >(G-E) the dye exciton will not directly excite the semiconductor. Both these maximise the efficiency of electron injection.
In all cases hole injection in the dark will not occur for W<I. Photo-injection of holes can be ignored; any such holes will return due to the applied field across the PDA.
The electron arrival detector F can be a p-type semiconductor as shown in FIG. 8. The electron arriving at this electrode can enter the conduction band of the semiconductor provided W-E G >A. The electron is then a minority carrier in the p-type semiconductor and can recombine rapidly by emission of a photon of energy E G . The conditions for such recombination are identical to those required in a semiconductor laser or light-emitting diode, and thus well established. F is then analogous to an LED with the n-type electron injector replaced by the PDA multilayer. It is necessary that W<I so that dark injection of holes does not occur. There is a large range of semiconductors of various E G and W developed for LED technology from which to choose, including GaAs, GaSb, InP, InAs, InSb, HgTe. The symbols in FIG. 8 have the same meaning as in FIG. 6.
Alternatively, F can be a dye molecule. In a reversal of the exciton auto-ionisation of FIG. 7, FIG. 9 shows creation of the exciton by tunnelling of the arriving electron to the electrode. This process requires W-A>(G-E), and that F be a monolayer for efficiency. The subsequent rapid dye fluorescence is the signature of the electron arrival. The symbols in FIG. 9 have the same meaning as in FIG. 7.
FIG. 10 shows a further scheme not relying on such a tunnelling process in a monolayer, and which would work with thicker dye layers. The symbols have the same meaning as in FIG. 9. The process involves the following steps:
1. Electron: g→w, Heat release: W-G.
2. Electron: cb→e, Heat release: E-A.
3. Fluorescence: e→g, Light emission: G-E.
The net result is an energy release of W-A. For the process to work it is necessary that E>A, G<W, I>W.
Step 1 occurs spontaneously in the dark and creates positively charged dye molecules. In other than a monolayer of dye the positive charge will migrate in the applied field to the dye molecules adjacent to the PDA. The arriving electron, which is highly mobile along the PDA chain, can then hunt in the plane of the film and find the positively charged dye molecule. At Step 2 the electron enters the dye and forms the exciton. Step 3 is the rapid dye fluorescence. Migration of this exciton can be prevented by the methods described above.
Fluorescing dyes in the required range have been studied at length for their use in dye lasers. Dyes can be put in layers by evaporation. If a dye of suitable values of E and G is incorporated in a molecule from which LB layers can be formed, then the dye can be put as mono- or multilayer at the D or F side of the PDA multilayer. For example, LB layers can be formed from lightly substituted anthracene derivatives with aliphatic side chains, for example a derivative where the side chain has four CH 2 units (known as C4) and a derivative where it has six CH 2 units (known as C6). Attention is directed in this connection to the journal Phys. Technol. Vol. 12, 1981 pp 69 to 87. Also, LB films can be formed of derivatives of perylene to obtain perylene fluorescence in the same way.
The above description has referred to the layers of the memory as being of PDA. However, other materials which form LB films can be used instead. Preferably, these are large conjugated organic molecules, because in such molecules the value of I-A is small and there is therefore less chance of impurity and defect trapping of the electrons destroying the spatial coherence of the memory. For example, the molecules C4 and C6 mentioned above might be used for the memory, as might a derivative of perylene.
Among polydiacetylenes, suitable materials include compounds of the formula
H(CH.sub.2).sub.m --C.tbd.C--C.tbd.C--(CH.sub.2).sub.n COOH
where m and n are integers. Film-forming compounds of this general formula are known where the values of (m,n) are (12,8), (10,8), (14,8), (16,2) or (16,0).
A plurality of independent information holding devices can be created in unit area of a film. Three ways in which this can be done are:
(a) The substrate can have a plurality of independent electrodes fabricated by conventional microelectronic techniques before deposition of the LB layers.
(b) A plurality of independent electrodes can be placed on the LB layers after their deposition.
(c) The LB layers of monomer can be polymerised by UV light. If the light passes through a plurality of holes in a mesh, created by conventional microelectronic technique, a corresponding plurality of information holding devices is created.
These present techniques allow a maximum of the order of 10 5 devices per mm 2 . This gives a minimum device fabrication per device of 10 -11 m 2 , as used in the numerical example given herein. In a device of this area with n PDA layers n bits can be held. This compares with conventional devices in which an area several times this size is needed to hold just one bit.
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A memory comprises a multilayer Langmuir-Blodgett film (1) in which each layer (2) is capable of carrying a charge. A photo-injector layer (D) is located on one side of the film for introducing charges into the film in a time sequence which corresponds to the information to be carried. Voltage source (6) is provided for applying a voltage between the faces of the film to cause the charge carried by any layer to be transferred to the adjacent layer. The sequence of charges carried by the film may be read out by a photon-emitting electron arrival detector (F) on the opposite side of the film, or by a method of current differentiation. The film (1) is preferably formed of a polydiacetylene.
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CROSS-REFERENCE TO RELATED U.S. APPLICATIONS
Not applicable.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
Not applicable.
NAMES OF PARTIES TO A JOINT RESEARCH AGREEMENT
Not applicable.
REFERENCE TO AN APPENDIX SUBMITTED ON COMPACT DISC
Not applicable.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to the techniques used in the construction of residential housing.
More specifically, the subject of the present invention is a new type of building for which the majority of components, about 80% including the interior works, are prefabricated in a plant.
The subject of the present invention is also not only the means for manufacture of the components but also for erecting the building.
2. Description of Related Art Including Information Disclosed Under 37 CFR 1.97 and 37 CFR 1.98
Traditionally residential housings, such as individual homes or small condominiums, are constructed on site by assembling various construction materials. For the construction of the bearing or non-bearing walls, bricks or building blocks are used. For creating the building openings, prefabricated door and window frames are used. For the roofing, use is made of structural timbers such as prefabricated girders that have been adapted so they can support a roof cover consisting of tiles.
The construction of a residential building therefore requires several skilled workers that need to convene on the site in accordance with a pre-established scheduling which keeps track not only of the order in which these different skilled workers work but also of the duration of their individual activities.
This widely used mode of operation is subject, most of the time, to the uncertainties of weather which interrupt for shorter or longer periods of time particularly the construction of outside walls and the roof. These delays which are beyond anybody's control interfere with the scheduling plan by postponing the periods of activity of the different trades at the risk of one of them not being available at the required time.
The cost of construction is directly linked to the competence of the personnel employed as well as to the quality of the construction materials being used. Ordinarily the cost for labor and the contractor represents between 70 and 80% of the total cost whereas the materials represent only 20 to 30% of the cost of construction.
Another factor that affects the cost of construction is the level of protection against natural disasters which the construction can provide its occupants because of its design.
Those structures which can provide a high level of protection against fire, earthquakes, tornadoes etc. are especially expensive and consequently inaccessible to persons with modest incomes.
The in-plant manufacture of housing modules and their assembly on site is well known. The in-plant manufacture of these modules allows the builder to free himself of weather-related uncertainties and the caisson design of the various modules makes them highly resistant to natural disasters. However, this construction method offers few architectural variations thereby limiting the number of housing models that can be offered.
Also, the dimensions of each caisson are limited by the constraints imposed by the clearance limitations of road transport.
From prior art, one is also familiar with building manufacturing methods which consist of the erection of a bearing frame on a horizontal slab formed on site and of the fastening of prefabricated panels to this framework. The problem with this type of construction lies in the low resistance to earthquakes, unless metal frames are used.
One also knows from prior art, prefabricated buildings that are placed on foundations that are also prefabricated. Such a method can be illustrated in particular with the patent application US 2001/0023563 (PHILLIPS) concerning a permanent foundation for a prefabricated house. This permanent foundation consists of reinforced concrete beams with an upstanding T section put into the ground not in a grid, but parallel to each other at regular intervals. These girders are not joined to each other and cannot confer to the foundation all the rigidity it needs to have.
From the Australian application AU 27958 (SIGAL), one is also familiar with a building that comprises a peripheral foundation and some pads 11 that are implanted in the soil within the space demarcated by the foundation. But these pads are not connected to the peripheral foundation and cannot form together with the latter a rigid grid all in one piece. Such an arrangement is not apt to form an anchorage in the ground that is dimensionally stable and capable of resisting the weight load represented by the building and capable of mechanically resisting any seismic shocks.
From the U.S. Pat. No. 6,085,432 (VAN DER SLUIS) one also knows a positioning device that provides a certain orientation to an upright that is designed to receive a pylon. This device is not suitable for placing the upper face of the upright in the horizontal position.
BRIEF SUMMARY OF THE INVENTION
The aim of the present invention is to mitigate the afore-mentioned problems by providing a building, the components of which are in large part prefabricated in a plant and which are assembled on site in order to reduce the building costs and to be independent of weather-related uncertainties.
A further goal of the present invention is to provide a building that is capable of resisting natural disasters without additional expenditures for construction.
Another goal of the present invention is to provide a building the elements of which can be assembled on site without the traditional know-how, by using methods and tools that are adapted to the prevailing conditions on site.
Another aim of the present invention is to considerably reduce the length of time needed to construct the building.
A further aim of the present invention is the integration at a level equal to at least 80% of the interior construction.
For this purpose, the residential housing building in particular whose components are mostly prefabricated, including a foundation that supports a building slab, walls erected on the slab, a ceiling supported by the walls and a roofing structure supported by the walls. The foundation is constituted of foundation blocks that are poured on site in appropriate trenches, rigidly linked by shapes of longitudinal ties also poured on site in appropriate trenches. Each foundation block is equipped with a vertical prefabricated pillar with a horizontal upper plane face, the upper plane faces of the various foundation pillars all being positioned in the same horizontal plane above the ground and bearing, away from the ground, the building slab and each vertical pillar being rigidly attached to the foundation block that supports it.
The shapes of longitudinal ties will be arranged in a mesh of rows and columns, the blocks being positioned at the intersection of such rows and columns. The different elements of this foundation (ties and blocks) are solidly interconnected and form a rigid whole of one piece anchored in the ground, being capable of spreading the loads and of withstanding seismic shocks without breaking.
An advantage of this arrangement is to keep the construction base away from the ground. In this way a sanitary space is created between the ground and the construction base. Another advantage of this arrangement is that it limits the extent of the contact areas between the ground and the base so one can dispose, at the level of these mechanical contacts, of means to limit and absorb the seismic energy that is likely to be transmitted by the ground.
According to another characteristic of the invention the pillars are placed on site and put at adequate height before the shapes of longitudinal ties and the foundation blocks are poured.
In this way, the prefabricated pillars can be cast-in, in their lower area, into the concrete, constituting the blocks which support them.
In order to strengthen the anchorage of the pillars to their blocks, the metal reinforcement (re-bars) inside each pillar, according to another aspect of the invention, emerges vertically from the lower face of the pillar to be cast in the concrete of the corresponding block. In this way a particularly sturdy attachment of the pillars to their blocks is obtained.
According to another characteristic of the invention, the base plate is constituted by a base frame arranged as a grid and by a floor resting on the base frame and rigidly attached to the latter. The base frame consists of prefabricated, prestressed longitudinal ties resting at their ends on the vertical pillars, being interconnected at their ends, and the floor consists of a stone floor in a meshwork including anchorage that is itself arranged in grid form, the anchorage being rigidly attached both to the stone floor and to the base frame. The meshwork of the base frame and the meshwork of the floor are being in correspondence with each other. This arrangement gives the base high rigidity and high mechanical strength.
The meshwork formed by the base frame comprises rows and columns at the intersection of which the foundation pillars are placed. The meshwork represented by this base is thus superposed over the grid which forms the foundation. In this manner, two rigid and strong grids are placed one on top of the other.
According to another characteristic of the invention, the flooring plate of the floor is formed by the juxtaposition of prefabricated, self-supporting, re-enforced plates that are arranged in meshwork and by a meshed anchorage the loops of which are peripheral to those of the flooring plate and attached to the latter.
According to another characteristic of the invention, each slab forming the floor comprises along one of its longitudinal edges a longitudinal structural rebate that is meant to receive, following the abutment of the slabs, a reinforcing and linking anchorage constituted by concrete and an internal metallic reinforcement (re-bar) presenting itself in the form of a rod, with said anchorage being linked to the peripheral anchorage of the floor.
According to another characteristic of the invention, the metallic reinforcement in the form of a rod extends over the two end faces of the longitudinal tie to become integral with the peripheral anchorage included in the floor, this anchorage being poured on site.
According to another characteristic of the invention, each slab has on one of its longitudinal edges a kind of tongue and on the opposite edge a kind of groove.
With such a disposition the slabs are assembled together by engaging the tongues in the grooves. Such an arrangement strengthens the connection of the different slabs to each other.
According to another characteristic of the invention associated with the floor are inner-partition elements which are covered on their inside face to the building with a cold insulation, the elements and the insulation on the one hand and the opposite slab edge faces on the other hand constitute the lateral flanks of the formwork of the anchorage of the floor.
The advantage of this arrangement lies in the utilization of actual construction elements for execution of the formwork of this anchorage.
According to another characteristic of the invention, the floor anchorage is rigidly connected to the base frame, in particular to the concrete, ensuring the connection of the longitudinal ties among themselves.
According to another characteristic of the invention, the connection between the longitudinal ties of the base frame and the peripheral anchorage of the floor is obtained by one single pouring of concrete.
In this manner one obtains a mono-block assembly, constituted by the base frame and the floor, presenting an especially high degree of solidity and this without the formation of a thermal bridge.
For regions where the risk of earthquakes is low or non-existent, the two rigid assemblies which constitute the foundation and the base may be rigidly connected one to the other.
So, according to another aspect of the invention, each pillar contains a vertical reinforcement in readiness, emerging from its upper face, intended to be lodged in the gap between the end front faces of the prefabricated longitudinal ties, and each prefabricated, prestressed longitudinal tie is provided with internal, longitudinal metal reinforcement emerging from its frontal faces arriving also in the afore-mentioned gap which eventually is filled with bonding concrete.
One obtains thus a particularly rigid connection between the base frame formed by the longitudinal ties and the support pillars.
But for regions where the risk of earthquakes cannot be neglected, the invention in accordance with another of its aspects provides for the interposition between the pillars and the base frame of mechanical isolating devices suitable for limiting or suppressing the spread of seismic waves from the ground to the construction.
According to a first form of execution, each isolating device consists of a metallic, horizontal base plate integral with the upper face of the corresponding pillar, and a side friction block in sliding support on the base plate and integral with the base frame.
Such an arrangement filters the horizontal seismic vibrations between the foundation and the base frame, but does not filter the vertical vibrations.
According to another characteristic of the invention that aims to resolve the afore-mentioned problem, the isolating device consists of an elastomer pad sandwiched between two horizontal metallic plates one of which is made integral with the corresponding pillar and the other with the base frame. Such an arrangement isolates only partially the base frame as far as the horizontal components of a seismic wave are concerned and softens the vertical components of this wave.
According to another variant execution of the isolating device, the latter is composed of a combination of the two preceding devices.
According to another characteristic of the invention, the building walls are formed on the base and are constituted by abutment and assembly of prefabricated wall panels.
According to another characteristic of the invention, plane facade panels are used, and possibly angled panels in the form of dihedrons.
According to another characteristic of the invention, the facade and angled panels each include a rigid, horizontal lower compression plate and internal reinforcement which is mechanically linked to the compression plate and includes several elongated elements extending in vertical anchorage housing which are vertically placed in the panel, with at least one of these reinforcement elements extending above the upper edge of the panel and being fitted above said edge, as a handling and lifting device.
According to another characteristic of the invention, each prefabricated wall panel includes in its lower part a rigid bearing and support plate which is mechanically connected to a re-bar extending vertically in the wall and to which re-bar, in the upper part of the wall, at least one lifting and shipping tie rod is rigidly attached.
Because of this disposition, the hoisting effort will be transmitted to the rigid compression plate by the internal reinforcement re-bar in the wall panel.
According to another characteristic of the invention, the compression plate is made of reinforced concrete and the wall panel is created by assembling construction blocks on the compression plate.
According to another characteristic of the invention, the horizontal feet protruding laterally in relation to one of the large wall panel faces are attached to the rigid compression plate of each wall panel, said wall panel being attached to the floor more particularly by these feet.
According to another characteristic of the invention, the wall panels are attached to the floor by glueing their base to the anchorage of the floor. To obtain this bond, an adhesive mortar is used preferably.
The point of these last two arrangements is to allow a fast attachment of the wall panels to the floor, in an operation which does not require the traditional know-how.
According to another characteristic of the invention, the wall panels are connected to each other by a mechanical assembly of their reinforcement re-bars on both sides of their mating surfaces and by glueing along their vertical abutting edges.
According to another characteristic of the invention, the wall panels are assembled in their upper part by a continuous horizontal anchorage, the protruding reinforcement elements on the upper edges of the panels being tied into this anchorage.
According to another characteristic of the invention, each vertical edge of each panel features a continuous vertical groove running over the entire height of the panel, this groove receiving against its bottom face one of the reinforcement elements of the panel, this element being attached to the bottom face of said groove.
According to another characteristic of the invention, in areas of significant seismic risk, the connection between the panels is reinforced by concrete being poured in the compartments formed each by the anchorage grooves of two adjacent panels so as to create a wedging. In this hypothetical case, the grooves will be deeper.
This bonding concrete attaches itself to the peripheral anchorage of the floor thereby further strengthening the mechanical connection of the panels at the base of the construction.
According to another characteristic of the invention, for panels with an opening such as a door, window or French window, the lintel of the frame of said opening presents a U-section and forms a horizontal anchorage volume intended to receive a reinforcement and a concrete, said reinforcement penetrating by its two ends into the two vertical anchorage recesses which the panel presents. Such an arrangement is primarily intended for buildings that are put up in earthquake-prone areas.
The take-up of the anchorage of the lintel in the other two vertical anchorages of the panel tends to strengthen the framing of the opening.
According to another characteristic of the invention, in order to form the corners of the construction, corner panels are provided which present the same characteristics as the flat panels, this corner panel forming a dihedral angle presenting furthermore a vertical anchorage volume that is at a right angle to the peripheral anchorage of the floor, this volume of anchorage receiving a fastener to the peripheral anchorage of the floor.
According to yet another characteristic of the invention, the various corner panels or wall fronts are each provided, along their upper edge, with a horizontal recess which joins the two lateral recesses they each have, said horizontal recess constituting a horizontal volume of anchorage into which the fasteners penetrate that are installed in the vertical volumes of anchorage formed by the lateral recesses.
According to another characteristic of the invention, at least one of the wall panels presents a vertical cutout in which a power line or a wastewater pipe is installed.
According to another characteristic of the invention, the bearing ceiling, resting on the walls and attached to the latter, consists of a meshed slab formed by juxtaposition of prefabricated plates and attached to each other and by a reinforced meshed anchorage forming rigid frames around and in the slab, said slab being attached to said anchorage.
According to yet another characteristic of the invention, the ceiling slab organized along the mesh is formed by prefabricated assembly of ceiling plates, presenting each along one of their longitudinal vertical edges a tenon and along the opposite longitudinal edge a mortise, the different plates being attached to each other by fitting the mortises of the ones into the tenons of the others, said plates resting on a frame formed by abutment of wall panels of small height.
According to another characteristic of the invention, each ceiling plate, perpendicular to the tenon, includes a longitudinal rebate intended to receive, after assembly of the plates, a reinforcing anchorage formed of concrete and steel reinforcement in lateral overlap to be taken up in the horizontal peripheral anchorage at the ceiling.
According to another characteristic of the invention, the self-bearing roofing is formed by glued assembly along their lateral edge of prefabricated self-bearing roofing plates, the roofing slab being mechanically connected to the anchorage of the floor and an anchorage formed along the upper surfaces of the gable wall.
As a variant, according to another characteristic of the invention, the roofing framework is formed by small prefabricated girders and the ceiling is formed by plaster slabs suspended from the framework.
In this hypothetical case, the peripheral anchorage which allows connecting the bottom part of the construction, by creating an upper belt, will be established by blocks of cellular concrete presenting an anchorage channel in which an appropriate reinforcement is placed and concrete is poured.
According to yet another characteristic of the invention, the different components of the building are assembled to each other by a continuous anchorage forming a framework.
Such a building constructed in this manner is particularly sturdy and its walls can now be built on a perfectly horizontal base by virtue of the adjustment of the height of the pillars before the foundations are poured, the reason for such an arrangement is to ensure the surface evenness and the horizontal position of the base even in the event that the foundation is not level.
The present invention is relative also to a manufacturing process of wall panels of the building according to the invention. This process consists essentially of manufacturing a continuous wall pane by assembly, blocks in successive rows and to make vertical cuts in the wall pane in order to divide it into wall panels.
According to another characteristic of the method according to the invention, the building blocks are assembled by glueing.
According to another characteristic, the method according to the invention consists of the height calibration of the wall pane, before the vertical cuts are made.
According to another characteristic, the method according to the invention consists of making the anchorage channels and bore holes for handling in the panes, after cutting the panes (into panels).
The invention is also relative to an installation for the implementation of the method defined above. The installation includes a mobile linear conveyor facing a block glueing and assembling station, a height calibration station, a wall panel cutting station, a lateral grooving station, an angle grooving station and a panel drilling station for their handling.
The subject of the present invention is also installation equipment for the prefabricated elements.
Thus, in accordance with another characteristic of the invention, each prefabricated pillar is placed by using an adjustable support comprising a pillar holding structure, in the form of a sheath, said structure being mounted on at least three height-adjustable feet.
Finally, another advantage related to the building mode is the manufacture of the building components, in hidden time, during the drying of the foundation, the adequate duration of drying being approximately one month.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
Other advantages, goals and characteristics of the invention will become apparent when reading the description of a preferred form of execution given on a non-limiting basis, by referring to the attached drawings.
FIG. 1 is a perspective view of a building according to the invention, with roofing according to a first form of execution.
FIG. 2 is an exploded view of the building shown in FIG. 1 .
FIG. 3 is a perspective view of a building according to the invention, with roofing according to a second form of execution.
FIG. 4 is an exploded view of a building according to FIG. 3 .
FIG. 5 is a perspective view of the foundation and the base frame of the base of the building.
FIG. 6 shows the different forms of execution of the means to isolate the foundation from the base.
FIG. 7 is a perspective view of the base of a building.
FIG. 8 is a cross-sectional view of a drawing of a base showing the detail of the floor of the latter.
FIG. 9 is a perspective view of a floor with the means of floor panel heating.
FIG. 10 is a perspective view of the assembly of two facade panels to an angle panel.
FIG. 11 is a detailed top plan view of the assembly according to FIG. 10 .
FIG. 12 is a detailed top plan view of the assembly of two facade panels to an angle panel for earthquake-prone areas.
FIG. 13 is an elevational view of a panel with a window-type opening.
FIG. 14 is a sectional view along the line AA of FIG. 13 .
FIG. 15 is an elevational view of a panel with a French-window type opening.
FIG. 16 is a sectional view along the line AA of FIG. 15 .
FIG. 17 is a side-face elevational view of a wall panel with means of fastening to the floor.
FIG. 18 is a perspective view of a bearing ceiling.
FIG. 19 is an elevational view of a bearing ceiling.
FIG. 20 is a perspective view of roofing for earthquake-prone areas.
FIG. 21 is a side-face elevational view of the roofing according to FIG. 20 .
FIG. 22 is an elevational view of the roofing according to FIG. 20 .
FIG. 23 shows a perspective view of the tools keeping the wall panels vertical and the mold pouring the bonding concrete of the longitudinal ties of the base frame.
FIG. 24 shows a perspective view of the pillar placing support.
FIGS. 25 and 26 are front and rear perspective views of a wall panel manufacturing jig used for making a facade wall panel.
FIG. 27 is a front perspective view of the jig according to FIGS. 25 and 26 , used for making an angle wall panel.
FIG. 28 is a perspective view of a panel presenting a reduced height.
FIG. 29 is a perspective view of a handling device for low height wall panels.
FIG. 30 is a sectional view of a handling device according to FIG. 29 , the wall panel being placed on said device.
FIG. 31 is a cross-sectional view of a drawing showing the joint of two panels forming one of the angles of the construction.
FIG. 32 is a perspective view of an automatic continuous manufacturing installation for wall panels.
DETAILED DESCRIPTION OF THE INVENTION
As shown, the building according to the invention includes a foundation 1 on which, away from the ground, a building base 2 is installed, supporting walls 5 on which a ceiling structure 6 and roofing 7 are installed, these different components, aside from certain elements of the foundation, being prefabricated in a plant.
Foundation 1 includes blocks 10 which have been poured in trenches made in the soil, are joined by longitudinal ties 11 that have also been poured in trenches made in the soil, the blocks 10 being equipped with prefabricated vertical pillars 12 on which rests the building base 2 , the vertical pillars 12 being rigidly integral with the blocks which support them.
The blocks 10 and the longitudinal ties 11 are arranged in a four-sided grid comprising rows and columns that are perpendicular to each other. The columns and the rows are formed by the longitudinal ties; the blocks are formed at the intersection of the rows and columns.
Between the base and the longitudinal ties, it is possible to position inner partition elements to close off the crawl space created under said base.
Each pillar 12 has internal rebars of which at least one end is outside of the pillar and forms a lower reinforcement on hold. The other end can also be outside of the pillar and form an upper reinforcement on hold.
The upper plane faces of the pillars 12 are placed in a single horizontal base plane place above and at a distance from the ground.
The base 2 rests on the upper face of the pillars 12 either directly or through the intermediary of means 13 of mechanical isolation capable of suppressing or limiting the propagation of seismic waves.
In case the base must rest directly on the pillars 12 , a rigid attachment of the latter to the base will be established. In this hypothetical case each pillar 12 will include the upper reinforcement bar or rebar on hold by which it will be fastened to the base as described further down.
According to a first form of execution, the means of isolation is constituted by two horizontal base plates 130 made of steel, that are integral respectively with the upper face of the pillar 12 and the base 2 , and with a side-friction block 131 made of bronze that is placed between the two steel plates.
According to another form of execution, the means of isolation 13 are constituted by an elastomer block 132 serving as a shock absorber sandwiched between two metallic plates 133 that are integral with the pillar 12 and the base 2 respectively.
One can also provide a means of isolation 13 consisting of the combination of the preceding means, that is to say by steel plates 133 holding between them a shock absorber 132 , with one plate being attached to the upper face of the pillar 12 and with the other one receiving the sliding support of a side-friction block 131 in bronze on which rests a steel plate 130 which is attached to the base 2 .
The base 2 is constituted by a base frame 20 arranged in a grid pattern and by a floor 21 resting on the base frame 20 and rigidly fastened to the latter.
The base frame 20 is constituted by prefabricated, pre-stressed longitudinal ties 200 , resting at their ends on the vertical pillars 12 either directly or through the intermediary of means of isolation. The ties are fastened to each other at their ends. As one can see, the longitudinal ties 200 are arranged in a grid which strengthens the mechanical strength of the base.
Each of these longitudinal ties contains a pre-stressing steel armature, jutting out of its frontal face in order to form reinforcement on hold.
By these reinforcements and concrete, several adjacent longitudinal ties 200 are attached to each other.
In the case where these longitudinal ties 200 rest directly on the pillars 12 , the rebar contained in the latter are also covered in the bonding concrete of the longitudinal ties 200 . In this manner, the fastening of the base to the pillars 12 is assured.
The floor 21 is supported by the base frame and is integral with the latter.
This floor consists of a slab that is associated with the meshed anchorage 210 that is connected to the slab on the one hand and to the concrete bonding the longitudinal ties among each other on the other hand The slab perpendicular to the grid of the base frame 20 is constituted by assembly of plates 211 that are each provided along their longitudinal edges with a tenon and a mortise, the assembly of the plates 211 being achieved by fitting together the tenons and the mortises as well as glueing. One will notice that this assembly of slabs 211 constitutes a floor grid containing a peripheral anchorage with armature 214 . It should be noted that the anchorage 210 of the floor 21 is formed between the slab and external elements of inner partitions 212 . Each are covered along their inner face to the building with a thermal insulating material 213 . These elements of inner partitions and their insulating material prevent the thermal bridge between the anchorage and the outside of the building.
Each slab 211 includes along one of its longitudinal edges a receptacle 215 which forms, by abutment with another slab, a volume of anchorage. An armature 216 is placed in the form of a concrete reinforcing bar, and concrete is poured. The concrete reinforcing bar extends over the lateral faces of the slab to be joined to in the anchorage of the floor.
The slabs 211 can each be equipped with a tenon and a mortise for joining.
The floor 21 of the building can accept, after it has been boxed up, floor panel heating of the low temperature type which can include cellular circulating conduits 217 , for instance in polyethylene, that are implanted in a preformed insulating material 218 that is placed directly on the slab. These conduits are provided to be then connected to a unit heating station installed in an appropriate location in the building. These conduits 217 are intended to convey a heat-transfer fluid, such as water for instance.
Floor plates 219 placed on top of the insulating material 218 provide protection of the floor heating installation, as these protection plates can receive a facing of the tile type 220 . Advantageously these floor plates 219 will be attached in a removable manner, by screws for example, so that they can be easily removed to grant easy access to the circulating conduits 217 .
The walls are formed by assembly along their vertical edges of plane shaped prefabricated panels 50 as far as the facades are concerned and possibly in the shape of right angle 51 with respect to the corners of the building.
Each wall panel 50 , 51 includes, according to a first form of execution, a horizontal lower rigid support footing 52 on which, along three or four of their faces, construction blocks 53 are assembled by glueing and arranged in successive courses.
The rigid footing 52 can be made of reinforced concrete.
Preferably the footing, on its outer face to the building receives an element of interior partition made of cellular concrete which is lined with a thermal insulation material. In this way, one avoids any thermal bridge on account of the presence of the footing.
Each wall panel features an internal reinforcing armature that is mechanically connected to the bearing footing 52 . This reinforcement includes several elongated elements 54 which extend into vertical recesses of anchorage formed in the panel along its entire height or along most of its entire height. These elements 54 or certain ones among them receive above the upper edge of the panel a handling device in the form of an eye bolt.
The vertical anchorage recesses can be constituted by channels 55 made in the vertical edges of the panel and/or by vertical cylindrical shafts placed in the heart of the panel.
The wall panels 50 , 51 are by their footing 52 bearing down on the peripheral anchorage of the floor 21 and are attached to this floor 21 by a bond through adherence and by a bond through friction.
The bond through adherence is realized by glueing of the lower edge of each panel 50 , 51 to the floor 21 , and the bond through friction is realized by fasteners, nails for instance, that are engaged on the one hand in drill holes created in the horizontal feet 57 that are integral with the support footing 52 , and on the other hand in the floor slab.
The wall panels 50 and 51 are connected to each other by glueing of their respective vertical edges but also in upper areas, above their horizontal edges, by the mechanical connection of their armatures.
In this regard, the reinforcement elements 54 lodged in the vertical channels 55 will be connected in their upper part 58 by bolts or weldments.
Each element of reinforcement 54 can consist of a flat iron fastened by studding in the channel 55 and taken up in the footing 52 .
In FIG. 12 , one can see that by abutment of the wall panels 50 , 51 on either side of each abutment plane a recess formed by two vertical channels 55 facing each other. To strengthen the connection between the wall panels, reinforcement in the form of a re-bar is placed in this recess and concrete is then poured into the latter. In this manner, a reinforced connecting key 59 will be created between two adjacent panels.
The wall panels will be connected in their upper part by an anchorage that runs along their upper horizontal edge. In this anchorage, the upper overlapping parts of the reinforcement elements 54 of the panels 50 , 51 will be joined.
The building openings, such as doors, windows or French-windows will be made and equipped in the plant with appropriate framing. In the case of a window 8 ( FIG. 13 ), the rise area of the window support 80 is covered with an appropriate insulating material 81 . Against this insulating material, an interior partition 82 is positioned. In the case of a French-window 9 ( FIGS. 15 and 16 ) or of a door, the lintel 90 will be reinforced and the reinforcement of the lintel 90 will penetrate into the lateral anchorage channels 55 to be taken up by the vertical anchorages. This lintel will be created by blocks with a U profile presenting an anchorage recess into which the afore-mentioned armature is inserted and then concrete is poured.
On the upper anchorage connecting the wall panels 50 , 51 with each other, a ceiling 6 is installed which consists of a slab 60 formed by assembly of plates 61 of the same type as those used for the floor. In this way, these self-bearing plates feature each along one of their longitudinal edges a tenon and along the opposing longitudinal edge a mortise. The different plates 61 being connected to each other by fitting the mortises of the ones into the tenons of the others. The slab 60 rests on a frame 62 created by abutment of appropriate elements of low height, and it is connected to this frame by an anchorage 63 which is associated with inner partition elements 64 which are covered on their inner face with a thermal insulation 65 . This arrangement eliminates thermal bridges at the anchorage.
The plates 61 feature perpendicular to their tenon, a longitudinal rebate 66 to receive, upon assembly to an adjacent plate, a reinforcing anchorage made of concrete and a re-bar 67 in lateral overlap to be taken up in the horizontal peripheral anchorage of the ceiling 6 .
The self-bearing roofing 7 , known as such, is formed by assembly by glueing along their lateral edge of prefabricated, self-bearing roofing plates 70 , the roofing slab being mechanically connected to the anchorage of the floor and to an anchorage formed along the upper faces of the gable walls.
The roofing will be equipped with a ridge anchorage. Also, on the periphery of each roof slope an anchorage can be created, the ridge anchorage constituting the upper segment of the latter.
Finally the various anchoring of the building are tied together to form a rigid framework without any point of discontinuity.
According to another form of execution, such as shown in FIG. 28 , the wall panels 50 are of a lesser height and have no bottom footing. For example, the height of such panels will be around 1.50 meters.
The advantages of such an arrangement are multiple. It facilitates in particular the handling operations of such panels 50 and this present also increased stability in comparison with panels of greater height, thereby limiting as much the danger of capsizing on the construction site as well as the danger of accidents.
FIGS. 29 and 30 show a handling device 19 for such wall panels. This device 19 is constituted by 2 vertical columns 190 , connected by horizontal cross-members 191 . Each column features, at its lower end, a horizontal drift pin 192 , support, which is meant to be engaged in a drilled hole 501 in the wall panel 50 to be handled. This handling device 19 comprises furthermore a holding structure 193 that is articulated to the two columns 190 and can be folded down on the wall panel 50 . The holding structure 193 is equipped with a hook element 194 that comes in front of the wall panel 50 to keep it stable against the columns 190 . Finally the device 19 includes a lifting cross-member 195 with an eye bolt 196 , this cross-member being mounted on two horizontal upper arms 197 that are rigidly attached to the columns 190 . The lifting cross-member 195 is placed perpendicular to the position of the center of gravity of the wall panel 50 when the panel is in place in the device 19 . In order to be able to adjust the position of this lifting cross-member and more precisely the position of the eye bolt 196 relative to this center of gravity, the horizontal upper arms 197 are each provided with an oblong through-hole. The cross-member is fastened to the arms by bolts, the shaft of their threaded part being engaged in the through-hole of the corresponding arm. Adjustment is made by moving the cross-member along the arms.
According to another form of execution, as shown in FIG. 31 , the corners of the building are no longer formed by corner panels 51 , but by wall panels 50 with the vertical edge of one panel coming to bear on the large internal face of the other panel. This vertical edge and this large face featuring each a vertical groove matching up with the other groove so as to form a space for vertical anchorage in which a metal reinforcement will be placed and a bonding concrete will be poured.
The installation of the wall panels 50 is made from one corner of the building to another corner of this building. The accumulation of the dimensional tolerances can be such that the two grooves 55 of the panels forming the last corner of the building are unable to match up with each other. To eliminate such a risk which would deprive the corner of the building of its vertical anchorage, one of the two grooves 55 is wider than the other. In this way, the narrower groove 55 will always be matching up with the wider groove. These two grooves 55 may feature a cross-section in dovetail shape, a square or rectangular cross-section.
For the execution of facade and corner panels, an installation jig 16 will be used which features at least one lower plane suspension face 160 , for reference, a plane dorsal face 161 for reference perpendicular to the preceding one and at least one plane lateral face 162 for reference by alignment, perpendicular to the two preceding ones. The prefabricated footing of the panel is placed on the lower face 160 against the dorsal wall 161 and against the lateral sidewall 162 . The different rows of blocks rest by the dorsal face of the blocks against the dorsal face of the jig, the first block of each row resting also against the lateral face 162 of the jig.
The jig 16 will also be equipped with running gear for easy movement on the ground.
On this jig will be assembled by glueing, on at leas three of their faces, the different building blocks 53 that make up the wall panel. It should be noted that the assembly of the blocks to each other is made by glueing thin joints thereby reducing the thermal bridges.
The anchorage wells which are contained in at least the corner panels will be obtained by alignment of through-holes drilled in the building blocks.
The wall panels 50 , 51 built with these jigs 16 will then be checked for their geometry and cut to adequate dimensions along their vertical edges using an appropriate cutting instrument equipped with a cutting head guided by sliding rails and containing a cutting tool of the circular saw type for instance. Such an arrangement is favorable for obtaining a high degree of precision in the geometry of the panel as well as in its dimensions. Thus, the degree of precision from wall to wall will be in the range of a millimeter. It should be noted that the cutting planes can be perpendicular to the large faces of the panels or oblique relative to these faces, since the cutting head is adjustable. Such an oblique cutting position allows the creation of housing angles that are different from a right angle.
The different anchorage grooves as described will be machined in the panels.
The wall panels 50 can also be made continuously with an appropriate manufacturing installation. Such an installation is shown in FIG. 31 . This installation 30 includes a mobile linear conveyor 31 facing a station 32 where blocks are placed in juxtaposed rows and assembled by glueing, a height calibration station 33 , a wall panel cutting station 34 , a lateral grooving station 35 , an angle grooving station 36 and a station 37 where panel are drilled for their handling.
The face of the wall is built on the linear conveyor. The latter is of any known type.
The purpose of the height calibration station is to ensure either by cutting or abrasion that the different panels are of equal height.
The panel cutting station will be equipped with a cutting head with a cutting blade of the circular type for instance. This cutting head will be guided by vertical slide rails and will be adjustable by pivoting around a vertical axis in order to achieve cuts along a plane that is perpendicular to one of the large faces of the wall panel or along a plane forming an acute or obtuse angle.
The purpose of the grooving stations 35 and 36 is to make the anchorage grooves in the panel.
The purpose of the panel drilling station is to make in the lower row of blocks of each panel at least one drilled hole 501 through the thickness of said panel.
From the inside faces in the wall panels or only in certain ones of these, different cuts will also be made to accommodate the different energy conduits such as electric conduits to hold the electric cables, gas lines, water pipes and waste water drain pipes. Each cut will be dedicated to one particular type of conduit and the different cuts made in the wall panel will be made at a certain distance from each other so as to ensure the physical separation of the various conduits. Furthermore, an electrical separation will also be achieved because of the electrically insulating nature of the building blocks forming the wall panel.
The wall panel will be advantageously equipped in the plant with the different energy and wastewater drain conduits as well as with the majority of installations associated with these conduits. Thus, the panel for the electrical equipment will be pre-wired, therefore being equipped with electric sockets and switches, control panels etc.
Prior to the installation of equipment associated with the conduits, the wall panel will receive a facing sheet to ensure the covering of the inside face of the wall panel. The cuts and the conduits contained in them are thus protected by this facing sheet. Such an arrangement avoids the use of coatings and other products usually applied for filling up the cuts.
The facing sheet will be advantageously attached to the panel in a non-permanent way, so that it can be removed, if necessary, for easy access to the conduits contained in the panel.
Preferably this facing sheet will be attached by stapling.
It should be noted that this facing sheet advantageously complements the insulation properties of the wall panel. It should also be noted that this facing sheet presents a finished inside face that is ready to be painted, plastered or covered with wallpaper.
It becomes clear that panels are delivered to the construction site that are to a large extent equipped with the interior works which translates into significant time and labor savings.
On the site, the electric wiring contained in the wall panels will be connected to appropriate terminal blocks, advantageously placed in the attic of the building. With respect to the gas, water and wastewater systems that may be contained in the panel, they can be connected to conduits of the same type located in the crawl space between the ground and the base or may be under the floor plates that the floor is equipped with.
For keeping the wall panels upright during their installation and in order to avoid their warping, removable clamps 17 placed on the upper part and this on both sides of the joining faces as well struts will be used to ensure the panels are kept upright.
Removable forms 18 , including vertical form partitions and removable clamps will be used for pouring concrete between the longitudinal ties of the base frame.
Finally, the different building blocks and the different plates used for the construction will be made of cellular autoclave concrete.
The advantage of using concrete of this type is manifold. In effect, it has a mechanical strength that is at least equal to other materials but in addition to that its low density in the range of 400 kg/m 3 greatly facilitates the handling of the completed panels. The low weight of the panels will result in lower inertia of the latter which is always an advantage for buildings that may be susceptible to earthquakes. Another advantage of a low weight is that it has a favorable influence on the cost of transportation.
This concrete also features a high level of sound and thermal insulation so that the panels produced with it will have these characteristics. Finally, once it is dry, this type of concrete can easily be machined. It will thus be easy to make cuts, grooves and cutouts in every wall panel.
Another asset in the utilization of such a material is that it allows the evacuation of water vapor because of the very favorable value of resistance to the diffusion of water vapor. Therefore the finished walls breathe and contribute the quality of ambient air of the residential units.
Such a material is known particularly under the commercial name of Thermopierre™ or thermostone.
It should be noted that the glue used to bond the blocks between themselves as well as the panels and other elements has, after it has dried, a mechanical strength that is superior to that of the material the blocks are made of.
For placement of the prefabricated pillars 12 , an adjustable placement support 15 is preferably used which includes a pillar holding structure 150 in the form of a sheath. The structure is mounted on at least three feet the height of which is individually adjustable. The structure of the sheath 150 will be constituted for example by parallel steel jackets that are inter-connected by posts, some of which include through-screws 152 that press against the pillar 12 in order to ensure its (vertical) retention inside the structure.
With such a device it is possible to position the pillars 12 , by their upper face all at the same height and in a coplanar manner.
Preferably the pillars 12 will be positioned on the site before the foundation blocks and longitudinal ties above the trenches made for pouring of the blocks.
It goes without saying that the present invention may accept any arrangements and variants in the area of technical equivalents without thereby leaving the framework of the present patent.
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The residential building whose majority of components are prefabricated in a factory, includes a foundation supporting a bed, walls erected on the bed, a ceiling supported on the walls and a roof supported on the walls. The foundation is formed of foundation blocks that are cast on-site, in appropriate excavations, and joints by forms of stringers also cast on-site in appropriate excavations. Each foundation block is provided with a vertical pillar prefabricated in a factory, each vertical pillar having a horizontal upper planar face. The upper planer faces of the pillars are arranged along the same horizontal plane, receiving and supporting, at a distance from the ground, the bed of the building. The invention also relates to a method and device used for realizing the wall elements manually or automatically in a continuous manner.
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This application is a 371 of PCT/IB94/00407 filed Dec. 8, 1994 which is a continuation of Ser. No. 08/194,553 filed Feb. 10, 1994, now abandoned.
BACKGROUND OF THE INVENTION
The present invention relates to indole derivatives, intermediates for their preparation, pharmaceutical compositions containing them, and their medicinal use. The active compounds of the present invention are potent agonists and antagonists at the benzodiazepine receptor. Agonists and antagonists of the benzodiazepine receptor are useful in the treatment, prevention and diagnosis of anxiety, memory loss, sleep disorders or seizures. The compounds of the invention are also useful in the treatment of an overdose of benzodiazepine drugs.
The use of benzodiazepine receptor ligands in the treatment of anxiety and other disorders has been discussed in "New Trends in Benzodiazepine Research", 24 Drugs of Today, 649-663 (1988).
European Patent Publication 499,527, which was published on Aug. 19, 1992, refers to β-carboline derivatives which possess an affinity for benzodiazepine receptors and as such are useful agents in the treatment of degenerative central nervous system disorders, such as Alzheimer's disease.
U.S. Pat. No. 5,243,049, which issued on Sep. 7, 1993, refers to pyrroloquinoline derivatives which are γ-amino butyric acid (GABA) receptor antagonists. These pyrroloquinoline derivatives are claimed to be useful for the treatment of anxiety, sleep disorders, seizures and for enhancing memory.
U.S. Pat. No. 5,066,654, which issued on Nov. 19, 1991, refers to 2-aryl-3-heterocyclicmethyl-3H-imidazo 4,5-B!pyridines that are stated to be useful as anxiolytics and anticonvulsants.
A series of planar azadiindoles, benzannelated pyridoindoles, and indolopyridoimidazoles have been described as molecular probes that are useful for the definition of the molecular recognition elements of the benzodiazepine receptor in J. Med. Chem., 35, 4105-4117 (1992).
International Patent Application WO 93/23396; published Nov. 25, 1993, refers to fused imidazole and triazole derivatives as 5-HT 1 receptor agonists that are useful for the treatment of migraine and other disorders.
SUMMARY OF THE INVENTION
The present invention relates to compounds of the formula ##STR2## wherein X and Y are independently carbon or nitrogen;
R 1 and R 2 are independently selected from hydrogen, (C 1 -C 6 )alkyl, aryl, --(C 1 -C 3 )alkylaryl, --(CH 2 ) n --(C 4 -C 7 )cycloalkyl, --(CH 2 ) n CHO, --(CH 2 ) n CO 2 R 7 , --(CH 2 ) n CONR 7 R 8 , 3-succinamido, unsaturated heterocycle, benzo-fused heterocycle, --(C 1 -C 3 )alkyl-unsaturated heterocycle, and --(C 1 -C 3 )alkyl-benzo-fused heterocycle; wherein said unsaturated heterocycle and unsaturated heterocycle moiety of said --(C 1 -C 3 )alkyl-unsaturated heterocycle are selected, independently, from pyrrolyl, furyl, thienyl, oxazolyl, isoxazolyl, imidazolyl, thiazolyl, isothiazolyl, pyrazolyl, triazolyl, tetrazolyl, 1,3,5-oxadiazolyl, 1,2,4-oxadiazolyl, 1,3,5-thiadiazolyl, 1,2,4-thiadiazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, 1,3,5-triazinyl, 1,2,5-thiadiazinyl, 1,2,5-oxathiazinyl, and 1,2,6-oxathiazinyl; wherein said benzo-fused heterocycle and the benzo-fused heterocyclic moiety of said --(C 1 -C 3 )alkyl-benzo-fused heterocycle are selected, independently, from benzoxazolyl, benzothiazolyl, benzimidazolyl, thianaphthenyl, isothianaphthenyl, benzofuranyl, isobenzofuranyl, chromenyl, isoindolyl, indolyl, indazolyl, isoquinolyl, quinolyl, phthalazinyl, quinoxalinyl, quinazolinyl, cinnolinyl and benzoxazinyl; wherein each of said unsaturated heterocycle, benzo-fused heterocycle, --(C 1 -C 3 )alkyl-unsaturated heterocycle and --(C 1 -C 3 )alkyl-benzo-fused heterocycle may optionally be substituted on one or more ring carbon atoms with from zero to three substituents, said substituents being independently selected from bromo, chloro, fluoro, (C 1 -C 5 )alkyl, (C 1 -C 5 )alkoxy, (C 1 -C 5 )alkylthio, (C 1 -C 5 )alkylamino, (C 1 -C 4 )alkylsulfonyl, (C 1 -C 5 )dialkylamino, hydroxy, amino, nitro, cyano, trifluoromethyl, ##STR3## wherein said aryl groups and the aryl moieties of said (C 1 -C 3 )alkylaryl groups are independently selected from phenyl and substituted phenyl, wherein said substituted phenyl may be substituted with from one to three substituents independently selected from (C 1 -C 4 )alkyl, halogen (e.g., fluorine, chlorine bromine or iodine), hydroxy, cyano, carboxamido, nitro, and (C 1 -C 4 )alkoxy;
R 3 , R 4 , R 5 , and R 6 are independently selected from hydrogen, (C 1 -C 6 )alkyl, aryl, --(C 1 -C 3 )alkylaryl, --CN, --CHO, CO 2 R 9 , --NO 2 , --CONR 9 R 10 , --(CH 2 ) p OH, --(CH 2 ) p OR 9 , --(CH 2 ) p NR 9 R 10 and halogen (e.g., fluorine, chlorine bromine or iodine); wherein said aryl groups and the aryl moieties of said --(C 1 -C 3 )alkylaryl groups are independently selected from phenyl and substituted phenyl, wherein said substituted phenyl may be substituted with from one to three substituents independently selected from (C 1 -C 4 )alkyl, halogen (e.g., fluorine, chlorine bromine or iodine), hydroxy, cyano, carboxamido, nitro, and (C 1 -C 4 ) alkoxy;
R 7 , R 8 , R 9 , and R 10 are independently selected from hydrogen, (C 1 -C 6 )alkyl, aryl, --(C 1 -C 3 )alkylaryl, unsaturated heterocycle, benzo-fused heterocycle, --(C 1 -C 3 )alkyl-unsaturated heterocycle, and --(C 1 -C 3 )alkyl-benzo-fused heterocycle; wherein said unsaturated heterocycle and unsaturated heterocycle moiety of said --(C 1 -C 3 )alkyl-unsaturated heterocycle are selected, independently, from pyrrolyl, furyl, thienyl, oxazolyl, isoxazolyl, imidazolyl, thiazolyl, isothiazolyl, pyrazolyl, triazolyl, tetrazolyl, 1,3,5-oxadiazolyl, 1,2,4-oxadiazolyl, 1,3,5-thiadiazolyl, 1,2,4-thiadiazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, 1,3,5-triazinyl, 1,2,5-thiadiazinyl, 1,2,5-oxathiazinyl, and 1,2,6-oxathiazinyl; wherein said benzo-fused heterocycle and the benzo-fused heterocyclic moiety of said --(C 1 -C 3 )alkyl-benzo-fused heterocycle are selected, independently, from benzoxazolyl, benzothiazolyl, benzimidazolyl, thianaphthenyl, isothianaphthenyl, benzofuranyl, isobenzofuranyl, chromenyl, isoindolyl, indolyl, indazolyl, isoquinolyl, quinolyl, phthalazinyl, quinoxalinyl, quinazolinyl, cinnolinyl and benzoxazinyl; wherein each of said unsaturated heterocycle, benzo-fused heterocycle, --(C 1 -C 3 )alkyl-unsaturated heterocycle and --(C 1 -C 3 )alkyl-benzo-fused heterocycle may optionally be substituted on one or more ring carbon atoms with from zero to three substituents, said substituents being independently selected from bromo, chloro, fluoro, (C 1 -C 5 )alkyl, (C 1 -C 5 )alkoxy, (C 1 -C 5 )alkylthio, (C 1 -C 5 )alkylamino, (C 1 -C 4 )alkylsulfonyl, (C 1 -C 5 )dialkylamino, hydroxy, amino, nitro, cyano, trifluoromethyl, ##STR4## wherein said aryl groups and the aryl moieties of said --(C 1 -C 3 )alkylaryl groups are independently selected from phenyl and substituted phenyl, wherein said substituted phenyl may be substituted with from one to three substituents independently selected from (C 1 -C 4 )alkyl, halogen (e.g., fluorine, chlorine bromine or iodine), hydroxy, cyano, carboxamido, nitro, and (C 1 -C 4 )alkoxy;
n is 0, 1, 2, or 3;
p is 0, 1, or 2;
and the pharmaceutically accepted salts thereof.
The present invention also relates to the pharmaceutically acceptable acid and base addition salts of compounds of the formula I. The acids which are used to prepare the pharmaceutically acceptable acid addition salts of the base compounds of this invention are those which form non-toxic acid addition salts, i.e., salts containing pharmacologically acceptable anions, such as hydrochloride, hydrobromide, hydroiodide, nitrate, sulfate or bisulfate, phosphate or acid phosphate, acetate, lactate, citrate or acid citrate, tartrate or bitartrate, succinate, maleate, fumarate, gluconate, saccharate, benzoate, methanesulfonate and pamoate i.e., 1,1'-methylene-bis-(2-hydroxy-3-naphthoate)! salts.
Those compounds of the formula I which are also acidic in nature (e.g., where R 2 contains a carboxylate) are capable of forming base salts with various pharmacologically acceptable cations. The chemical bases that are used as reagents to prepare the pharmaceutically acceptable base salts of this invention are, those that form non-toxic base salts with the herein described acidic compounds of formula I. These non-toxic base salts include those derived from such pharmacologically acceptable alkali metal or alkaline-earth metal cations as sodium, potassium, calcium and magnesium.
Preferred compounds of the invention are compounds of the formula I wherein X is carbon, Y is carbon and R 1 is hydrogen.
Particularly preferred compounds of the invention are compounds of the formula I wherein R 3 , R 5 and R 6 are hydrogen. Specific particularly preferred compounds of the invention are the following:
5-cyano-1-(indol-5-yl)benzimidazole;
5-cyano-1-(3-formylindol-5-yl)benzimidazole;
1-(indol-5-yl)-5-methylbenzimidazole;
5-cyano-1-(3-(cyclohexen-1-yl)indol-5-yl)benzimidazole;
1-(3-formylindol-5-yl)-3H-pyrido 4,5-b!imidazole;
1-(3-(cyclohexen-1-yl)indol-5-yl)-5-methylbenzimidazole;
1-(3-cyclohexylindol-5-yl)-5-methylbenzimidazole; and
1-(3-benzoylindol-5-yl)-5-methylbenzimidazole;
and the pharmaceutically acceptable salts of the foregoing compounds.
Other compounds of formula I include the following:
5-ethyl-1-(3-indol-5-yl)benzimidazole;
5-ethyl-1-(3-methylindol-5-yl)benzimidazole;
5-ethyl-1-(3-ethylindol-5-yl)benzimidazole;
1-(3-cyclohexylindol-5-yl)-5-ethylbenzimidazole;
5-methyl-1-(3-methylindol-5-yl)benzimidazole;
1-(3-ethylindol-5-yl)-5-methylbenzimidazole;
1-(3-isopropylindol-5-yl)-5-methylbenzimidazole;
1-(3-cyclopentylylindol-5-yl)-5-methylbenzimidazole;
1-(indol-5-yl)-5-methoxybenzimidazole;
1-(3-methylindol-5-yl)-5-methoxybenzimidazole;
1-(3-ethylindol-5-yl)-5-methoxybenzimidazole;
1-(3-cyclohexylindol-5-yl)-5-methoxybenzimidazole;
5-chloro-1-(indol-5-yl)benzimidazole;
5-chloro-1-(3-methylindol-5-yl)benzimidazole;
5-chloro-1-(3-ethylindol-5-yl)benzimidazole;
5-chloro-1-(3-cyclohexylindol-5-yl)benzimidazole;
5-methyl-1-(3-methylindol-5-yl)pyrido 4,5-b!imidazole;
1-(3-cyclohexylindol-5-yl)-5-methylpyrido 4,5-b!imidazole;
5-carboxamido-1-(indol-5-yl)benzimidazole;
5-carboxamido-1-(3-methylindol-5-yl)benzimidazole;
5-carboxamido-1-(3-ethylindol-5-yl)benzimidazole;
5-carboxamido-1-(3-cyclohexylindol-5-yl)benzimidazole;
5-formyl-1-(indol-5-yl)benzimidazole;
5-formyl-1-(3-methylindol-5-yl)benzimidazole;
5-formyl-1-(3-ethylindol-5-yl)benzimidazole;
5-formyl-1-(3-cyclohexylindol-5-yl)benzimidazole;
1-(indol-5-yl)-5-phenylethylbenzimidazole;
1-(3-methylindol-5-yl)-5-phenylethylbenzimidazole;
1-(3-ethylindol-5-yl)-5-phenylethylbenzimidazole;
1-(3-cyclohexyindol-5-yl)-5-phenylethylbenzimidazole;
1-(indol-5-yl)-5-methoxymethylbenzimidazole;
1-(3-methylindol-5-yl)-5-methoxymethylbenzimidazole;
1-(3-ethylindol-5-yl)-5-methoxymethylbenzimidazole;
1-(3-cyclohexylindol-5-yl)-5-methoxymethylbenzimidazole;
5-dimethylaminomethyl-1-(indol-5-yl)benzimidazole;
5-dimethylaminomethyl-1-(3-methylindol-5-yl)benzimidazole;
5-dimethylaminomethyl-1-(3-ethylindol-5-yl)benzimidazole; and
5-dimethylaminomethyl-1-(3-cyclohexylindol-5-yl)benzimidazole.
This invention also relates to a method for treating or preventing a condition or disorder selected from anxiety, panic attacks, sleep disorders, seizures, memory loss, convulsions, and drug abuse in a mammal, preferably a human, comprising administering to said mammal requiring such treatment or prevention an amount of a compound of formula I, or a pharmaceutically acceptable salt thereof, effective in treating or preventing such condition or disorder.
This invention also relates to a pharmaceutical composition for treating or preventing a disorder or condition selected from anxiety, panic attacks, sleep disorders, seizures, memory loss, convulsions, and drug abuse in a mammal, preferably a human, comprising an amount of a compound of formula I, or a pharmaceutically acceptable salt thereof, effective in treating or preventing such disorder or condition and a pharmaceutically acceptable carrier.
This invention also relates to a method for treating or preventing a condition or disorder arising from an increase or decrease in benzodiazepine receptor neurotransmission in a mammal, preferably a human, comprising administering to said mammal requiring such treatment or prevention an amount of a compound of formula I, or a pharmaceutically acceptable salt thereof, effective in treating or preventing such condition or disorder.
This invention also relates to a pharmaceutical composition for treating or preventing a disorder or condition arising from an increase or decrease in benzodiazepine receptor neurotransmission in a mammal, preferably a human, comprising an amount of a compound of formula I, or a pharmaceutically acceptable salt thereof, effective in treating or preventing such condition or disorder and a pharmaceutically acceptable carrier.
This invention also relates to a method for antagonizing or agonizing the benzodiazepine receptor in a mammal, preferably a human, comprising administering to said mammal a benzodiazepine receptor antagonizing or agonizing amount of a compound of formula I, or a pharmaceutically acceptable salt thereof.
This invention also relates to a pharmaceutical composition for antagonizing or agonizing the benzodiazepine receptor in a mammal, preferably a human, comprising administering to said mammal a benzodiazepine receptor antagonizing or agonizing amount of a compound of formula I, or a pharmaceutically acceptable salt thereof, and a pharmaceutically acceptable carrier.
This invention also relates to a method for treating or preventing a condition or disorder selected from anxiety, panic attacks, sleep disorders, seizures, memory loss, convulsions, and drug abuse in a mammal, preferably a human, comprising administering to said mammal a benzodiazepine receptor antagonizing or agonizing amount of a compound of formula I, or a pharmaceutically acceptable salt thereof.
This invention also relates to a pharmaceutical composition for treating or preventing a disorder or condition selected from anxiety, panic attacks, sleep disorders, seizures, memory loss, convulsions, and drug abuse in a mammal, preferably a human, comprising administering to said mammal a benzodiazepine receptor antagonizing or agonizing amount of a compound of formula I, or a pharmaceutically acceptable salt thereof, and a pharmaceutically acceptable carrier.
This invention also relates to a compound of the formula ##STR5## wherein X and Y are independently carbon or nitrogen;
R 1 and R 2 are independently selected from hydrogen, (C 1 -C 6 )alkyl, aryl, --(C 1 -C 3 )alkylaryl, --(CH 2 ) n --(C 4 -C 7 )cycloalkyl, --(CH 2 ) n CHO, --(CH 2 ) n CO 2 R 7 , --(CH 2 ) n CONR 7 R 8 , 3-succinamido, unsaturated heterocycle, benzo-fused heterocycle, --(C 1 -C 3 )alkyl-unsaturated heterocycle, and --(C 1 -C 3 )alkyl-benzo-fused heterocycle; wherein said unsaturated heterocycle and unsaturated heterocycle moiety of said --(C 1 -C 3 )alkyl-unsaturated heterocycle are selected independently from pyrrolyl, furyl, thienyl, oxazolyl, isoxazolyl, imidazolyl, thiazolyl, isothiazolyl, pyrazolyl, triazolyl, tetrazolyl, 1,3,5-oxadiazolyl, 1,2,4-oxadiazolyl, 1,3,5-thiadiazolyl, 1,2,4-thiadiazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, 1,3,5-triazinyl, 1,2,5-thiadiazinyl, 1,2,5-oxathiazinyl, and 1,2,6-oxathiazinyl; wherein said benzo-fused heterocycle and the benzo-fused heterocyclic moiety of said --(C 1 -C 3 )alkyl-benzo-fused heterocycle are selected independently from benzoxazolyl, benzothiazolyl, benzimidazolyl, thianaphthenyl, isothianaphthenyl, benzofuranyl, isobenzofuranyl, chromenyl, isoindolyl, indolyl, indazolyl, isoquinolyl, quinolyl, phthalazinyl, quinoxalinyl, quinazolinyl; cinnolinyl and benzoxazinyl; wherein each of said unsaturated heterocycle, benzo-fused heterocycle, --(C 1 -C 3 )alkyl-unsaturated heterocycle and --(C 1 -C 3 )alkyl-benzo-fused heterocycle may optionally be substituted on one or more ring carbon atoms with from zero to three substituents, said substituents being independently selected from bromo, chloro, fluoro, (C 1 -C 5 )alkyl, (C 1 -C 5 )alkoxy, (C 1 -C 5 )alkylthio, (C 1 -C 5 )alkylamino, (C 1 -C 4 )alkylsulfonyl, (C 1 -C 5 )dialkylamino, hydroxy, amino, nitro, cyano, trifluoromethyl, ##STR6## wherein said aryl groups and the aryl moieties of said (C 1 -C 3 )alkylaryl groups are independently selected from phenyl and substituted phenyl, wherein said substituted phenyl may be substituted with from one to three substituents independently selected from (C 1 -C 4 )alkyl, halogen (e.g., fluorine, chlorine bromine or iodine), hydroxy, cyano, carboxamido, nitro, and (C 1 -C 4 )alkoxy;
R 3 , R 4 , R 5 , and R 6 are independently selected from hydrogen, (C 1 -C 6 )alkyl, aryl, --(C 1 -C 3 )alkylaryl, --CN, --CHO, CO 2 R 9 , --NO 2 , --CONR 9 R 10 , --(CH 2 ) p OH, --(CH 2 ) p OR 9 , --(CH 2 ) p NR 9 R 10 and halogen (e.g., fluorine, chlorine bromine or iodine); wherein said aryl groups and the aryl moieties of said --(C 1 -C 3 )alkylaryl groups are independently selected from phenyl and substituted phenyl, wherein said substituted phenyl may be substituted with from one to three substituents independently selected from (C 1 -C 4 )alkyl, halogen (e.g., fluorine, chlorine bromine or iodine), hydroxy, cyano, carboxamido, nitro, and (C 1 -C 4 ) alkoxy;
R 7 , R 8 , R 9 , and R 10 are independently selected from hydrogen, (C 1 -C 6 )alkyl, aryl, --(C 1 -C 3 )alkylaryl, unsaturated heterocycle, benzo-fused heterocycle, --(C 1 -C 3 )alkyl-unsaturated heterocycle, and --(C 1 -C 3 )alkyl-benzo-fused heterocycle; wherein said unsaturated heterocycle and unsaturated heterocycle moiety of said --(C 1 -C 3 )alkyl-unsaturated heterocycle are selected independently from pyrrolyl, furyl, thienyl, oxazolyl, isoxazolyl, imidazolyl, thiazolyl, isothiazolyl, pyrazolyl, triazolyl, tetrazolyl, 1,3,5-oxadiazolyl, 1,2,4-oxadiazolyl, 1,3,5-thiadiazolyl, 1,2,4-thiadiazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, 1,3,5-triazinyl, 1,2,5-thiadiazinyl, 1,2,5-oxathiazinyl, and 1,2,6-oxathiazinyl; wherein said benzo-fused heterocycle and the benzo-fused heterocyclic moiety of said --(C 1 -C 3 )alkyl-benzo-fused heterocycle are selected independently from benzoxazolyl, benzothiazolyl, benzimidazolyl, thianaphthenyl, isothianaphthenyl, benzofuranyl, isobenzofuranyl, chromenyl, isoindolyl, indolyl, indazolyl, isoquinolyl, quinolyl, phthalazinyl, quinoxalinyl, quinazolinyl, cinnolinyl and benzoxazinyl; wherein each of said unsaturated heterocycle, benzo-fused heterocycle, --(C 1 -C 3 )alkyl-unsaturated heterocycle and --(C 1 -C 3 )alkyl-benzo-fused heterocycle may optionally be substituted on one or more ring carbon atoms with from zero to three substituents, said substituents being independently selected from bromo, chloro, fluoro, (C 1 -C 5 )alkyl, (C 1 -C 5 )alkoxy, (C 1 -C 5 )alkylthio, (C 1 -C 5 )alkylamino, (C 1 -C 4 )alkylsulfonyl, (C 1 -C 5 )dialkylamino, hydroxy, amino, nitro, cyano, trifluoromethyl, ##STR7## wherein said aryl groups and the aryl moieties of said --(C 1 -C 3 )alkylaryl groups are independently selected from phenyl and substituted phenyl, wherein said substituted phenyl may be substituted with from one to three substituents independently selected from (C 1 -C 4 )alkyl, halogen (e.g., fluorine, chlorine bromine or iodine), hydroxy, cyano, carboxamido, nitro, and (C 1 -C 4 )alkoxy;
n is 0, 1, 2, or 3; and
p is 0, 1, or 2.
The compounds of the formula III are useful as intermediates in preparing the compounds of formula I.
Unless otherwise indicated, the alkyl groups referred to herein, as well as the alkyl moieties of other groups referred to herein (e.g. alkoxy), may be linear or branched, and they may also be cyclic (e.g. cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl) or be linear or branched and contain cyclic moieties.
DETAILED DESCRIPTION OF THE INVENTION
The compounds of formula I can be prepared according to the methods of scheme 1. In the reaction scheme and discussion that follow, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , X and Y, unless otherwise indicated, are as defined above for formula I. ##STR8##
Compounds of formula III can be prepared by reacting a compound of formula IV with a compound of formula V, wherein LG is a leaving group such as, for example, fluoro, chloro, bromo, iodo, methylmercapto (SCH 3 ), methanesulfonyl (SO 2 CH 3 ), thiophenyl (SPh), or phenylsulfonyl (SO 2 Ph), under acidic, neutral, or basic conditions in an inert solvent. Basic conditions are preferred. Suitable bases include sodium hydrogen carbonate, sodium carbonate, trialkylamines (including, for example, triethylamine), sodium, and sodium hydride. Triethylamine is the preferred base. Suitable solvents include (C 1 -C 4 )alcohols, dioxane, diethyl ether, tetrahydrofuran, acetonitrile, N,N-dimethylformamide, and N-methylpyrrolidine. Ethanol is the preferred solvent. The reaction is usually conducted at a temperature from about 25° C. to about 154° C., preferably about 70° C. to about 80° C.
Compounds of formula II can be prepared from a reduction of compounds of formula III in an inert solvent. This reduction can be mediated either by transition metals or other metal reducing agents. When a transition metal mediates the reduction, a hydrogen source is also used. Suitable transition metals include palladium on carbon, palladium hydroxide on carbon, and platinum oxide. Palladium on carbon is preferred. Suitable hydrogen sources include hydrogen gas, ammonium formate, and formic acid. Hydrogen gas at a pressure of about one to about three atmospheres is the preferred hydrogen source. Three atmospheres of hydrogen gas is the preferred pressure. Suitable solvents include (C 1 -C 4 )alcohols, acetonitrile, N,N-dimethylformamide, and N-methylpyrrolidine. Ethanol is the preferred solvent. Other metal reducing agents include iron sulfate (FeSO 4 ) and zinc (metal)(Zn) in aqueous hydrochloric acid. Of this group, FeSO 4 is preferred. When FeSO 4 is the reducing agent, suitable solvents include aqueous ammonium hydroxide mixed with ethanol and concentrated aqueous hydrochloric acid. Aqueous ammonium hydroxide (mixed with ethanol) is the preferred solvent. All of the above reduction reactions are usually conducted at a temperature of from about 25° C. to about 100° C., preferably about 25° C. to about 50° C. Compounds of formula II are used directly from the reduction reaction with no purification.
Compounds of formula I are prepared from the reaction of a compound of formula II with a formic acid synthon under neutral or acidic conditions in an inert solvent. Formic acid synthon refers to any molecule that is equivalent to formic acid such that it is capable of reacting with a nuceophile to produce a formyl residue. Suitable formic acid synthons include dimethylformamide dimethylacetal, trimethyl orthoformate, triethyl orthoformate, ethoxymethylenemalononitrile, and diethyl ethoxymethylene malonate. Ethoxymethylenemalononitrile is the preferred formic acid synthon. While neutral conditions are preferred, suitable acid catalysts may accelerate the reaction. Suitable acid catalysts include p-toluenesulfonic acid, hydrochloric acid and acetic acid. Suitable solvents include (C 1 -C 4 )alcohols, dioxane, diethyl ether, tetrahydrofuran, acetonitrile, N,N-dimethylformamide, and N-methylpyrrolidine. 2-Propanol is the preferred solvent. The reaction is usually conducted at a temperature of from about 25° C. to about 154° C., preferably about 75° C. to about 85° C.
Compounds of formula I wherein R 2 is hydrogen can be further modified to form additional compounds of formula I wherein R 2 is as described for formula I using methods known to those skilled in the art. For example, treatment of a compound of formula I wherein R 2 is hydrogen with a base (preferably an alkyl magnesium halide) in an inert solvent (preferably benzene) at a temperature from about 0° C. to about 80° C., forms a basic indole salt. The indole salt, so formed, is capable of reacting with electrophiles (i.e., alkyl halides, Michael acceptors, isocyanides, ketone, aldehydes, acid chlorides, anhydrides) at the C3 position of the indole ring, in an inert solvent (preferably benzene) at a temperature from about 0° C. to about 80° C. leading to compounds of formula I wherein R 2 is (C 1 -C 6 )alkyl, --(C 1 -C 3 )alkylaryl, --(CH 2 ) n --(C 4 -C 7 )cycloalkyl, --(CH 2 ) n CHO, --(CH 2 ) n CO 2 R 7 , --(CH 2 ) n CONR 7 R 8 , 3-succinamido, unsaturated heterocycle, benzo-fused heterocycle, --(C 1 -C 3 )alkyl-unsaturated heterocycle, and --(C 1 -C 3 )alkyl-benzo-fused heterocycle. Alternatively, a compound of formula I wherein either R 1 or R 2 is hydrogen can be reacted under neutral or acidic conditions with electrophiles leading to compounds of formula I wherein R 1 or R 2 may independently be (C 1 -C 6 )alkyl, aryl, --(C 1 -C 3 )alkylaryl, --(CH 2 ) n --(C 4 -C 7 )cycloalkyl, --(CH 2 ) n CHO, --(CH 2 ) n CO 2 R 7 , --(CH 2 ) n CONR 7 R 8 , 3-succinamido, unsaturated heterocycle, benzo-fused heterocycle, --(C 1 -C 3 )alkyl-unsaturated heterocycle, and --(C 1 -C 3 )alkyl-benzo-fused heterocycle. The procedures and conditions for carrying out these reactions are known to those skilled in the art, for example, in "Properties and Reactions of Indoles, Isoindoles, and Their Hydrogenated Derivatives," W. A. Reimers, in The Chemistry of Heterocyclic Compounds (A. Weissberger and E. C. Taylor, editors), Vol. 25, Part I (W. J. Houlihan, editor), Wiley-Interscience, New York (1972). pp. 70-134, which is hereby incorporated by reference in its entirety.
Compounds of formula IV and formula V are either commercially available or known to those skilled in the art.
Unless indicated otherwise, the pressure of each of the above reactions is not critical. Generally, the reactions will be conducted at a pressure of about one to about three atmospheres, preferably at ambient pressure (about one atmosphere).
The compounds of the formula I which are basic in nature are capable of forming a wide variety of different salts with various inorganic and organic acids. Although such salts must be pharmaceutically acceptable for administration to animals, it is often desirable in practice to initially isolate a compound of the formula I from the reaction mixture as a pharmaceutically unacceptable salt and then simply convert the latter back to the free base compound by treatment with an alkaline reagent, and subsequently convert the free base to a pharmaceutically acceptable acid addition salt. The acid addition salts of the base compounds of this invention are readily prepared by treating the base compound with a substantially equivalent amount of the chosen mineral or organic acid in an aqueous solvent medium or in a suitable organic solvent such as methanol or ethanol. Upon careful evaporation of the solvent, the desired solid salt is obtained.
The compounds of the formula I which are acidic in nature are capable of forming a wide variety of different salts with various inorganic and organic bases. These salts are all prepared by conventional techniques well known to those of ordinary skill in the art. In general, these salts can easily be prepared by treating the corresponding acidic compounds with an aqueous solution containing the desired pharmacologically acceptable cations, and then evaporating the resulting solution to dryness, preferably under reduced pressure. Alternatively, they may also be prepared by mixing lower alkanolic solutions of the acidic compounds and the desired alkali metal alkoxide together, and then evaporating the resulting solution to dryness in the same manner as before. In either case, stoichiometric quantities of reagents are preferably employed in order to ensure completeness of reaction and maximum product yields of the desired final product.
The compounds of the formula I and the pharmaceutically acceptable salts thereof (hereinafter, also referred to as "the active compounds of the invention") are useful psychotherapeutics and have high affinity for benzodiazepine receptors in the central nervous system. The active compounds of the invention are agonists, partial agonists, antagonists, partial antagonists, or reverse antagonists of the benzodiazepine receptor. The active compounds of the invention which are agonists may be used in the treatment of anxiety, and degenerative central nervous system disorders (e.g. Alzheimer's disease). The active compounds of the invention which are antagonists can be used as anti-convulsants or for the treatment of prevention of seizures or memory loss. The active compounds of the invention which are partial or reverse antagonists may also be useful for memory enhancement.
The affinity of these compounds for benzodiazepine receptors may be measured in an in vitro receptor binding assay such as that described by P. Supavilai and M. Karobath in Eur. J. Pharm., Vol. 70, 183 (1981).
An alternate in vitro receptor binding assay may be used in which guinea pig cerebellum can be the receptor source and 3 H!flunitrazepam as the radioligand according to the following process. Either of the above two binding assays may be used to distinguish antagonists, agonists, partial or reverse antagonists and partial agonists. The 3 H!flunitrazepam assay is summarized below.
Male Hartley guinea pigs may be decapitated and the cerebellums removed by dissection. Each cerebellum may then be homogenized in 50 mMolar TRIS Acetate buffer (tris hydroxymethyl!aminomethane acetate). The homogenate may then be centrifuged for 10 minutes at 40,000 g.
The supernatant may then be decanted and the residual pellet diluted with fresh TRIS Acetate buffer. The pellet may then be resuspended and then centrifuged again for 10 minutes at 40,000 g. The supernatant may then be decanted and the pellet washed one more time using the same procedure just described.
After the last wash cycle, the pellet may be resuspended in 50 mM TRIS Acetate buffer. The benzazeipine binding of a compound of formula I can be determined by adding to a tube 750 μl of the tissue suspension prepared according to the above methods with 100 μl of drug or buffer, 150 μl of 3H!-flunitrazepam such that the final concentration of the 3H!-flunitrazepam is 1 nM. The tissue, drug and flunitrazepam may then be incubated for 90 minutes at 0° C. in the dark.
Non-specific binding may be determined by incubating the tissue with flunitrazepam and alprazolam (10 μM) or chlordiazepoxide (10 μM).
After 90 minutes, incubation may be terminated by rapid filtration under vacuum through glassfiber filters (eg., Whatman GF/B®) presoaked in 1% polyethyleneimine (PEI) using a cell harvester. The filter may then be washed three times with ice cold 5 mM TRIS Hydrochloride buffer (pH 7.2). The filters may then be placed in a scintillation vial and soaked in 6 mL of scintillation fluid and allowed to sit overnight.
After standing overnight, the vials may then be vortexed and the radioactivity may be quantified by liquid scintillation counting according to methods well known in the art.
Percent inhibition of specific binding may be calculated for each dose of a compound of formula I. An IC 50 value may then be calculated from the percent inhibition data. Active compounds of the invention are those which have an IC 50 of less than 250 nM for the benzodiazepine receptor as measured by either of the above procedures.
The compositions of the present invention may be formulated in a conventional manner using one or more pharmaceutically acceptable carriers. Thus, the active compounds of the invention may be formulated for oral, buccal, intranasal, parenteral (e.g., intravenous, intramuscular or subcutaneous) or rectal administration or in a form suitable for administration by inhalation or insufflation.
For oral administration, the pharmaceutical compositions may take the form of, for example, tablets or capsules prepared by conventional means with pharmaceutically acceptable excipients such as binding agents (e.g., pregelatinised maize starch, polyvinylpyrrolidone or hydroxypropyl methylcellulose); fillers (e.g., lactose, microcrystalline cellulose or calcium phosphate); lubricants (e.g., magnesium stearate, talc or silica); disintegrants (e.g., potato starch or sodium starch glycollate); or wetting agents (e.g., sodium lauryl sulphate). The tablets may be coated by methods well known in the art. Liquid preparations for oral administration may take the form of, for example, solutions, syrups or suspensions, or they may be presented as a dry product for constitution with water or other suitable vehicle before use. Such liquid preparations may be prepared by conventional means with pharmaceutically acceptable additives such as suspending agents (e.g., sorbitol syrup, methyl cellulose or hydrogenated edible fats); emulsifying agents (e.g., lecithin or acacia); non-aqueous vehicles (e.g. almond oil, oily esters or ethyl alcohol); and preservatives (e.g., methyl or propyl p-hydroxybenzoates or sorbic acid).
For buccal administration, the composition may take the form of tablets or lozenges formulated in conventional manner.
The active compounds of the invention may be formulated for parenteral administration by injection, including using conventional catheterization techniques or infusion. Formulations for injection may be presented in unit dosage form (e.g., in ampules or in multi-dose containers), with an added preservative. The compositions may take such forms as suspensions, solutions or emulsions in oily or aqueous vehicles, and may contain formulating agents such as suspending, stabilizing and/or dispersing agents. Alternatively, the active ingredient may be formulated in powder form for reconstitution with a suitable vehicle, (e.g., sterile pyrogen-free water, before use).
The active compounds of the invention may also be formulated in rectal compositions such as suppositories or retention enemas, (e.g., containing conventional suppository bases such as cocoa butter or other glycerides).
For intranasal administration or administration by inhalation, the active compounds of the invention are conveniently delivered in the form of a solution or suspension from a pump spray container that is squeezed or pumped by the patient or as an aerosol spray presentation from a pressurized container or a nebulizer, with the use of a suitable propellant, (e.g., dichlorodifluoromethane, trichlorofluoromethane, dichlorotetrafluoroethane, carbon dioxide or other suitable gas). In the case of a pressurized aerosol, the dosage unit may be determined by providing a valve to deliver a metered amount. The pressurized container or nebulizer may contain a solution or suspension of the active compound. Capsules and cartridges (made, for example, from gelatin) for use in an inhaler or insufflator may be formulated containing a powder mix of a compound of the invention and a suitable powder base such as lactose or starch.
Appropriate dosages of the active compounds of the invention for oral, parenteral, rectal or buccal administration to the average adult human for the treatment of the conditions referred to above will generally range from about 0.1 mg to about 200 mg of the active ingredient per unit dose. Preferably, the unit dosage will range from about 1 mg to about 100 mg. Administration may be repeated, for example, 1 to 4 times per day. Variations may nevertheless occur depending upon the species of animal being treated and its individual response to said medicament, as well as on the type of pharmaceutical formulation chosen and the time period and interval at which such administration is carried out. In some instances, dosage levels below the lower limit of the aforesaid range may be more than adequate, while in other cases still larger doses may be employed without causing any harmful side effect, provided that such larger doses are first divided into several small doses for administration throughout the day.
Aerosol formulations for treatment of the conditions referred to above (e.g., migraine) in the average adult human are preferably arranged so that each metered dose or "puff" of aerosol contains 20 μg to 1000 μg of the compound of the invention. The overall daily dose with an aerosol will be within the range 100 μg to 10 mg. Administration may be several times daily, for example 2, 3, 4 or 8 times.
The following Examples illustrate the preparation of the compounds of the present invention. Commercial reagents were utilized without further purification. Melting points are uncorrected. NMR data are reported in parts per million (d) and are referenced to the deuterium lock signal from the sample solvent and were obtained on a Bruker 300 MHz instrument. Chromatography refers to column chromatography performed using 32-63 μm silica gel and executed under nitrogen pressure (flash chromatography) conditions. Room temperature refers to 20°-25° C.
EXAMPLE 1
General Synthesis of 1-Indolyl-1H-benz b!imidazoles and 1-Indolyl-1H-pyrido 4,5-b!imidazoles
A mixture of a 5-(2-nitroarylamino)-1H-indole (2.00 mmol) and 10% Paladium (Pd) on carbon (20% by weight) in .absolute ethanol (20 mL) was shaken under a hydrogen atmosphere (3 atm) at room temperature for 8 hours. The resulting reaction mixture was filtered through diatomaceous earth, Celite®, and the filtrate was evaporated under reduced pressure to afford crude 5-(2-aminoarylamino)-1H-indole, which was used directly. Alternatively, a mixture of a 5-(2-nitroarylamino)-1H-indole (2.00 mmol) and iron sulfate (FeSO 4 ) (5.5 g, 20 mmol, 10 equivalents) in ammonium hydroxide/water/ethanol 1:5:3, respectively, 27 mL total volume! was stirred at room temperature for 24 hours. The resulting reaction mixture was then filtered through diatomaceous earth, Celite®. The ethanol was removed from the filtrate by evaporation under reduced pressure. The remaining aqueous mixture was extracted with methylene chloride (3×25 mL), and the organic extracts were combined, dried over magnesium sulfate (MgSO 4 ), and evaporated under reduced pressure to afford crude 5-(2-aminoarylamino)-1H-indole, which was used directly in the next step.
The 5-(2-aminoarylamino)-1H-indole was then combined with either dimethylformamide dimethylacetal (10 mL), triethyl orthoformate/formic acid (5 mL/5 mL), or ethoxymethylene-malononitrile (0.49 g, 4.01 mmol, 2.0 equivalents) in 2-propanol (10 mL) and heated at reflux under nitrogen for 1 to 24 hours, depending on the substrate. When dimethylformamide dimethylacetal was used, the reaction solvent is changed to toluene after 1 hour, a catalytic mount (5 mg) of p-toluenesulfonic acid was added, and the reaction solution was heated at reflux under nitrogen for 12-24 hours depending on the substrate. The resultant reaction solution was then evaporated under reduced pressure, and the residue was triturated or column chromatographed using silica gel (approximately 50 g) and an appropriate solvent system to afford the appropriate 1-indolyl-1H-benz b!imidazole or 1-indolyl-1H-pyrido 4,5-b!imidazole.
Following this procedure the following compounds were prepared.
A. 5-Cyano-1-(indol-5-yl)benzimidazole
5-(4-Cyano-2-nitrophenylamino)-1H-indole (0.56 g, 2.0 mmoles) was reduced by catalytic hydrogenation, to form 5-(4-cyano-2-aminophenylamino)-1H-indole (0.50 g, 2.0 mmole). The 5-(4-cyano-2-aminophenylamino)-1H-indole was cyclized using ethoxymethylenemalononitrile (0.49 g, 2.0 mmoles) in propanol, and the cyclization reaction was heated for 24 hours. Column chromatography using ethyl acetate/hexanes 1:1! afforded the title compound (94%) as a yellow solid. Mp, 263.0°-264.0° C.; 13 C NMR (DMSO-d 6 ) δ147.2, 143.5, 137.5, 135.8, 128.5, 128.1, 127.3, 127.0, 125.3, 120.2, 118.2, 116.7, 113.1, 112.6, 104.8, 102.2; HRMS calculated for C 16 H 10 N 4 258.0904, found 258.0904. Analytical calculated for C 16 H 10 N 4 : C, 74.40; H, 3.90; N, 21.69. Found: C, 74.20; H, 3.92; N, 21.69.
B. 1-(Indol-5-yl)-5-methylbenzimidazole
5-(4-Methyl-2-nitrophenylamino)-1H-indole (0.47 g, 2.0 mmoles) was reduced by catalytic hydrogenation to form 5-(4-methyl-2-aminophenylamino)-1H-indole (0.41 g, 2.0 mmoles). The 5-(4-methyl-2-aminophenylamino)-1H-indole was cyclized with ethoxymethylenemalononitrile (0.49 g, 2.0 mmole) in propanol, while being heated for 14 hours. Column chromatography using 10% ethyl acetate in methylene chloride afforded the title compound (81%) as a yellow solid. Mp, 215.0°-216.0° C.; R f =0.3 in 10% ethyl acetate in methylene chloride; 1 H NMR (DMSO-d 6 ) δ11.43 (br s, NH), 8.42 (s, 1H), 7.76 (d, J=1.4 Hz, 1H), 7.61 (d, J=8.4 Hz, 1H), 7.56 (d, J=0.5 Hz, 1H), 7.52 (t, J=2.6 Hz, 1H), 7.42 (d, J=8.3 Hz, 1H), 7.30 (dd, J=8.5 and 1.7 Hz, 1H), 7.12 (br d, J=8.3 Hz, 1H), 6.56 (dd, J=2.7 and 0.9 Hz, 1H), 2.44 (s, 3H); 13 C NMR (DMSO-d 6 ) δ156.5, 144.3, 143.8, 137.2, 134.0, 130.0, 129.1, 128.0, 126.4, 119.7, 119.0, 117.3, 113.4, 111.7, 103.0, 21.6; FAB LRMS (m/z, relative intensity) 249 (23), 248 ( MH! + , 100); HRMS calculated for C 16 H 13 N 3 247.1107, found 247.1092.
EXAMPLE 2
5-Cyano-1-(3-formylindol-5-yl)benzimidazole
Phosphorus oxychloride (0.54 mL, 5.81 mmol, 1.5 eq) was added to dimethylformamide (10 mL) at room temperature, and to this solution was added 5-cyano-1-(indol-5-yl)benzimidazole (1.00 g, 3.87 mmol). The resulting reaction solution was heated at 40° C. under nitrogen for 2 hours. An aqueous solution of 10% sodium hydroxide (10 mL) was then added, followed by enough solid sodium hydroxide to adjust the pH to above 13. This mixture was heated at reflux under nitrogen for 1 hour, cooled, and the precipitated solid was filtered to afford the title compound (1.00 g, 90%) as an off-white solid. Mp, greater than 200° C.; IR (KBr) 2225, 1675 cm -1 ; 1 H NMR (DMSO-d 6 ) δ10.00 (s, 1H), 8.82 (s, 1H), 8.49 (s, 1H), 8.38 (d, J=0.7 Hz, 1H), 8.26 (d, J=2.0 Hz, 1H), 7.78 (d, J=8.6 Hz, 1H), 7.73 (dd, J=8.5 and 1.4 Hz, 1H), 7.67 (d, J=8.4 Hz, 1H), 7.54 (dd, J=8.6 and 2.2 Hz, 1H); LRMS (m/z, relative intensity) 287 (18), 286 (M + , 100), 258 (18), 230 (11). HRMS calculated for C 17 H 10 N 4 O: 286.0853. Found: 286.0870.
EXAMPLE 3
5-Cyano-1-(3-(cyclohexen-1-yl)indol-5-yl)benzimidazole
A solution of sodium methoxide (0.25 g, 4.6 mmol, 3 equivalents), 5-cyano-1-(indol-5-yl)benzimidazole (0.40 g, 1.54 mmol), and cyclohexanone (0.175 mL, 1.69 mmol, 1.1 equivalents) in N,N-dimethylformamide (8 mL) was heated at 130° C. under nitrogen for 12 hours. The solvent was removed by evaporation under reduced pressure, and the residue was partitioned between ethyl acetate (25 mL) and water (25 mL). The organic layer was separated, dried (MgSO 4 ), and evaporated under reduced pressure. Column chromatography of the residue (0.16 g) using silica gel (approximately 5 g) and elution with ethyl acetate/hexanes 1:1! afforded the title compound. (19%) as a pale yellow solid. R f =0.3 in ethyl acetate/hexanes 1:1!; 1 H NMR (CDCl 3 ) δ10.35 (br s, 1H), 8.18 (s, 1H), 8.05 (s, 1H), 7.80 (s, 1H), 7.45-7.43 (m, 3H), 7.21 (s, 1H), 7.07 (dd, J=8.5 and 1.9 Hz, 1H), 6.04 (br m, 1H), 2.32 (br m, 2H), 2.08 (br m, 2H), 1.72-1.60 (m, 2H), 1.60-1.50 (m, 2H); 13 C NMR (CDCl 3 ) δ145.7, 142.4, 137.5, 136.7, 130.9, 126.8, 125.7, 124.8, 123.8, 123.6. 122.5, 119.5, 119.2, 118.2, 117.2, 112.7, 112.1, 105.6, 28.4, 25.5, 22.9, 22.2.
EXAMPLE 4
1-(3-Formylindol-5-yl)-3H-pyrido 4,5-b!imidazole
A mixture of 5-(3-nitropyrid-2-ylamino)-1H-indole (5.50 g, 21.63 mmol) and 10% palladium on carbon (1.00 g) in absolute ethanol (75 mL) was shaken under a hydrogen atmosphere (3 atm) for 5 hours. The resulting mixture was filtered through Celite®, and the filtrate was evaporated under reduced pressure. The residue (4.95 g) was dissolved in dimethylformamide dimethylacetal (25 mL), and the resulting solution was heated at reflux under nitrogen for 12 hours. The resulting reaction solution was evaporated under reduced pressure, and the residue was suspended in a solution of 10% aqueous sodium hydroxide and ethanol (5:1, respectively, 75 mL). The resulting mixture was heated at reflux under nitrogen for 3 hours. The pH of this mixture was adjusted to pH 7 with concentrated hydrochloric acid (HCl) followed by a saturated solution of sodium hydrogen carbonate. The resulting aqueous mixture was extracted with ethyl acetate (3 times 75 mL). The organic extracts were combined, dried (MgSO 4 ), and evaporated under reduced pressure. The residue was adhered to silica gel (approximately 10 g) using methanol, and this mixture was placed on top of a silica gel plug (200 g). A solution of 5% methanol in ethyl acetate 5 Liters (L) was passed through this silica gel filter. The last 3 L of solvent was evaporated under reduced pressure. Trituration of the residue in hot ethyl acetate afforded the title compound (1.54 g, 29%) as an off-white powder. Mp, >280° C.; R f =0.2 in ethyl acetate; 1 H NMR (DMSO-d 6 ) δ12.45 (br s, NH), 9.99 is, 1H), 8.86 is, 1H), 8.51 (d, J=1.8 Hz, 1H), 8.45 (s, 1H), 8.43 (dd, J=4.7 and 1.6 Hz, 1H), 8.22 (dd, J=8.0 and 1.5 Hz, 1H), 7.73 (d, J=8.7 Hz, 1H), 7.69 (dd, J=8.7 and 1.9 Hz, 1H), 7.39 (dd, J=8.0 and 4.7 Hz, 1H); LRMS (m/z, relative intensity) 263 (19), 262 (M + , 100), 234 (57), 233 (37), 206 (17). Analytical calculated for C 15 H 10 N 4 O.0.25 H 2 O: C, 67.54; H, 3.97; N, 21.00. Found: C, 67.82; H, 3.99; N, 20.68.
EXAMPLE 5
1-(3-(Cyclohexen-1-yl)indol-5-yl)-5-methylbenzimidazole
To a stirred solution of sodium (0.325 g, 14.2 mmol, 7.0 equivalents) in absolute methanol (10 mL) was added 1-(indol-5-yl)-5-methylbenzimidazole (0.500 g, 2.02 mmol) and cyclohexanone (0.84 mL, 8.08 mmol, 4.0 equivalents), and the resulting reaction solution was heated at reflux under nitrogen for 12 hours. The resulting mixture was evaporated under reduced pressure, and the residue was column chromatographed using silica gel (approximately 25 g) and eluted with 20% ethyl acetate in methylene chloride to afford the title compound (0.160 g, 0.49 mmol, 24%) as a pale yellow foam. Mp, 101.0°-102.0° C.; R f =0.75 in 5% MeOH in methylene chloride; 1 H NMR (CD 3 OD) d 8.25 (s, 1H), 7.88 (s, 1H), 7.53-7.50 (m, 2H), 7.35-7.33 (m, 2H), 7.21 (br d, J=8.5 Hz, 1H), 7.12 (d, J=8.2 Hz, 1Hz), 6.14 (br m, 1H), 4.90 (s, 1 exchangeable H), 2.46 (s, 3H), 2.19 (br m, 2H), 1.86-1.75 (m, 2H), 1.75-1.63 (m, 2H); IR (KBr) 2929, 2859, 1615, 1579, 1494, 1447 cm -1 .
EXAMPLE 6
1-(3-Cyclohexylindol-5-yl)-5-methylbenzimidazole
A mixture of 1-(3-(cyclohexen-1-yl)indol-5-yl)-5-methylbenzimidazole (0.110 g, 0.34 mmol), 10% Pd on carbon (0.027 g), and absolute ethanol (2 mL) was shaken under an atmosphere of hydrogen (3 atm) for 72 hours. The resulting reaction mixture was filtered through Celite®, and the filtrate was evaporated under reduced pressure to afford the title compound (0.090 g, 80%) as a dark brown foam. Mp, decomposes 120° C.; 1 H NMR (DMSO-d 6 ) d 11.5 (br s, NH), 8.41 (s, 1H), 7.73 (s, 1H), 7.56-7.52 (m, 2H), 7.39 (d, J=8.4 Hz, 1H), 7.27-7.24 (m, 2H), 7.13 (d, J=8.0 Hz, 1H), 2.88-2.75 (m, 1H), 2.45 (s, 3H), 2.10-1.60 (m, 10 H); IR (KBr) 2924, 2851, 1612, 1580, 1492, 1447 cm -1 ; FAB LRMS (m/z, relative intensity) 331 (25), 330 ( MH! + , 100). HRMS calculated for C 22 H 23 N 3 : 329.1887. Found: 329.1874.
EXAMPLE 7
1-(3-Benzoylindol-5-yl)-5-methylbenzimidazole
To a stirred solution of 1-(indol-5-yl)-5-methylbenzimidazole (1.00 g, 4.04 mmol, 2.0 equivalents) in anhydrous benzene (10 mL) at 0° C. under nitrogen was added a solution of ethyl magnesium bromide in ether (3.0M, 1.33 mL, 4.00 mmol, 2.0 equivalents) dropwise, and the resulting reaction solution was stirred at 0° C. under nitrogen for 30 minutes. Then, benzoyl chloride (0.23 mL, 1.98 mmol) was added dropwise rapidly to the reaction solution, and the resulting mixture was stirred at room temperature under nitrogen for 30 min. A saturated solution of sodium hydrogen carbonate (25 mL) was then added to the reaction mixture, and the resulting aqueous mixture was extracted with ethyl acetate (2×25 mL). The extracts were combined, dried (MgSO 4 ), and evaporated under reduced pressure. The residue (2.1 g) was column chromatographed using silica gel (approximately 100 g) and eluted with ethyl acetate/hexanes (1:1) to afford the title compound (0.045 g, 0.13 mmol, 6%) as a white foam. R f =0.65 in ethyl acetate/hexanes (1:1); 1 H NMR (CD 3 OD) d 8.05-7.95 (m, 3H), 7.81 (d, J=6.8 Hz, 1H), 7.71 (d, J=8.5 Hz, 1H), 7.61-7.39 (m, 7H), 7.18 (d, J=8.4 Hz, 1H), 2.48 (s, 3H); FAB LRMS (m/z, relative intensity) 352 ( MH! + , 78%), 248 ( MH! + --Ph(CO), 100).
EXAMPLE 8
General Synthesis of 5-(2-Nitroarylamino)-1H-indoles
A solution of the 5-amino-1H-indole (2.00 mmol), a 2-nitrohaloarene (3.00 mmol, 1.5 eq), and a base (3.00 mmol) in an appropriate inert solvent (10 mL) was heated at reflux under nitrogen for 1 to 24 hours, depending on the substrate. The solvents were evaporated under reduced pressure, and the residue was column chromatographed using silica gel (approximately 50 g) and eluted with an appropriate solvent system to afford the 5-(2-nitroarylamino)-1H-indole derivative. In some cases recrystallization of the solid obtained from chromatography was performed to obtain analytically pure samples of the appropriate 5-(2-nitroarylamino)-1H-indole.
Following this procedure the following compounds were prepared.
A. 5-(4-Cyano-2-nitrophenylamino)-1H-indole
5-Aminoindole (0.264 g, 2.00 mmoles) and 4-chloro-3-nitrobenzonitrile (0.444 g, 3.00 mmoles) were combined with triethylamine (0.42 ml, 3.01 mmoles) in absolute ethanol and the reaction was heated at reflux under nitrogen for 3 hours. After evaporation of the solvent, the residue was chromatographed using ether/hexanes 1:1! to afford the title compound (79%) as a red amorphous solid. Mp, decomposes 134° C.; 13 C NMR (DMSO-d 6 ) δ146.9, 137.3, 134.8, 131.9, 131.3, 128.9, 128.3, 126.9, 119.8, 118.2, 117.9, 117.2, 112.5, 101.5, 97.4; LRMS (m/z, relative intensity) 278 (M + , 100), 261 (31), 244 (73), 231 (78). HRMS calculated for C 15 H 10 N 4 O 2 : 278.0802. Found: 278.0808. Analytical calculated for C 15 H 10 N 4 O 2 : C, 64.74; H, 3.62; N, 20.13. Found: 64.84; H, 3.57; N, 20.13.
B. 5-(4-Methyl-2-nitrophenylamino)-1H-indole
5-Aminoindole (0.264 g, 2.00 mmoles) and 4-fluoro-3-nitrotoluene (0.465 g, 3.00 mmoles) were combined with triethylamine (0.42 ml, 3.01 mmoles) in which 4-fluoro-3-nitrotoluene was the only solvent and the reaction was heated at 225° C. under nitrogen for 18 hours. Chromatography using ether/hexanes 1:1 ! afforded the title compound (90%) as a red amorphous solid. Mp, decomposes 94° C.; R f =0.55 in ethyl acetate/hexanes 1:1!; 13 C NMR (CDCl 3 ) δ143.4, 137.3, 134.2, 131.8, 131.1, 128.7, 126.1, 125.6, 120.8, 117.9, 116.2, 112.1, 102.8, 20.1; LRMS (m/z, relative intensity) 267 (M + , 45), 250 (5), 233 (20), 220 (13). HRMS calculated for C 15 H 13 N 3 O 2 : 267.1005. Found: 267.0993.
C. 5-(3-Nitropyrid-2-ylamino)-1H-indole
5-Aminoindole (0.264 g, 2.00 mmoles) and 2-chloro-3-nitropyridine (0.476 g, 3.00 mmoles) were combined with triethylamine (0.42 ml, 3.01 mmoles) in absolute ethanol. The reaction was heated at room temperature under nitrogen for 72 hours. The resulting reaction mixture was filtered to afford the title compound (69%) as a dark red solid. Mp, 162.0°-163.5° C.; R f =0.6 in diethyl ether; 13 C NMR (DMSO-d 6 ) δ155.6, 150.5, 135.5, 133.5, 129.7, 127.9, 127.6, 125.9, 118.5, 115.0, 113.4, 111.2, 101.2. Analytical calculated for C 13 H 10 N 4 O 2 : C, 61.41; H, 3.96; N, 22.04. Found: 61.22; H, 3.80; N, 22.08.
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The present invention relates to compounds of the formula ##STR1## The present invention also relates to intermediates for the preparation of compounds of the formula I, pharmaceutical compositions and method of use.
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BACKGROUND OF THE INVENTION
The present invention relates in general to the art of earth boring and more particularly to a rotary rock bit with an improved sealing system. The present invention is especially adapted for use on that type of rotary rock bit popularly known as a three cone bit; however, its use is not restricted thereto and the bearing system of the present invention can be used in other earth boring bits wherein an improved bearing system is required.
A three cone rotary rock bit is adapted to be connected as the lower member of a rotary drill string. As the drill string is rotated the bit disintegrates the formations to form an earth borehole. The three cone rotary rock bit includes three individual arms that extend angularly downward from the main body of the bit. The lower end of each arm is shaped to form a bearing pin or journal. A cone cutter is mounted upon each bearing pin and adapted to rotate thereon. The cone cutters include cutting structure on their outer surfaces that serves to disintegrate the formations as the bit is rotated.
A rotary rock bit must operate under very severe environmental conditions and the size and geometry of the bit is restricted by the operating characteristics. At the same time, the economics of petroleum production demand a longer lifetime and improved performance from the bit. In attempting to provide an improved bit, new and improved materials have been developed for the cutting structure of the cone cutters thereby providing a longer useful lifetime for the cone cutters. This has resulted in the bearing and sealing systems being generally the first to fail during the drilling operation. Consequently, a need exists for improved bearing and sealing systems to extend the useful lifetime of the bit. One of the problems encountered with radial seals in rock bits is that when the bearing is loaded the seal sees unequal squeeze on top and bottom. This will tend to knead the seal as well as cause leaks at the top where the squeeze is a minimum. The present invention minimizes this condition and promotes greater seal life and improves bit performance by causing the seal to run concentrically.
DESCRIPTION OF PRIOR ART
In U.S. Pat. No. 3,397,928 to E. M. Galle, patented Aug. 20, 1968, a seal means for drill bit bearings is shown. The seal means includes a shaft rigidly secured to a drill bit body with a bearing surface formed thereon. A cutter element is rotatably mounted to said shaft and includes a bearing surface thereon that opposes and engages the bearing surface on the shaft. A resilient packing ring is positioned in a groove in one of the surfaces. The packing ring, the groove and an opposing surface are sized such that upon assembly of the cutter element upon the shaft the cross sectional thickness of the packing ring is compressed by not less than substantially 10% of this thickness prior to assembly of the cutter element upon the shaft.
Other drill bit bearing sealing systems are shown in U.S. Pat. No. 1,884,965 to Baggett, U.S. Pat. No. 2,797,067 to Fisher, U.S. Pat. No. 3,075,781 to Atkinson, U.S. Pat. No. 3,096,835 to Neilson, U.S. Pat. No. 3,151,691 to Goodwin, U.S. Pat. No. 3,303,898 to Bercaru, U.S. Pat. No. 3,529,840 to Durham and U.S. Pat. No. 3,862,762 to Millsapps.
SUMMARY OF THE INVENTION
The present invention provides a rolling cutter earth boring bit with an improved sealing system. At least one cantilevered bearing pin extends from the arm of the bit. A rolling cone cutter is rotatably mounted on the bearing pin. A seal groove on the bearing pin is machined eccentrically to the bearing pin. The seal will run on concentric diameters with the rolling cutter and will see uniform squeeze around its circumference when the bearing is loaded. The above and other objects and advantages of the present invention will become more apparent from a consideration of the following detailed description of the invention when taken in conjunction with the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates one arm of a rotary rock bit constructed in accordance with the present invention.
FIG. 2 is an enlarged view of the lower portion of the seal groove of the bit shown in FIG. 1.
FIG. 3 is a sectional view of the bearing pin and a superimposed view of the rolling cone cutter of the bit shown in FIG. 1 with the bearing in an unloaded condition.
FIG. 4 is the view of FIG. 2 with the bearing in a loaded condition.
DETAILED DESCRIPTION OF THE INVENTION
Referring now to the drawings and to FIG. 1 in particular, illustrated therein and generally designated by the reference number 10 is a three cone sealed bearing rotary rock bit. The bit 10 includes a bit body 11, including an upper threaded portion 12. The threaded portion 12 allows the bit 10 to be connected to the lower end of a rotary drill string (not shown). Depending from the bit body 11 are three substantially identical arms with only the arm 13 being shown in FIG. 1. The lower end of each of the arms is provided with an extended bearing pin comprising a journal portion and the details of this journal portion will be discussed subsequently. Three rotary cone cutters are rotatably positioned on the respective three bearing pins extending from the arms. The cutter 14 is shown in FIG. 1. Each of the cutters includes cutting structure on its outer surface adapted to disintegrate the earth formations as the bit 10 is rotated and moved downward. The cutting structure is shown in the form of tungsten carbide inserts 15. However, it is to be understood that other cutting structures such as steel teeth may be used as a cutting structure on the cone cutters.
The bit 10 includes a central passageway extending along the central axis of body 11 to allow drilling fluid to enter from the upper section of the drill string (not shown) immediately above and pass downward through jet nozzles past the cone cutters. In use, the bit 10 is connected as the lower member of a rotary drill string (not shown) and lowered into the well bore until the cone cutters engage the bottom of the well bore. Upon engagement with the bottom of the well bore, the drill string is rotated, rotating bit 10 therewith. Drilling fluid is forced down through the interior passage of the rotary drill string by mud pumps located at the surface. The drilling fluid continues through the central passageway of bit 10, passing through the nozzles past the cutting structure of the cutters to the bottom of the well bore, thence upward in the annulus between the rotary drill string and the wall of the well bore, carrying with it the cuttings and debris from the drilling operation.
The bearing system of the bit, including the seal, must insure free rotation of the cone cutters under the severe drilling environmental conditions. The improved sealing system of the present invention provides an earth boring bit with a long lifetime and that will withstand the conditions encountered in drilling a deep well. The elongated lower portion of arm 13 forms the bearing pin 18 comprising a journal portion and the rotatable cutter 14 is mounted upon the journal portion. A seal ring is positioned between the cutter and bearing pin. The prior art bearings would cause the journal and cutter to run eccentrically, resulting in excessive squeezing of the seal in the loaded area and reduced squeeze in the unloaded area of the journal. The present invention causes the seal centerline and cutter centerline to coincide when the bit is loaded and produce more evenly distributed squeeze on the seal. The loaded portion of the bearing pin includes an eccentrically machined seal groove.
A series of ball bearings (not shown) that bridge between raceways 16 and 17 insure that rotatable cutter 14 is rotatably locked on bearing pin 18. The rotatable cutter 14 is positioned upon bearing pin 18 and the series of ball bearings inserted through a bore extending into arm 13. After the ball bearings are in place, a plug is inserted in the bore and welded therein. A flexible seal 9 forms a seal between a bushing 20 in cutter 14 and groove 19 in bearing pin 18 to prevent loss of lubricant or contamination of the lubricant from materials in the well bore. The seal 9 is positioned in the eccentric groove 19 in the bearing pin.
Referring now to FIG. 2, an enlarged view of the groove 19 in bearing pin 18 is shown. One of the prior art rock bit sealing problems involves the clearance between the bearing pin and cutter. When the bit is loaded on the bottom of the borehole with the underside of the bearing pin in contact with the cutter, all the clearance is on the unloaded side of the bearing; thus, increasing O-ring squeeze in the loaded area and reducing O-ring squeeze in the unloaded area. The present invention permits the cone cutter to run offset from the bearing pin axis but concentric and with the seal groove in the bearing pin to equalize squeeze on the O-ring seal at both the upper, unloaded and the loaded areas of the bearing.
The bearing system of the present invention insures free rotation of the cone cutters under the severe drilling environmental conditions. The improved sealing system of the present invention provides an earth boring bit with a long lifetime and that will withstand the conditions encountered in drilling a deep well. The elongated lower portion of arm 13 forms the bearing pin 18 and the rotatable cutter 14 is mounted upon the bearing pin. The prior art bearing and sealing systems allow the cutter and seal to run eccentrically on the bearing pin, resulting in excessive squeezing of the rubber O-ring in the loaded area and reduced and possibly insufficient squeeze in the unloaded area of the bearing pin. The present invention causes the cone cutter centerline and seal centerline to coincide when the bit is loaded and produce more evenly distributed squeeze on the O-ring seal. This will be illustrated with reference to FIGS. 3 and 4.
Referring now to FIG. 3, a sectional view of cutter 14 and bearing pin 18 is shown with the bit in an unloaded condition. The seal groove 19 is provided by offset grinding or machining. The central axis 23 of the seal groove 19 is offset from the central axis 22 of the bearing pin. The offset of axis 23 with respect to axis 22 is in the direction of the unloaded area on the upper portion of bearing pin 18. When the bit is in the unloaded condition as shown in FIG. 3 the central axis 22 of the bearing pin 18 and the central axis of rolling cutter 14 coincide. The radius of the bearing pin 18 and the inner radius R 1 of the bushing 20 in rolling cutter 14 extend about axis 22. The radius R 2 of the seal groove 19 extends about axis 23.
Referring now to FIG. 4, a sectional view of cutter 14 and bearing pin 18 is shown with the bit in a loaded condition. The loading of the bit has resulted in the bearing pin 18 being moved downward with respect to the rolling cutter 14 by the amount of necessary assembly clearance therebetween. The central axis 23 of the seal groove 19 and the central axis of the rolling cutter now coincide. The radius R 2 of the seal groove 19 still extends about axis 23, however, the radius R 1 of the inner surface 21 of the bushing 20 in rolling cutter 14 now also extends about axis 23. Since the radius R 2 and radius R 1 extend about coincident axes, the squeeze on the seal will be uniform.
The present invention improves the sealing effect of O-ring seal 9. The prior art bearings allowed the seal to run eccentrically, resulting in excessive squeezing of the rubber O-ring in the loaded area and reduced, possibly insufficient, squeeze in the unloaded area of the bearing pin. The present invention allows the seal axis and cutter axis to coincide and produce more evenly distributed squeeze on the O-ring seal when the bit is loaded. The lifetime and performance of the O-ring seal will be extended because of the improved even loading.
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A rolling cone cutter earth boring bit is provided with a sealing system that results in the seal being squeezed uniformly around the seal circumference during drilling. A seal groove is machined in the bearing pin. The seal groove is machined about an axis that is offset from the central axis of the bearing pin in the direction of the unloaded side of the bearing pin. When the bit is drilling and the bearing pin is loaded the seal will run on a diameter concentric with the diameter of the rolling cutter and will see uniform squeeze around its circumference.
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CROSS REFERENCE TO RELATED APPLICATIONS
This application claims the priority of U.S. Provisional Application Ser. No. 60/032,195, which was filed on Dec. 2, 1996.
TECHNICAL FIELD
This invention relates to the art of apparatus for securing a wheelchair to a vehicle. The invention is particularly useful for securing one or more wheelchairs to a bus.
BACKGROUND
Persons using wheelchairs often wish to ride in a vehicle such as a bus, train, or airplane while remaining in the wheelchair. In these instances, the wheelchair must be secured to the vehicle to ensure the safety of the passenger. When the vehicle is a public bus, an additional concern is the ease by which the operator can secure and release the wheelchair so that a minimum of time is spent in this activity. Further, it is often necessary to provide a vehicle with a plurality of tie-down stations whereby a plurality of passengers in wheelchairs can be accommodated simultaneously.
Prior wheelchair tie-downs are awkward in use. For example, one such tie-down comprises a number of receptacles in the floor of a transit vehicle and an equal number of straps, each with a hook at one end for engaging the frame of the wheelchair and a lug at the opposite end for engaging one of the receptacles. This system is very difficult in use because it requires the operator first to locate the straps and then to attach the straps to the chair and the floor and adjust their lengths, which requires reaching, bending, and the like. Moreover, the straps are often not available, having been lost between uses because they are not attached to the bus when not in use, and when found, they are usually dirty from contact with the floor or storage in a box with other items. Securing the straps to the floor during periods of non-use is not feasible because their presence would restrict movement of the wheelchair into or out of the station and would present a hazard, possibly tripping others walking in the bus. Further, the heel of a high-heeled shoe is easily caught in the receptacles themselves, resulting in personal injury, property damage, and delay.
SUMMARY OF THE INVENTION
In accordance with the invention a strong, safe, and easily applied tie-down for wheelchairs is provided. The tie-down finds particular utility in a public bus, where the safe and efficient ingress and egress of wheelchair passengers is very important to ensure safety and reduce delays for all passengers. Moreover, the tie-down of the invention does not require dedicated floor space, thus allowing other passengers to use the same floor space when wheelchair passengers are not present.
In the preferred embodiment, the tie-down of the invention is located in a bus adjacent chairs that fold against the side of the bus to expose the floor space beneath the chairs. Two wheelchairs are preferably arranged in this space with both of them facing forward, either on respective sides of the vehicle or in tandem.
A first securing element is fixed to the bus at one end of the space to be occupied by a wheelchair, and a second securing element is movably attached to the other end of the space to be occupied by that wheelchair. The second securing element is preferably pivotally attached to the bus for movement horizontally, whereby it may be placed in an unobtrusive storage position adjacent the side of the bus and moved to an operative, securing position, extending perpendicularly from the side of the bus when required. Each of the first and second securing elements carries straps with hooks for engaging the structure of the wheelchair to hold it to the securing elements. The straps are preferably carried by winches that can be operated easily and quickly to release or retract the straps whereby they may be attached and tightened, or released and detached easily.
When the space is to be occupied by more than one wheelchair, a third securing element is fixed to the bus at the opposite end of the wheelchair space, such that the movable securing element, when in its operational position, is midway between front and rear securing elements. In the preferred embodiment, the rearmost securing element is fixed and the central and front securing elements are pivotal.
The movable securing element includes means for holding it in the storage and operational positions. The particular means may be any of several designs, but the preferred design for holding this element in the operational position is a vertically-movable pin carried by the movable element for engaging an aperture in a floor plate when the securing element is in the operational position. This pin includes a handle at its upper end for easy grasping by the operator to push the pin into the recess when a wheelchair is being secured and to pull it from the recess to move the securing element to the storage position. The pin is preferably a "Ball-lok" pin that includes retractable retaining balls near the end of the pin. These balls are controlled by a central shaft that is axially movable. The shaft is spring-biased to a position where the balls are in the locking position, and the shaft can be moved by pressing on one end to a position where the balls move inward to release the pin from the floor plate. Thus, when the pin is placed in an aperture in the floor plate, the balls will protrude from the sides of the pin to engage the aperture and prevent removal of the pin. The operator can remove the pin from the floor plate by depressing the button formed by the end of the shaft and lifting the pin from engagement with the floor plate.
Other means may be used for securing the movable element. For example, the latch for retaining the movable element in the storage position may be located near the pivot axis. Thus, the end of the movable element near the wall could be provided with an element, such as a disk with apertures for cooperating with a removable pin for holding the disk and the movable securing element in any of several predetermined positions, including the operational and storage positions.
It will be appreciated that the movable securing element may be mounted for movement in other than a horizontal plane. For example, this element may be mounted for movement vertically in those situations where passengers not in wheelchairs will not be bothered by the presence of the movable element in the storage position. Also, the movable element could be made such that it telescopes outwardly from the side wall of the bus. In this arrangement, storage would be in a collapsed configuration, and operation would be from an expanded configuration. As well, the vertically movable element could be telescoping whereby the stored position would not interfere with other passengers.
In operation, a wheelchair passenger approaches the space having the tie-down such that one end of the wheelchair is adjacent one of the front or rear securing elements. If the entire space is unoccupied, this is very easy because the movable element will be in its storage position. If the space is already occupied by a first wheelchair, it may be necessary for the bus operator to move the movable element slightly to facilitate entry of the second wheelchair. In either situation, the wheelchair is positioned in the wheelchair area with one end of the wheelchair adjacent one set of securing elements located at opposite ends of the area, and the central movable element is moved into position adjacent the other end of the wheelchair. The operator presses the pin into the recess to secure the movable element, and the straps are attached to the frame of the wheelchair. In the preferred embodiment, there are four straps with hooks or looped belts that engage the frame. The straps are carried by winches, which are turned by the operator to tighten the straps. When a wheelchair passenger desires to exit the bus, the operator releases the straps by actuating release buttons on the winches, removes the hooks from the wheelchair, and, if necessary, moves the movable element to allow the passenger to exit the bus.
An advantage of the movable element is that it may be moved to provide aisle clearance when required.
The above description has focused on operation with regard to a wheelchair having a tubular frame. The invention may be used equally well for other types of vehicles, such as electric powered vehicles with non-tubular frames, such as "scooters." Securing such a vehicle merely requires that straps be located on the fixed and movable elements with engaging elements designed for the frame of this type of vehicle. In this connection it is noted that the term "wheelchair" as used herein refers generally to any type of personal vehicle.
It is an object of this invention to provide a tie-down for a wheelchair that provides passenger safety and is easy to operate, resulting in significantly reduced time required by the vehicle operator.
Another object of this invention is to provide a tie-down for a wheelchair that makes economical use Of the available space on a vehicle.
Yet another object of this invention is to provide a unique method for securing wheelchairs to a vehicle.
Still another object of the invention is to provide a tie-down for a wheelchair that retains the securing straps in safe, permanent location that is isolated from debris normally found in high-use vehicles, whereby the straps are maintained in better condition readily available for use.
These and other objects will be apparent from the following detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side elevation view of a tie-down in accordance with the invention.
FIG. 2 is a top plan view of a tie-down in accordance with the invention installed on a bus.
FIG. 3 is a perspective of a movable element used in the embodiment shown in FIGS. 1 and 2.
FIG. 4 is a perspective of a second movable element used in the embodiment shown in FIGS. 1 and 2.
FIG. 5 is a top plan view of the floor plate.
FIG. 6 is an exploded view of the floor plate of FIG. 4 and partially in cross section.
FIG. 7 is a perspective of another embodiment of a movable element.
FIGS. 8a and 8b are perspectives of a further embodiment of a movable element.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
FIGS. 1 and 2 illustrate a tie-down in accordance with a preferred embodiment of the invention installed in a bus. The tie-down shown in these figures is arranged to accommodate two wheelchairs in a wheelchair securing area and comprises a central movable securing element 2 located between the wheelchairs, a fixed securing element 4 at the rear of the area, and a second movable securing element 5 at the front of the area. The wheelchair securing area may also be occupied by side-facing seats 6, which are shown in their folded-up positions. Thus, the space occupied by the tie-down to be described is used by passengers in seats such as 6 when not occupied by passengers in wheelchairs and seats 6 are folded down.
The movable securing element 2 is mounted for pivotal movement to and from the operational position, shown in solid lines in FIG. 1, where it extends perpendicularly from the side wall 8 of the bus. When not in use, the movable securing element 2 may be moved to a storage position, which is shown in phantom lines. As well, element 5 is constructed similarly to that of the movable element 2 and may be moved to a storage position, also shown in phantom lines, when not in use.
The end of the movable securing element nearer the side wall of the bus is pivotally connected to the bus. With reference also to FIG. 3, the connection is provided by a bracket 10, which is bolted to the side wall of the bus at flanges 12. The lower part of the bracket includes a U-shaped pivot bracket 14, which receives a pivot pin 16. The pin 16, in turn, engages a second U-shaped bracket 17 in the end of the movable element 2 to provide pivotal movement of the element 2 about the pin.
A releasable locking mechanism is provided on the movable securing element remote from the pivot pin 16. In the preferred embodiment, the locking element includes a vertically-movable locking pin 18 and a floor plate 20 with a recess therein, which will be more fully described below with respect to FIGS. 5 and 6. The recess in the floor plate receives the pin 18 to secure the movable element 2 in the operational position when the pin is moved downward. The upper end of the pin 18 has a handle 22 for facilitating upward movement of the pin by the operator to disengage the pin from the recess, whereby the movable element 2 may be pivoted forward or rearward. The pin 18 is preferably of the type sold under the trademark "Bal-lok," which has locking balls at one end that are controlled by a spring-loaded, central shaft. The upper end of the shaft forms a button 23 for allowing the operator to depress the shaft and release the balls by pressing on the button. When the balls are held outward by the shaft, the pin 18 will be secured in the recess, and depression of the button will release the pin.
Each of the fixed and movable securing elements includes at least two adjustable straps 24, each of which has a hook 26 for engaging the frame of a wheelchair. Each strap is contained in a housing 28, which is attached to the securing element at desired locations. The housings may provide a hand-operated winch for allowing the operator to tighten the strap after the hook is applied to the frame of the wheelchair by rotation of the winch. Preferably, the housings carrying straps for the front of the wheelchair include winches, while those for engaging the rear of the chair do not require that structure. The housings include quick-release features as are known in the art to allow the straps to be released easily for unrolling the straps, disengaging the hooks, and freeing the wheelchair. The housings 28 are preferably arranged in spaced pairs for engaging the left and right sides of the front and rear of the wheelchairs at angles that will be the most effective. Such angles have been determined and are generally known to those of skill in the art.
With reference to FIGS. 1 and 2, the passenger seat belts 25 are also provided, which are carried in housings 29. Generally, the desirable arrangement is for the passenger lap belt housings 29 to be spaced more widely than that of housings 28 for the rear wheelchair-restraining belts. Thus, in the configuration shown in the figures, where the wheelchairs are both facing forward, the housings 29 having lap belts for the front passenger are more widely spaced than are the housings 28 that contain wheelchair restraining belts for the rear of the front wheelchair. In the embodiment shown, one of the housings 29 is placed on an outboard end of the movable element 2, and the other is placed on the mounting bracket 10, for example, at threaded opening 11. The housings 28 for the wheelchair restraining belts for the fronts of the wheelchairs are spaced more widely than are the housings for the rear of a wheelchair and are preferably spaced at the same distance as are the housings for the passenger restraining belts. Clearly, other arrangements may be useful for other situations.
The housings 28 and 29 are preferably mounted to the movable securing element 2 and 5 by respective mounting brackets 30 and 32. These brackets are secured to the movable elements, as by welding, and include mounting holes for receiving mounting bolts (not shown) that extend through the bracket and engage threaded openings in the belt housings. The mounting brackets preferably mount the housings on top of the movable element, as shown, to provide ready access for the operator and to reduce the likelihood they will become contaminated with dirt, water, and the like from the floor of the vehicle. The housings are preferably mounted with washers that allow the housings to pivot and align automatically with the angle of the tension placed on the belts themselves.
As noted, the movable elements 2 and 5 may be moved to non-operational positions when there are no wheelchair passengers and the chairs 6 are in use. The elements are retained in the non-operational positions, shown in phantom lines in FIGS. 3 and 4, by second floor plates 21, which are the same as floor plates 20.
The fixed securing element 4 is a rigid, L-shaped element bolted to the side wall and floor of the vehicle in known manner and may include a partition as illustrated.
FIG. 4 is a perspective of front movable element 5. This element includes mounting brackets 32, which mount only two housings 28 for securing the front of the wheelchair of the front passenger. Also, the bracket 10 shown in FIG. 4 is of an optional configuration wherein one flange 12 attaches to the side wall of the vehicle, and the other flange attaches to the floor of the vehicle. That configuration may be used for the central securing element, as well.
FIGS. 5 and 6 illustrate a preferred embodiment of the floor plate. The floor plate includes a cover assembly 34, which comprises a cover 36 hinged to a top plate 38. A securing plate 40 is welded to the bottom of the top plate and includes a hole 42 therein for receiving the locking pin 18. A lower cover plate 44 is the lowermost part of the assembly and includes a pan portion 46 for being placed in an opening in the floorboard of the vehicle. A seal 48 made of flexible material such as Neoprene is placed between the top cover assembly and the lower cover plate to prevent accumulation of debris in the pan 46 through the hole 42. In turn, the pan 46 seals the assembly from entry of debris from below the assembly.
The cover 36 is attached by hinges 50, which are known in the art, for allowing the cover to be easily opened and to have a full 180° range of motion.
FIG. 7 illustrates an embodiment wherein the movable securing element 2 is mounted for vertical motion with respect to the vehicle. This is attained by providing a pivotal mounting bracket 14', which is rotated 90° with respect to the bracket 14, and a second bracket 17' also rotated 90° with respect to bracket 17. Thus, a pivot pin 16' is horizontal to provide vertical movement of the movable-element 2. A storage position of the movable element is shown in FIG. 7 in phantom lines. The movable element may be held in the storage position in any of several ways, such as by a known strap or latch.
FIGS. 8a and 8b show yet another embodiment wherein the movable element 2 telescopes. Thus, the bracket 10, includes a fixed horizontal portion 58 that receives a reduced diameter portion 60 of movable element 2 whereby the movable element can be moved between the storage position of FIG. 8a and the operative position of FIG. 8b by sliding the portion 60 with respect to fixed horizontal portion 58. In this embodiment, the movable element 2 is held in the storage position of FIG. 8a by engagement between the locking pin 18 and a second floor plate 62, which is located inboard of floor plate 20. The movable element 2 is held in the operative position shown in FIG. 8b by engagement between the locking pin 18 and the recess and floor plate 20.
In operation, the system of the invention greatly facilitates transportation of passengers in wheelchairs. A significant advantage of the invention is that the time required for securing or releasing a wheelchair is greatly reduced from prior systems. Further, because the straps are permanently attached, they will be readily available for use, which obviates the drivers searching for loose straps, as in the prior art systems. The straps are also clean and in good repair because they are retained in the housings when not in use. Still further, the invention allows the wheelchair area to be used by other passengers when the seats 6 are placed in their operational positions (not illustrated). Of course, the area designated for wheelchairs may be used exclusively for wheelchairs. The securing elements are shown in FIGS. 1 and 2 in the configuration wherein the wheelchairs are placed in tandem, with both facing forward. It is also possible for the securing elements to be placed such that the wheelchairs are facing each other, or more preferably, arranged with a single wheelchair facing forward on each side of the vehicle. In this latter case, each arrangement would be very much like that for the rear wheelchair in FIGS. 1 and 2. In the case of a single wheelchair station, however, the brackets on the movable element for the housings would have the configurations shown in FIG. 4.
The wheelchairs are easily attached to the securing elements by pivoting the movable elements to positions that will allow the wheelchairs to be rolled into the desired positions. Guide bars 54 are placed along the side walls to assist in positioning the wheelchairs in a direction transverse to the bus. Then, the operator places the movable elements in the positions shown in FIGS. 1 and 2 and attaches the wheelchair restraining straps and the passenger safety belts. In the configuration shown in FIGS. 1 and. 2 shoulder belts 52 are used as well as lap belts to ensure safety.
Modifications within the scope of the appended claims will be apparent to those if skill in the art.
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Apparatus for securing one or more wheelchairs to a vehicle includes a plurality of straps for holding the wheelchairs to the vehicle. Some of the straps are attached to a movable element that can be moved into or out of the area to be occupied by the wheelchairs. This allows the area to be utilized by other passengers when no wheelchairs are present and also facilitates ingress and egress of the wheelchairs. In the preferred embodiment, movable elements, which carry housings for wheelchair-engaging belts and passenger restraint belts, are mounted to the side wall of the vehicle for pivotal movement about vertical axes between storage positions and operative positions. The apparatus allows an operator to quickly and easily secure or release a passenger in a wheelchair and maintains the integrity of the straps.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] Example embodiments relate generally to cooling electronic devices, and more particularly to a method and apparatus for a variable heat conductor positionable between an electronic device and a heat sink to facilitate rapid warming of the electronic device during startup of the electronic device at low temperatures.
[0003] 2. Related Art
[0004] Electronic devices, such as integrated circuits, processors, memory chips, field-programmable gate arrays (FPGA), logic chips, etc., generally require cooling in order to operate efficiently and effectively, especially at high temperatures. In order to facilitate such cooling, a conventional thermal stack-up 10 is often employed, as shown for instance in FIG. 1 . The thermal stack-up 10 may include a heat conductor 4 in contact with an electronic device 2 and a heat sink 6 . The heat conductor 4 is generally made from a material, such as a metal, that offers a high heat conductivity in order to efficiently conduct and transmit heat from the electronic device 2 to the heat sink 6 . In particular, the heat conductor 4 absorbs thermal energy from the electronic device 2 via convection, radiation, and mostly notably conduction, and facilitates the transfer of this energy to the heat sink 6 . Because conduction is the primary mode of the thermal energy transmission, the heat conductor 4 often directly contacts both the electronic device 2 and the heat sink 6 .
[0005] The heat sink 6 often times takes the form of an enclosure, a cooling plate, a housing, a support, fins, ribs, or any other suitable structure that facilitates heat expulsion from the heat conductor 4 .
[0006] Conventionally, a thermal stack-up 10 is effective in removing thermal heat from an electronic device 2 , allowing the electronic device 2 to operate in an appropriate temperature operating range even at high ambient temperatures (or, even in confided spaces, where operation of the electronic device 2 may cause significant heat emission). However, while a conventional thermal stack-up 10 is effective in removing heat, this heat removal can be counterproductive during periods of electronic device 2 startup, especially when the startup occurs at low temperatures. The startup of ever more highly-integrated circuits, with services required to operate in wide temperature ranges (for instance, in temperature ranges between −40° C. and 85° C.), act to exacerbate startups at very low temperatures. For instance, conventional high-performance central processing units (CPUs) currently are not rated to be able to quickly turn-on at −40° C. Therefore, at very low temperatures, electronic devices 2 in a conventional thermal stack-up 10 may either take an exceptionally long period of time to startup, or the electronic devices 2 may not be able to turn-on and function, at all.
BRIEF DESCRIPTION OF INVENTION
[0007] Example embodiments provide a method and an apparatus for a variable heat conductor that is able to increase heat conduction capacity based on operating temperature. Specifically, the variable heat conductor may act as a thermal isolator at lower temperatures, and the variable heat conductor may fully conduct heat at higher temperatures that are at or above a desired temperature set-point.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] The above and other features and advantages of example embodiments will become more apparent by describing in detail, example embodiments with reference to the attached drawings. The accompanying drawings are intended to depict example embodiments and should not be interpreted to limit the intended scope of the claims. The accompanying drawings are not to be considered as drawn to scale unless explicitly noted.
[0009] FIG. 1 is a simplified diagram of a conventional thermal stack-up;
[0010] FIG. 2 is a simplified diagram of a thermal stack-up, in accordance with an example embodiment;
[0011] FIG. 3 is a detailed view of a variable heat conductor, in accordance with an example embodiment;
[0012] FIG. 4 is a view of the fully-assembled variable heat conductor of FIG. 3 , in accordance with an example embodiment;
[0013] FIG. 5 is an overhead and cross-sectional view of the fully-assembled variable heat conductor of FIG. 4 , in accordance with an example embodiment;
[0014] FIG. 6 is a magnified view of detail B of FIG. 6 , in accordance with an example embodiment;
[0015] FIG. 7 is a detailed view of another variable heat conductor, in accordance with an example embodiment;
[0016] FIG. 8 is an overhead and cross-sectional view of the fully-assembled variable heat conductor of FIG. 7 , in accordance with an example embodiment; and
[0017] FIG. 9 is a magnified view of detail D of FIG. 8 , in accordance with an example embodiment; and
[0018] FIG. 10 is a flowchart of a method of making and using a variable heat conductor, in accordance with an example embodiment.
DETAILED DESCRIPTION
[0019] Detailed example embodiments are disclosed herein. However, specific structural and functional details disclosed herein are merely representative for purposes of describing example embodiments. Example embodiments may, however, be embodied in many alternate forms and should not be construed as limited to only the embodiments set forth herein.
[0020] Accordingly, while example embodiments are capable of various modifications and alternative forms, embodiments thereof are shown by way of example in the drawings and will herein be described in detail. It should be understood, however, that there is no intent to limit example embodiments to the particular forms disclosed, but to the contrary, example embodiments are to cover all modifications, equivalents, and alternatives falling within the scope of example embodiments. Like numbers refer to like elements throughout the description of the figures.
[0021] It will be understood that, although the terms first, second, etc. may be used herein to describe various elements, these elements should not be limited by these terms. These terms are only used to distinguish one element from another. For example, a first element could be termed a second element, and, similarly, a second element could be termed a first element, without departing from the scope of example embodiments. As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items.
[0022] It will be understood that when an element is referred to as being “connected” or “coupled” to another element, it may be directly connected or coupled to the other element or intervening elements may be present. In contrast, when an element is referred to as being “directly connected” or “directly coupled” to another element, there are no intervening elements present. Other words used to describe the relationship between elements should be interpreted in a like fashion (e.g., “between” versus “directly between”, “adjacent” versus “directly adjacent”, etc.).
[0023] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments. 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”, “comprising,”, “includes” and/or “including”, when used herein, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
[0024] It should also be noted that in some alternative implementations, the functions/acts noted may occur out of the order noted in the figures. For example, two figures shown in succession may in fact be executed substantially concurrently or may sometimes be executed in the reverse order, depending upon the functionality/acts involved.
[0025] FIG. 2 is a simplified diagram of a thermal stack-up 12 , in accordance with an example embodiment. The stack-up 12 is similar to the conventional thermal stack-up 10 of FIG. 1 . However, stack-up 12 utilizes a variable heat conductor 8 that acts as a thermal isolator at lower temperatures, and fully conducts heat at higher temperatures that are at or above a desired temperature set-point, as described in detail herein.
[0026] FIG. 3 is a detailed view of a variable heat conductor 8 , in accordance with an example embodiment. The heat conductor 8 may conic in two major parts that may include a main body 20 and a lid 30 . While FIG. 3 depicts the main body 20 in the shape of a square, the main body 20 may be formed of any shape. The main body 20 may include a lip 22 capable of securely retaining lid 30 . The main body 20 may include a till material 24 , and a post 26 , with an upper surface of the fill material 24 and the post 26 existing at the same elevation. A high-thermal-expansion material 40 may be anchored to the main body 20 . An upper surface of the high-thermal-expansion material 40 may exist at an elevation that is slightly lower than the elevation of the fill material 24 and post 26 , in order to account for the thermal expansion of the high-thermal-expansion material 40 (this difference in elevation is best depicted in FIG. 6 ).
[0027] The high-thermal-expansion material 40 may be formed from a material that is different from a material that is used to form the remainder of the variable heat conductor 8 . That is to say, the lid 30 , the lip 22 , the fill material 24 and post 26 of the heat conductor 8 may be formed of one common material (indicated as Material A in Table 1, below), whereas the high-thermal-expansion material 40 may be formed from a different material (indicated as Material B in Table 1, below). As shown in Table 1, Material A includes materials with lower thermal expansion coefficients (a) relative to the materials listed as Material B.
[0000]
TABLE 1
Linear Expansion
Thermal Conductivity
α (10 −6 /K)
λ (W/mK)
Material A
Diamond
1.3
2300
Copper
16.8
380
Material B
Aluminum
23.8
180
Indium
56
82
[0028] Table 1 is a non-exhaustive list of potential materials for the variable heat conductor. Due to the differences in thermal expansion between Material A and Material B, the materials listed as Material B experience a greater change in length per increment of temperature change (see the formula for linear expansion in Equation 1, below).
[0000] Δ l=l 0 ·α·Δt Equation 1
[0029] wherein Δl=change in length of a material
l 0 =an original length of the material. α=the linear thermal expansion of the material Δt=change in temperature
[0033] It is important to note that variable heat conductors will perform more effectively when Material A and Material B possess a greater disparity in thermal expansion. This is because materials with a greater disparity in thermal expansion will experience a greater disparity in thermal growth (relative to each other) over a given temperature range, causing gaps within the heat conductor to close at a more precisely determined temperature (see the gaps in FIGS. 6 and 9 ), as described herein in more detail. Therefore, a heat conductor formed from Diamond and Indium will perform more effectively than a heat conductor formed from Aluminum and Copper, using the example materials shown in Table 1.
[0034] It should also be understood that the heat conductor 8 components made from Material A (as described above) may also be made from more than one material. Likewise, the heat conductor 8 components made from Material 13 (also described above) may also be made from more than one material. The only requirement for material selection is that the Material B components are formed from a material possessing a greater rate of thermal expansion as compared to the Material A components.
[0035] FIG. 4 is a view of the fully-assembled variable heat conductor 8 of FIG. 3 , in accordance with an example embodiment. As shown in FIG. 4 , the lid 30 of heat conductor 8 has been pressed into the top of main body 20 , where lid 30 is being held in place by lip 22 . In the full-assembled configuration, heat conductor 8 includes two major surfaces, major surface 12 a (on top of the heat conductor) and major surface 1213 (below the heat conductor). When inserted into thermal stack-up 12 ( FIG. 2 ), one of the major surfaces 12 a / 12 b of heat conductor 8 may be positioned to contact heat sink 6 , and the other major surface 12 a / 12 b may be positioned to contact electronic device 2 . While the heat conductor 8 may operate more effectively when major surface 12 b is contacting the electronic device 2 (as the high-thermal-expansion material 40 is anchored to the bottom of main body 20 , allowing heat transmission from electronic device 2 directly to high-thermal-expansion material 40 via conduction), the heat conductor 8 will operate adequately in either configuration.
[0036] FIG. 5 is an overhead and cross-sectional view of the fully-assembled variable heat conductor 8 of FIG. 4 , in accordance with an example embodiment. The overhead view more clearly depicts the layout of the fill material 24 and post 26 locations relative to the high-thermal-expansion material 40 . Cross-section A-A more clearly depicts lid 30 being retained by lip 22 of main body 20 .
[0037] FIG. 6 is a magnified view of detail B of FIG. 6 , in accordance with an example embodiment. In particular, detail B identifies gaps G 1 /G 2 between components of heat conductor 8 , which account for the disparity in thermal expansion between the Material A and Material B materials. Specifically, gap G 1 is a small gap that is provided between high-thermal-expansion material 40 and an inner surface of lid 30 . This gap G 1 accounts for growth in the length of high-thermal-expansion material 40 in an y-axis direction. Gap G 2 is also provided between fill material 24 and high-thermal-expansion material 40 , accounting for growth in the length of high-thermal-expansion material 40 in a x-axis direction (gap G 2 being purposefully larger than gap G 1 , as high-thermal-expansion material 40 has a greater length in the x-axis direction).
[0038] FIG. 6 depicts gaps G 1 /G 2 in a state in which the temperature of heat conductor 8 is relatively cool. A precise determination of the size of gap G 1 may be determined (via Equation 1) to ensure that the gap G 1 may close at a desired temperature set-point. That is to say, as heat conductor 8 is warmed within thermal stack-up 12 (as electronic device 2 experiences startup, at a relatively cold temperature, and begins to emit heat energy), gap G 1 will begin to narrow and eventually close. Therefore, an optimally sized gap G 1 will close at the desired temperature set-point, ensuring that heat conductor 8 will begin to fully conduct heat energy at or above the desired temperature set-point (as high-thermal-expansion material 40 expands and fully contacts the inner surface of lid 30 ). Because gap G 1 exists in a plane that intersects an expected direction of heat transmission through conductor 8 , the closing of gap G 1 will facilitate heat conduction through conductor 8 . Furthermore, if gap G 1 is approximately perpendicular to the shortest distance of travel for heat transmission from electronic device 2 to heat sink 6 (i.e., gap G 1 exists in a plane along the x-axis), gap G 1 will offer the greatest efficiency of heat conduction (as gap G 1 transitions from an open to closed position).
[0039] Gap G 2 is provided to allow high-thermal-expansion material 40 to also grow in the x-axis direction. Because gap G 2 is defined to exist at an angle that is approximately parallel to the flow of heat transmission from electronic device 2 to heat sink 6 (i.e., gap G 2 exists in a plane along the y-axis), gap G 2 therefore does not necessarily need to be sized to close precisely at the desired temperature set-point. This is because the closing of gap G 2 is not as critical to the transmission of heat.
[0040] FIG. 7 is a detailed view of another variable heat conductor 8 a , in accordance with an example embodiment. Heat conductor 8 a includes a main body 20 a with a lid 30 a . The lid 30 a may include strips 40 a made from a high-thermal-expansion material that are anchored to an inner surface of the lid 30 a . The main body 20 a may include a fill material 24 a with ribs 26 a that define slots 28 a sized to accept accommodate the high-thermal-expansion material strips 40 a when fully assembled. Lip 22 a may be provided to retain lid 30 a when lid 30 a is placed on main body 20 a.
[0041] Similar to heat conductor 8 ( FIG. 3 ), the components of heat conductor 8 a ( FIG. 7 ) may be formed from two materials, identified as Material A and Material B, respectively, as listed in the non-exhaustive list of potential materials, shown in Table 1. Specifically, the high-thermal-expansion material strips 40 a may be formed from Material B, whereas all other components (lid 30 a , main body 20 a , lip 22 a , fill material 24 a and ribs 26 a ) may be formed from Material A.
[0042] FIG. 8 is an overhead and cross-sectional view of the fully-assembled variable heat conductor 8 a of FIG. 7 , in accordance with an example embodiment. The overhead view more clearly depicts the layout of the slots 28 a housing strips 40 a . Cross-section C-C more clearly depicts lid 30 a being retained by lip 22 a of main body 20 a . Heat conductor 8 a may be inserted into thermal stack-up 12 ( FIG. 2 ) such that one of major surfaces 11 a / 11 b of heat conductor 8 a may directly contact electronic device 2 , whereas the other of the major surfaces 11 a / 11 b may directly contact heat sink 6 (with a preference for major surface 11 b contacting electronic device 2 , as the high-thermal-expansion material strips 40 a are anchored on lid 30 a , allowing a direct transmission of conductive heat energy from electronic device 2 to the high-thermal-expansion material strips 40 a ).
[0043] FIG. 9 is a magnified view of detail D of FIG. 8 , in accordance with an example embodiment. Gap G 4 purposefully exists along a plane that is perpendicular to the direct path of energy transmission from electronic device 2 to heat sink 6 (i.e., gap G 4 exists in a plane along the x-axis). Therefore, gap G 4 may be sized to close at a desired temperature set-point (allowing high-thermal-expansion material strips 40 a to frilly contact a bottom surface of slots 28 a ), in order to maximize heat conduction efficiency at the desired temperature set-point. Because gap G 3 exists in a plane that is parallel to the transmission of heat energy (i.e., the y-axis), gap G 3 does not necessarily need to be designed to close precisely at the desired temperature set-point. Instead, gap G 3 is to be sized simply to allow extra room for the thermal expansion of the high-thermal-expansion material strips 40 a in the x-axis direction with each slot 28 a.
[0044] FIG. 10 is a flowchart of a method of making and using a variable heat conductor 8 / 8 a , in accordance with an example embodiment. Specifically, step S 100 may include making a variable heart conductor 8 / 8 a by forming a first major body (such as the main body 20 of FIG. 3 , or the lid 30 a of FIG. 7 ) and a second major body (such as lid 30 , or main body 20 a ) from at least a first material. The first material may be a material listed as Material A (shown in Table 1).
[0045] Both the first/second major bodies may be formed of any shape which may be appropriate in order to cool an electronic device 2 . For instance, if the electronic device 2 is a large square-shaped device, the first/second major bodies may be in the form of a square shape that may be conformed to a side surface of the electronic device 2 . A depth/thickness of the first/second major bodies may vary, depending on the type of service (which may include the expected/desired amount of heat removal for the electronic device 2 , the temperature of a heat sink 6 , the materials chosen for the heat conductor 8 / 8 a , etc.). It should also be understood that more than one material may be used to make the first and/or second major bodies.
[0046] Step S 102 may include anchoring a high-thermal-expansion material 40 / 40 a to the first major body 20 / 30 a . The anchoring may be accomplished via welding, fasteners, adhesive, or any other suitable means of firmly affixing the high-thermal-expansion material 40 / 40 a to the first major body 20 / 30 a . The high-thermal-expansion material 40 / 40 a may be a material listed as Material B (shown in Table 1). However, other materials, besides the materials listed in Table 1, may also be used in order to make the high-thermal-expansion material 40 / 40 a and the first second major bodies of the heat conductor 8 / 8 a , so long as the high-thermal-expansion material 40 / 40 a is made from a material that offers greater thermal expansion as compared to the material(s) for the first and/or second major bodies.
[0047] Step S 104 may include defining a gap G 1 /G 4 between a distal end of the high-thermal-expansion material 40 / 40 a and an inner surface of the second major body 30 / 20 a . The gap G 1 /G 4 may exist in a plane that is about perpendicular to an expected direction of heat transmission through the heat conductor 8 / 8 a , in order to maximize the efficiency of the heat conductor 8 / 8 a . This gap G 1 /G 4 is to be designed to account for thermal expansion of the high-thermal-expansion material 40 / 40 a (which will thermally expand at a greater rate than the Material A portions of the heat conductor 8 / 8 a ) in the expected direction of heat transmission through heat conductor 8 / 8 a . In particular, a determination of a length of gaps G 1 /G 4 may be calculated via Equation 1 (above) to ensure that the gaps G 1 /G 4 close at a desired temperature set-point. That is to say, the length of the gap is determined in order to account for growth of the high-thermal-expansion material 40 / 40 a , which will be experienced as a temperature of the heat conductor 8 / 8 a changes between a cold start-up temperature of the electronic device 2 and the desired temperature set-point of the electronic device 2 .
[0048] The desired temperature set-point may be a temperature set-point that is specific to the electronic device 2 . That is to say, the desired temperature set-point may be a temperature that the electronic device 2 is rated to effectively operate at without any known performance problems.
[0049] Additional gaps G 2 /G 3 may also be provided on lateral sides of the high-thermal-expansion material 40 / 40 a , in order to account for the thermal expansion of the high-thermal-expansion material 40 / 40 a in other directions that may be about perpendicular to the expected direction of heat transmission through heat conductor 8 / 8 a.
[0050] Step S 106 may include inserting the heat conductor 8 / 8 a into a thermal stack-up 12 . Specifically, the heat conductor 8 / 8 a may be placed between the electronic device 2 and the heat sink 6 . In order to maximize the effectiveness of heat transmission between the electronic device 2 and the heat sink 6 , the heat conductor 8 / 8 a may directly contact both the electronic device 2 and the heat sink 6 (in order to maximize the amount of heat conduction through heat conductor 8 / 8 a ), though the direct contact of the heat conductor 8 / 8 a with either the electronic device 2 and/or the heat sink 6 is not mandatory (as the heat conductor 8 / 8 a may still transmit heat that is absorbed and/or transmitted via convection radiation, as opposed to conduction). The heat conductor 8 / 8 a may be positioned between the electronic device 2 and heat sink 6 by ensuring that the gaps G 1 /G 4 are positioned to exist in a plane that is about perpendicular to an expected direction of heat transmission through the heat conductor 8 / 8 a , in order to maximize the efficiency of the heat conductor 8 / 8 a.
[0051] Step S 108 may include stacking-up the electronic device 2 within the thermal stack-up 12 . Because gaps G 1 /G 4 exist in a plane that is perpendicular to the expected direction of heat transmission through the heat conductor 8 / 8 a , the gaps G 1 /G 4 will significantly reduce the amount of heat transmission flowing through the heat conductor 8 / 8 a at temperatures which are below the desired temperature set-point. This allows heat conductor 8 / 8 a to act as a thermal isolator at low temperatures (while electronic device 2 starts-up), allowing electronic device 2 to start-up more quickly and effectively than an electronic device 2 in a conventional thermal stack-up 10 .
[0052] Step S 110 may include allowing heat transmission from the electronic device 2 to flow through heat conductor 8 / 8 a , causing the high-thermal-expansion material 40 / 40 a to thermally expand at a greater rate than the Material A portions of heat conductor 8 / 8 a . By allowing this heat transmission to flow through heat conductor 8 / 8 a , and heat the heat conductor 8 / 8 a , the gaps G 1 /G 4 will then close at the desired temperature set-point. This will allow heat conductor 8 / 8 a to fully conduct heat at higher temperatures (at or above the desired temperature set-point), when heat transmission from the electronic device 2 to heat sink 6 is necessary and desired.
[0053] This written description uses examples to disclose the invention, including the best mode, and also enables any person skilled in the art to practice the on, including making and using any devices or systems and performing any incorporated methods. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.
[0054] Example embodiments having thus been 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 intended spirit and scope of example embodiments, 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.
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A method and apparatus for a variable heat conductor that is able to increase heat conduction capacity based on operating temperature. The variable heat conductor is to be positioned between an electronic device and a heat sink to facilitate cooling of the electronic device. During cold start-up of the electronic device, the variable heat conductor acts as a thermal isolator, causing the electronic device to warm more quickly following the cold start-up. The variable heat conductor may fully conduct heat at higher temperatures that are at or above a desired temperature set-point.
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CROSS REFERENCE TO RELATED APPLICATIONS
Co-Pending and Previously Submitted Patent Application
[0001] Methods for detection of ultraviolet light reactive alternative cellular energy pigments (ACE-pigments). William John Martin Submitted Dec. 24, 2007. Publication number 20090163831
[0002] Method of assessing and of activating the alternative cellular energy (ACE) pathway in the Therapy of Diseases. William John Martin Submitted Jan. 16, 2008. Publication number 20090181467
[0003] Enerceutical mediated activation of the alternative cellular energy (ACE) pathway in the therapy of diseases. Submitted May 8, 2008. Publication number 20090280193 Regenerative wound healing using copper-silver citrate composition. Publication number: 20100099758 Submitted Oct. 22, 2008.
[0004] Enerceutical activation of the alternative cellular energy (ACE) pathway in therapy of diseases. Submitted Feb. 11, 2009. Publication number 20090202442
[0005] Method of using the body's alternative cellular energy pigments (ACE-pigments) in the therapy of diseases Submitted Feb. 20, 2009. Publication number 20100215763 Urine as a source of alternative cellular energy pigments (ACE-pigments) in the assessment and therapy of diseases. Submitted Mar. 5, 2009. Publication number 20100196297
[0006] Moring a oil mediated activation of the alternative cellular energy pathway in the therapy of diseases. Submitted Feb. 24, 2010. Publication number 20110208110 Diagnostic value of systemic ACE pathway activation in the detection by fluorescence of localized pathological lesions. Submitted Jul. 26, 2010. Publication number 20100291000
[0007] Enerceutical mediated activation of the alternative cellular energy (ACE) pathway in the therapy of diseases. Submitted July 2010.
[0008] Energy Charged Liquids to Enhance Enerceutical Activation of the Alternative Cellular Energy (ACE) Pathway in the Therapy of Diseases. Submitted Dec. 17, 2010. Application Ser. No. 12/972,344
[0009] Energy Charged Alcoholic Beverages for Enhancing the Alternative Cellular Energy Pathway in the Prevention and Therapy of Diseases. Submitted January 2011.
[0010] Methods for Detecting and Monitoring the Activity of Energized Water and Other Liquids Useful for Enhancing the Alternative Cellular Energy Pathway in the Prevention and Therapy of Diseases. Submitted February 2011
[0011] Methods for Increasing the Kinetic Activity of Alcohol, Water and Other Liquids, so as to Render the Liquids More Useful in Enhancing the Alternative Cellular Energy Pathway in the Prevention and Therapy of Diseases. Submitted February 2011
[0012] Methods for Increasing the Kinetic Activity of Water and Other Liquids, so as to Render the Liquids More Useful in Enhancing the Alternative Cellular Energy Pathway and in Various Other Agricultural and Industrial Applications. Submitted June 2011. Use of Plants and Plant Extracts to Activate Water, Alcohol and Other Liquids. Submitted November 2011
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0013] Not applicable: No Federal funding was received in support of this patent application.
REFERENCE TO SEQUENCE LISTING, A TABLE OR A COMPUTER PROGRAM LISTING COMPACT DISK APPENDIX
[0014] Not applicable.
BACKGROUND OF THE INVENTION
[0015] It has been proposed that certain subtle properties of water can be modified by various methods, which typically utilize an external source of physical energy, such as magnets, electricity, vortex, sound and crystals. The reported beneficial properties of the treated and presumably “energized” water include amelioration of many human and animal illnesses; improved growth rate of plants; and reversal of corrosion of metal water pipes. How these effects are achieved is still controversial with a common oversimplification that the processed water is “restructured” into clusters, which differ in their sizes or in other qualities when compared to the clusters in unprocessed water. (It is usually assumed that the cluster size in the activated water is somewhat reduced or that the individual water molecules within the clusters are less tightly bound and even slightly expanded).
[0016] In the co-pending patent applications, incorporated herein by reference, I have disclosed the following major findings: 1. Neutral red particles sprinkled onto activated water will rapidly dissolve as linear streaks. Remaining un-dissolved material will also move throughout the solution, often in a to-and-fro manner. These movements are readily seen microscopically. Water obtained from various sources will differ in their levels of activity, with some water samples showing essentially no linear streaking of the dissolving neutral red dye, but rather slowly enlarging concentric circles of dye with stationary un-dissolved materials. The dissolving and movement patterns of neutral red (NR) dye in liquids is referred to as the NR-Kinetic assay. 2. Ethanol (absolute alcohol) and other alcohols, including alcoholic beverages, will show positive NR-Kinetic assays, when compared to water. 3. Various methods, including vortexing, stirring with a rotating magnet, exposure to sound, and bubbling through the liquid of gasses produced by electrolysis of water, will significantly enhance the NR-Kinetic activity of water, ethanol, other alcohols and alcoholic beverages. 4. Activated ethanol with neutral red dye will also fluoresce far more brightly under ultraviolet light illumination, than will regular ethanol. 5. Activated ethanol p[us neutral red dye, can lead to the activation of water and other liquids, even in the absence of direct physical contact. In one approach, the activated ethanol plus neutral red dye is placed into a sealable plastic bag, which is laid onto another liquid and the bag illuminated with a 13 Watt UV light (Halco, emitting at 365 nm, UV-A, wavelength). 6. Drinking the indirectly activated water or other beverages enhanced the sense of alertness, concentration and quality of sleep, with more vivid dreaming, of several test subjects. 7. Activated alcohol plus neutral red dye can also lead to the activation of an intrinsic alternative cellular energy (ACE) pathway used by the body in its defenses against virus infections and in wound healing. In one embodiment, a sealed plastic bag containing the activated alcohol plus neutral red dye is placed over a skin lesion, for example an outbreak of herpes simplex virus (HSV) infection and illuminated with a UV light. After several minutes, the underlying HSV skin lesion will become itself fluorescent when directly illuminated with the UV light. The direct UV illumination of the HSV skin lesion is continued till the fluorescence largely fades away (usually within 30-45 minutes. The fluorescing material within and in the vicinity of the HSV skin lesions is considered a source of cellular energy useful for the suppression of virus activity and repair of the infected cells. Another embodiment of this basic procedure is used for treating non-localized infections and especially for stealth adapted virus infections, which are not effectively recognized by the cellular immune system. In this embodiment, the plastic bag containing the activated alcohol and neutral red dye is placed onto an area of the body, such as the sole of the feet or palm of a hand and illuminated with UV light for up to an hour. Systemic activation of the ACE pathway can be confirmed by the induction or enhancement of direct UV fluorescence of the oral mucosa (tongue, palate and/or back of the throat) occurring during the treatment and persisting for some time after the treatment. Areas of induced skin fluorescence can also be occasionally observed using this procedure. Furthermore, with adults, the plastic bag containing the alcohol and neutral red dye can be placed into the mouth and directly illuminated).
[0017] In the most recent co-pending patent application, it was shown that activation of ethanol was also achievable using various plant products, including leaf powder and freshly harvested leaves and leaf powder from moring a oleifera trees. Leaves from the ashitaba plant ( Angelica keiskei ) could also be used. The present series of experiments were designed to address the question of whether various mineral products could also be used to directly activate water, ethanol and alcoholic beverages and, more importantly, can the level of activating activity of these mineral products be enhanced by prior exposure to UV illuminated activated ethanol with neutral red dye. The mineral containing compounds tested included humic acids, zeolites, magnesium oxide beads, touramaline and mica. Testing included the NR-Kinetic assay and clinical studies. Other incidental observations and applications of the underlying discoveries are also recorded.
BRIEF SUMMARY OF THE INVENTION
[0018] Various mineral products were shown to increase the NR-Kinetic activity of ethanol and other fluids. Direct contact of the ethanol and the mineral product was not essential for an effect to be observed. The activating capacity of the minerals, especially humic acids, was clearly enhanced by prior placement beneath a UV illuminated plastic bag containing activated ethanol plus neutral red dye. Unprocessed and post activated mineral products have been used not only to activate drinkable water and alcoholic beverages but also E85 gasoline (containing 85% ethanol). By using a combination of methods to activate ethanol, additional aspects of the interaction of ethanol with neutral red dye have been observed, which should facilitate an understanding of the forms of energies involved in the observed phenomena.
[0019] Of particular interest was the unanticipated demonstrated activation of humic acids, zeolites and magnesium oxide beads by passage of Water Gas generated by electrolysis of water. This method was previously used to directly activate ethanol and has been used by others to treat water. The Water Gas exposed mineral containing materials were added to water and to ethanol. When compared with similar amounts of the same mineral containing materials, the Water Gas exposed material was able to achieve a greater dynamic interaction of both water and alcohol, as assessed in the NR-Kinetic assay system.
[0020] Fluid activation methods, monitored using the NR-Kinetic assay, have been extended to several additional alcoholic beverages. These have included high alcohol content spirits, including 160 proof rum (Stroh), Everclear grain alcohol (151 proof) and E85 ethanol containing gasoline. Additional activation methods have included exposure to ozone and placement of insoluble beads of magnesium oxide and touramaline and flakes of mica. Additional aspects of the interaction of neutral red dye with highly activated alcohol containing fluids have been observed. Most importantly, the newer methods have been used clinically with encouraging results. Basically, I have discovered a range of methods, used singly or in various combinations to help enhance the ACE pathway and to provide means for further researching the nature of the energies being captured, stored and transferred.
BRIEF DESCRIPTION OF THE DRAWINGS
[0021] Not Applicable and none included
DETAILED DESCRIPTION OF THE INVENTION
[0022] Microscopic particles present in freshly mined and powdered humic acids suspended in water can display the same type of enhanced kinetic activity as seen when neutral red particles are suspended in ethanol. The kinetic activity of the microscopic particles greatly diminishes over several days and thereafter is no longer discernable. I was particularly interested in observing these movements since comparable movements of particles can be seen in long term tissue culture medium used for the culturing of stealth adapted viruses. Limited restoration of movements of humic acid particles can be achieved by exposure of a humic acid solution to sunlight, but the effects are minimal compared to those seen with initially prepared humic acids solution. I, therefore, investigated whether placing a UV illuminated, activated ethanol plus neutral red solution, in the vicinity dried powdered humic acids would modify the kinetic activity of the powder when subsequently added to water. In a particular embodiment, capsules of humic acids obtained from Morningstar Minerals, Farmington, N. Mex., were placed beneath a plastic bag containing 50 ml of ethanol plus approximately 1 mg of neutral red dye and illuminated with a 13 watt Halco UV-A spiral light bulb. At varying times from 1-12 hours, very small amounts of the humic acids material were added to water and the floating material observed for kinetic movements. Moreover, the dissolving patterns and movements of neutral red dye added to the water containing the humic acids were observed. Humic acids from control capsules not exposed to UV illuminated ethanol and neutral red dye was similarly added to water, with the subsequent addition of neutral red dye. A very clear distinction was seen between the rapid movements of humic acids after being exposed to the UV illuminated ethanol plus neutral red dye compared to the stationary particles seen with humic acids from the control capsules. While enhanced motility of the energy exposed humic acids was less evident when added to regular ethanol, the added humic acids clearly enhanced the kinetic activity of subsequently added neutral red dye. Confirmation was seen with other powdered humic acid preparations and with dilution solutions of humic acids. No effects were seen using capsules with some other powdered products, such as Milk Thistle or Saw Palmetto (dietary supplements obtained from Trader Joe, Monrovia Calif.).
[0023] Enhanced NR-Kinetic activity of water and ethanol could, however, be achieved using several preparations of zeolites by prior exposure to UV illuminated ethanol plus neutral red dye. Zeolites are structurally comparable to humic acids as mineral-rich clathrates, but differing in that the host or cage structure of zeolites comprises silica, while that of humic acids comprises carbon. Much of the zeolites used in the present study was obtained from Natural Extracts Australia Pty. Ltd., Hornsby, N.S.W., Australia.
[0024] While magnesium oxide powder is soluble in water, beads produced by heating magnesium oxide beyond 900 degrees centigrade are insoluble. There are internet reports of magnesium oxide prills (referring to beads) having beneficial effects on water, but there has been no suggestion of the use of such prills in fluids other than water. I, therefore, determined if magnesium oxide beads (Sigma Aldrich, catalogue 220361, 30 mesh) may be able to directly enhance the NR-Kinetic activity of ethanol and whether this property can be further enhanced by exposure of the beads to a UV illuminated ethanol plus neutral red dye solution. As with humic acids and zeolites, the NR-Kinetic assay showed a marked enhancement of the activity magnesium oxide beads using the UV illuminated ethanol plus neutral red dye solution. It was noted, however, that even unprocessed magnesium oxide beads have quite significant NR-Kinetic assay enhancement activity. The effects were seen using a range of quantities from 1-10 grams of beads per 100 ml of solution and for varying times from 1-24 hours.
[0025] The magnesium oxide beads were also used to test whether actual physical contact of the beads with the water or the ethanol was required to observe changes in the NR-Kinetic assay. Simply floating the beads in a plastic container placed onto the surface of water or ethanol was sufficient to achieve an overnight effect. In performing these and other experiments, I needed to be aware of the potential radiating effects of energized solutions on other nearby solutions. Similarly, it was not always possible to obtain water samples, which did not show significant NR-kinetic assay activity. Clearly there are environmental influences acting at different times, even on regular tap water. Still, with patience and detailed observations clear differential can be seen between test and control samples.
[0026] Although not as well characterized as with the humic acids, zeolites and magnesium oxide beads, stripped wafers of mica, particles of tourmaline and preparations of diatomaceous earth had both intrinsic ethanol activity (as assessed by the NR-Kinetic assay) and enhanced activity after exposure to UV illuminated ethanol plus neutral red dye solution.
[0027] A similar series of studies was performed using humic acids, zeolites and magnesium oxide beads added to alcoholic beverages, rather than absolute ethanol. This was done to help minimize the cost and also to have a consumer product for use of the technology. Among the alcoholic beverages tested were Everclear grain alcohol (151 proof as allowed in California) and Stroh 80 rum (160 proof). Effects essentially comparable to those seen with absolute ethanol were obtained with these high alcohol content beverages. Although, certainly not for human consumption, “denatured alcohol” (cleaning ethanol with added methanol), can also be activated using the described procedures. E85 ethanol (85% ethanol plus gasoline) can also be used but not in the presence of any plastics, which is soluble in gasoline.
[0028] The electrolysis of water generates hydrogen gas, oxygen gas and a form of water, which I have termed Water gas. The combination of gases is more commonly termed Brown's gas. I have regularly used a Brown's gas generator available through the internet from a company called Water-to-Gas. A pint sized jar with two electrodes extending from and through the plastic lid, is filled with approximately 300 ml of tap water to which approximately 30 grams of sodium bicarbonate is added. Leads from a 12-volt transformer running at 4.5 amps are attached to the electrodes. Gases evolving from the electrodes (hydrogen, oxygen and Water gas) are captured in a flowing stream of air from a small aquarium pump, which passes along a T shaped tubing connection with its stem passing through the cap. The output tube is typically used to allow the air and electrolysis generated gasses to pass into a liquid, such as ethanol. Rather than bubbling the gas through ethanol, I decided to pass the Water gas through powdered humic acids obtained by emptying a Moringstar Minerals, 800 mg capsules into the gas line. After 30 minutes, small portions of the humic acid powder were added to water and to ethanol. Markedly more movements and inter-particle attractions were shown by the Water gas exposed humic acids, than shown by similar quantities of humic acids not exposed to Water gas. Moreover, enhanced activity of neutral red dye, as assessed in the NR-Kinetic assay, occurred in the water and alcohol solutions using the humic acids exposed to Water gas than with the same type of fluid using non Water gas exposed humic acids. Similar observations were made when zeolites were exposed to exposed to Water gas and directly compared with the activity of zeolites prior to exposure to Water gas. Although, no movements of the Water gas exposed magnesium oxide beads occurred, these beads were clearly able to induce more neutral red activity in both water and ethanol than could non-Water gas exposed magnesium oxide beads. Overall, the bubbling of Water gas through the mineral products was less convenient than placing the materials in close proximity to UV illuminated activated ethanol with added small amounts of neutral red dye.
[0029] The relatively (10 minutes) brief UV illumination of sealed plastic containers of activated ethanol plus neutral red dye in a sealed plastic bag placed into a glass of wine was repeatedly been shown to improve the mellowness and taste of the wine. The taste of spirits, but not beer has also been improved in these incidental 6tystudies.
[0030] The more important focus has been on understanding the nature of the energy changes occurring in the ethanol and the role of neutral red in the transmission of a distantly acting energizing effect. In addition to enhanced directional solubility of much of the neutral red dye particles and rapidly increased movements of remaining un-dissolved neutral red particles, there is much more intense orange colored UV fluorescence of the activated ethanol solutions. Even the highly energized water will now typically fluoresce and not due to an elevated pH (which can cause fluorescence in neutral red solutions). The amount of neutral red dye required to evoke the fluorescence in activated ethanol is becoming minimal (<0.1 mg/ml). With more neutral red dye, I can commonly observe the formation of many fine strands of neutral red dye in the activated ethanol. Moreover, as noted earlier, many complex ring patterns were observed as the neutral red became deposited from the evaporating ethanol.
[0031] The NR-Kinetic assay is enhanced by heat and the activated solutions appear to heat more readily than control solutions from the microscope light. The UV light appears to be an added source of input energy but is not necessary to observe very dynamic kinetic activity.
[0032] The other important issue is the usefulness of the described procedures in preparing either drinkable fluids for consumption or activated solutions to be used with neutral red dye in a UV illuminated plastic container placed onto the body. When either the neutral red dye or the UV illumination is not used in the external application of the method, no clinical benefit has been reported. Drinking water and other fluids, which have been activated either with a UV illuminated sealed plastic placed into the fluid has clearly provided clinical benefits. Efforts are underway to assess the usefulness of such fluids in footbaths, whole body bathing, skin sprays and cosmetics. An additional way of energizing water, ethanol and other liquids, as assessed by the NR-Kinetic assay, comprises exposure to ozone, as supplied by an Othrea Toothbrush Sanitizer device. It is clear that multiple procedures exist for activating the kinetic activity of fluids. Many can be used in combination to achieve maximum activation. Each method is subject to refinements, such as showing that powdered moring a leaf powder is superior to olive leaf powder in its activating activity and that moring a seed powder can also be used for fluid activation. The finding that magnesium oxide can be used by itself in activation of ethanol and of Everclear drinking grain alcohol is consistent with mineral based components being the energy delivering active components in moring a and ashitaba leaf powders. (The later powder was obtained as Ashitaba Percent and supplied by Hachi Jo Island Corp. Japan.).
[0033] The basic premise of activated fluids providing an effective means of activating the ACE pathway in humans, animals and plants is a fundamental advance in biological science. The fluids are believed to be changed in such as manner that they can continually and more efficiently absorb both conventional and unconventional (e.g. etheric or zero pint) energies from the environment. The present patent application shows that intermediary activation and presumably energy collecting activity can also occur with certain solids. The processes can occur naturally as with moring a and other plant materials and with certain mineral containing organic and inorganic substances, such as humates and zeolites, respectively. Even if lost from these latter materials, energy can be restored using UV illumination of activated ethanol with neutral red dye. Simple mineral containing solids, such as magnesium oxide beads can also show intrinsic energy collecting and transmitting activities, which can be further enhanced.
[0034] Beyond its demonstration of clinical utility, activated fluids are anticipated to have many beneficial uses in animal husbandry, correction of animal illnesses, agricultural applications in the growth and quality of plants and industrial uses, such as having anti-corrosion effects, making of better cement, improving the performance of E85 gasoline, etc. Indeed, there are many applications of the methods described within the present application, only some of which are included in the following set of claims.
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The use of humic acids, zeolites, magnesium oxide beads and other mineral-containing materials in the activation of ethanol, alcoholic beverages and water is disclosed. Consumption of the energized liquids can have therapeutic benefits. The activated ethanol can be further used with neutral red dye and ultraviolet (UV) light illumination to indirectly enhance the environmental energy absorption properties of other liquids, including drinking water and of mineral containing materials. Mineral activated ethanol can similarly be used with neutral red dye and UV illumination to enhance the alternative cellular energy (ACE) pathway of an individual.
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This Application is a CIP of Allowed application Ser. No. 09/140,734 filed Aug. 26, 1998, U.S. Pat. No. 6,025,038.
TECHNICAL FIELD
The present invention relates to substrate systems, and more particularly is a system resulting from the practice of a method for depositing rare-earth borides onto the surface of a substrate which is submerged in an organic solution of borane and a rare-earth halide, said deposition being driven by application of electromagnetic radiation.
BACKGROUND
A particularly relevant, non-limiting, application of the present invention is in the fabrication of a variety of electron emitting electrodes and gas-discharge plasma display systems which comprise cathode(s) and electrically excitable gas(es). Fabrication of plasma display systems requires that cathode material(s) which can emit electrons be caused to be present in desired patterns on substrates which are situated in close proximity to said electrically excitable gas(es). Preferably said cathode material(s) should have a low work function such that electrons can be easily emitted therefrom in use, and said electrically excitable gas(es) should be capable of providing desired, (eg. visible), electromagnetic wavelengths when electrical discharge is caused to occur therein by application of electric potential to closely situated cathodes.
Approaches to improving gas-discharge plasma displays include:
a. development and use of improved cathode material(s);
b. development and practice of improved cathode material deposition; and
c. development and use of improved electrically excitable gas(es).
While the development and use of improved electrically excitable gas(es) is a very viable and worthy approach to improving operation of gas discharge display systems, the present invention is focused on development and use of improved cathode material(s) and development and improved procedures of cathode material(s) deposition onto substrates, which procedures can be adapted to fabrication of plasma discharge displays.
In view of the focus of the present invention, it is noted that various approaches to fabricating substrates which have cathode material(s) present thereon in desired patterns, have been investigated by previous researchers. Such techniques include:
a. screen printing;
b. plasma spray deposition;
c. vacuum deposition by sputtering or evaporation;
d. cluster-assisted deposition;
e. light-induced deposition from solution.
The present invention was arrived at by experimentation in the area of light-induced deposition of cathode material(s) from solution, (preferably organic solvent based), and the present invention is found in practice of a method and the results of the practice thereof.
A search of Patents focused upon gas-discharge plasma displays provided a Patent to Kolwa et al., U.S. Pat. No. 5,159,238, which describes a gas discharge panel with a plurality of electrically conductive oxide cathode electrodes formed from, for instance, lanthanum, chromite, lanthanum calcium chromite, aluminum doped zinc oxide, or antimony-doped tin oxide.
Continuing, and of somewhat more relevance, a Patent to Lafferty, U.S. Pat. No. 2,639,399, and a Patent to Kauer, U.S. Pat. No., 3,399,321 disclose that rare-earth hexaborides have low work functions and are very suitable to application in electron emitter and filament applications. A Patent to Yokono et al., U.S. Pat. No. 4,599,076 describes production of a discharge display involving the cathode forming steps of applying a paste prepared by mixing LaB 6 powder with alkali glass powder in proportion of 20-40% by weight to a base electrode, then burning the paste and then activating the paste by gas discharge with large current after an exhaustion step. A similar process leading to a similar result is also described in U.S. Pat. No. 4,600,397 to Kawakubo et al. A Patent to Kamegaya et al., U.S. Pat. No. 4,393,326 describes a gas discharge panel with an electrode comprised of a metal layer, (eg. Fe and Ni), and a metal compound layer, (eg. alkaline earth metal oxide or sulphide and rare-earth metal hexaboride), which are formed by a plasma spray technique. Another Patent which describes use of a rare-earth hexaboride such as LaB 6 in forming cathodes in a plasma discharge display is U.S. Pat. No. 4,727,287 to Alda et al. Another Patent, U.S. Pat. No. 5,277,932 to Spencer, describes application of chemical vapor deposition techniques to deposit metal boride films onto substrates utilizing metal borane cluster compound as a precursor. While this method is successful, it does not lend itself well to either selective area depositions, or to depositions in large scale area manufacturing where substrates can have dimensions of several inches.
The above Patents show that the use of low work function rare-earth hexaborides to form cathodes in electron emitter, filament and gas plasma displays is not new, and that various techniques exist for forming such rare-earth containing cathodes. However, no known Patent describes the formation of rare-earth containing cathodes by a method comprising light-induced deposition (LISD) from solution. This is even more so where the solution is organic solvent based. It is noted that organic-based solvent based solutions, (eg. those containing methanol, nitriles or amides), as opposed to aqueous solutions, absorb wavelengths in the ultraviolet and are therefore often overlooked in the practice of light-induced deposition from solution.
Additional searching performed with an eye to identifying the application of light-induced deposition from solution in formation of rare-earth containing electrodes provided very little. A Patent to Liepins, U.S. Pat. No. 4,464,416 describes a procedure which is purported to be applicable to forming a metallic coating on a polymeric substrate, comprising contacting the polymeric substrate with a fluid containing a metal compound at a temperature below 150 degrees centigrade for a time sufficient for the metal to be sorbed into the substrate, and then subjecting the substrate to a low pressure plasma. A perhaps somewhat more relevant Patent is U.S. Pat. No. 3,484,263 to Kushihashi et al. in which a process for forming a layer of semi-transparent gold on the surface of glass is described as comprising the steps of containing a water-soluable gold salt and a reducing agent in contact with said glass while subjecting said glass to short wavelength rays in the range of 250 to 500 nanometers, with the improvement being that the solution is maintained at a temperature of not more than 10 degrees centigrade. Another Patent, U.S. Pat. No. 4,511,595 to Inoue, describes the deposition of a metal to a substrate from a typically flowing solution, wherein a laser beam is directed onto the substrate over a localized area, to activate an interface between said localized area and said solution. A Patent to Braren et al., U.S. Pat. No. 5,260,108 describes deposition of a metal such as palladium onto a substrate such as a polyimide, silicon dioxide, tantalum oxide or polyethylene terephthalate by contacting the substrate surface with a solution of the metal, and then exposing the surface of the substrate to laser radiation characterized by a wavelength absorbable by the substrate and a power density and fluence effective to release electrons to promote deposition of the metal onto the substrate without thermal activation of the substrate or the solution. Finally, a Patent to van der Putten et al., U.S. Pat. No. 5,059,449 describes depositing a nobel metal such as platinum from a salt solution thereof, onto a substrate which can be an insulator, semiconductor or conductor, by use of a laser beam. The solution is described as consisting essentially of a solvent selected from the group consisting of ammonia, a cyclohexanel and an amine, and typical metals which can be deposited are described as Pd, Pt, Rh, Ir, Ru and Ag. Application of the laser through masking to define areas of metal deposition is also described.
Articles of which the inventors are aware include:
A paper which describes the low work function of rare-earth metal borides is titled "Thermionic Emission Properties of LaB 6 and CeB 6 In Connection With Their Surface States, Examination By XPS, Auger Spectroscopy And The Kelvin Method", Berrada et al., Surface Science 72, 177 (1978).
Application of rare-earth metal borides in thermionic emitters is discussed in:
"Microcircuits By Electron Beam", Broers et., Sci. Am. 227, 34 (1972);
"Lanthanum Hexaboride Electron Emitter", Ahmed et al., J. App. Phys. 43, 2185 (1972);
"Electron Beam Fabrication", Miller et al., Solid State Technology, 16, 25 (July 1973);
"Evaluation of a LaB 6 Cathode Electron Gun", Verhoeven et al., J. Phys. E, Scientific Instruments, Vol. 9 (1976);
"Field Emission Pattern Of LaB 6 -Single Crystal Tip", Shimizu et al., J. App. Phys., Vol. 14, No. 7, 1089 (1975);
"Highly Stable Single-Crystal LaB 6 Cathode For Conventional Electron Microprobe Instruments", Shimizu et al., J. Vac. Sci. Technol., 15(3), 922 (1978);
Articles which describe reaction of nido-decaborane and metal chlorides and subsequent chemical vapor deposition (CVD) of gadolinium hexaboride are:
"Chemical Vapor Deposition Of Metal Borides, 4: The Application Of Polyhedral Boron Vapor Deposition Formation Of Gadnolinium Boride Thin-Film Materials", Kher et al., Appl. Organ. Chem., Vol. 10, 297 (1996);
and the previously cited Patent, U.S. Pat. No. 5,277,932 to Spencer also discusses this topic.
Similar rare-earth boride deposition, (where gadolinium was not the rare-earth involved), is discussed in:
"The Deposition Of Metallic And Non-Metallic Thin Films Through The Use Of Boron Clusters", Zhang, Kim, Dowben & Spencer, Chemical Perspectives of Microelectronic Materials III, Ed. by C. R. Abernathy et al., Mat. Res. Soc. Symp. Vol. 131, Proc. 282, 185 (1993);
"Metallized Plastics 4: Fundamentals and Applied Aspects", Ed. Mittal et al., Mercel Dekker Inc., New York (1997).
Selective area deposition of copper metal films from solution is described in:
"Laser-Induced Selective Copper Deposition On Polyimides And Semiconductors", Hwang, Kher, Spencer & Dowben, Mat. Res. Symp. Proc., Vol. 282 (1983);
"Material Deposition", Bauerle, Chemical Processing with Lasers", ED. Queisser, Springer Verlag (1986);
"Surface Processing Leading To Carbon Contamination Of Photochemically Deposited Copper Films:, Houle et al., J. Vac. Sci Technol., A 4(6) 2452 (November/December 1986);
"Photochemical Generation And Deposition Of Copper From A Gas Phase Precursor", Jones et al., Appl. Phys. Lett., 46, 97 (January 1985);
"Laser Chemical Vapor Deposition Of Copper", Houle et al., Appl. Phys. Lett., 46(2), 204 (January 1985);
"LCVD Of Copper: Deposition Rates And Deposit Shapes", Moylan et al., Appl. Phys. Lett. A 40, 1 (1986);
"High-Speed Laser Chemical Vapor Deposition Of Copper: A Search For Optimum Conditions", Markwalder et al., J. Appl. Phys., 65(6), 2470 (March 1989);
"Laser Enhanced Electroplating And Maskless Pattern Generation", von Gutfeld et al., Appl. Phys. Lett., 35(9) (1979);
"Laser-Enhanced Jet Plating: A Method of High-Speed Maskless Patterning", von Gutfeld et al., Appl. Phys. Lett., 43(9), 876, (November 1983);
"High-Speed Electroplating Of Copper Using The Laser-Jet Technique", von Gutfeld et al., Appl. Phys. Lett. 46(10) (May 1985);
"Investigation Of Laser-Enhanced Electroplating Mechanisms", Puippe et al., J. Electrochem. Soc., Vol. 128, No. 12, 2539 (December 1981);
"Laser Induced Copper Plating", Al-Sufi et al., J. Appl. Phys. 54(6), 3629 (June 1983);
"Laser-Induced Decomposition Of Organometallic Compounds", Gerassimov et al., XII International Quantum Electronics Conference, (1982);
"Photoelectrochemical Deposition Of Microscopic Metal Film Patterns On Si and GaAs", Micheels et al., Appl. Phys. Lett., 39(5), 418 (September 1981).
Selective area deposition of complex compound material films from solution is described in:
"Structural And Electrical Properties Of Crystalline (1-x) Ta 2 O 5 -xAl 2 O 3 Thin Films Fabricated By Metalorganic Solution Deposition Technique"et al., Joshi et al., Appl. Phys. Lett. 71(10), 1341 (September 1997);
"Metalorganic Solution Deposition Technique", Joshi et al., Appl. Phys. Lett. 70(9), 1080 (March 1997).
A reference which describes a laser induced solution deposition process which involved copper chloride (Cu 2 Cl 2 ) and nido-decaborane is:
"Solution Deposition And Hetroepitaxial Crystalization Of LaNiO 3 Electrodes For Integrated Ferroelectric Devices", Cho et al., Appl. Phys. Lett. 71(20), 3013 (November 1997);
It is noted that Laser Induced Solution Deposition (LISD) requirements (eg. transparent solvent/solute mixture and solid surface area which acts as a dipole that has a large dielectric response. An article which makes clear that similar requirements apply where selective area chemical vapor deposition is practiced is:
"Designing Of Organometallics For Vapor Phase Metallization Of Plastics", Boag & Dowben, Metallized Plastics 4: Fundamental and Applied Aspects, ED Mittal, Marcel Decker, New York (1997).
Deposition of electrode material (eg. LaNiO 3 ) on substrates to which it does have a good lattice match is described in:
"Effect Of Textured LaNiO 3 Electrode On The Fatigue Improvement Of Pb(Zr 0 .53 Ti 0 .47)O 3 Thin Films", Chen et al., Appl. Phys. Lett. 68(10), 1430 (March 1996);
"Preparation of (100)-Oriented Metallic LaNiO 3 Thin Films On Si Substrates By Radio Frequency Magnetron Sputtering For The Growth Of Textured Pb(Zr 0 .53 Ti 0 .47)O 3 ", Yang et al., Appl. Phys. Lett. 66(20), 2643 (May 1995);
A reference which describes the results of metal deposition which is influenced by nucleation centers is:
"Deposition Of Thin Metal and Metal Silicide Films From The Decomposition Of Organometallic Compounds", Dowben et al., Mat. Sci. Eng. B2, 297 (1989).
A reference which describes vacuum reactor deposition of nickel boride is:
"Chemical Vapor Deposition Precursor Chemistry. 3. Formation And Characterization Of Crystalline Nickel Boride Thin Films From The Cluster-Assisted Deposition Of Polyhedral Borane Compounds", Kher et al., Chem. Mater., 4, 538 (1992);
A reference which describes fabrication of bulk gadolinium borides (an amorphous boron) as a result of thermolysis of a molecular precursor Gd 2 (B 10 H 10 ) 3 is:
"Synthesis Of Cerium And Gadolinium Borides Using Boron Cage Compounds As A Boron Source", Itoh et al., Mat. Res. Bul. 22, 1259 (1987).
Even in view of the large number of references, there remains need for additional, simple and efficient, techniques for selective area laser induced deposition of rare-earth borides onto substrates.
DISCLOSURE OF THE INVENTION
The present invention is primarily a system which results from practicing a method of depositing rare-earth boride, (eg. hexaboride), onto the surface of a substrate. Typical practice of the method begins with the dissolving borane and at least one rare-earth halide in an organic solvent, followed by providing and placing a substrate into said solution, so that a surface of said substrate is submerged but accessible by electromagnetic radiation. Next, a source of electromagnetic radiation is caused to expose the surface of said substrate to electromagnetic radiation, through said solution of borane and at least one rare-earth halide in said organic solvent. It is believed that as a result, at least one rare-earth halide in the vicinity of said substrate surface is fragmented into free halide and free rare-earth components and said free halide fractures said borane. Components of said fractured borane then combine with the free rare-earth to form rare-earth boride which deposits on said surface of said substrate.
The organic solvent is preferably comprised of at least one selection from the group consisting of: (methanol, THF, hexane, ether, benzene, a nitrile and an amide).
While not limiting, the substrate can be made of sodium glass. It should be appreciated in particular, that a deposited rare-earth boride need not be lattice matched to a substrate to achieve a very good, textured, rare-earth boride film deposition thereupon. That is, the deposited rare-earth borides appear to be at least substantially thermodynamically stable and thereby do not require a crystal template to effect formation thereof.
The source of electromagnetic radiation used to expose the surface of said substrate to electromagnetic radiation can be a laser, or a source of essentially white light which is passed through filtering means to provide favored wavelengths, (which are in the visible range where hv is nominally 2.4 eV). It is noted that use of wavelengths in the visible range greatly diminishes the problem of wavelength absorbtion, which can be very significant where organic solvents, and non-visible range wavelengths, are utilized. It is also noted that a favored source of electromagnetic radiation in the experimental work performed by the inventors to date is an Argon Ion Laser (I-90 Coherent).
Favored practice is to deposit rare-earth boride onto the surface of a substrate in patterns which are affected by exposing the surface of said substrate to electromagnetic radiation through an electromagnetic mask placed between said source of electromagnetic radiation and the surface of said substrate.
While most experimental work to date has been done utilizing Gadolinium (Gd), essentially any rare-earth halide can be utilized in practice of the present invention, (eg. Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu), and a preferred, but not limiting halide is chloride. In addition, it is noted that a preferred end result is deposition of rare-earth hexaboride on the surface of a substrate.
An exemplary method of depositing GdB x onto the surface of a substrate to form a present invention system, comprises the steps of:
a. disolving B 10 H 14 and said GdCl 3 in an organic solvent comprising methanol;
b. providing and placing a substrate in said solution of B 10 H 14 and said GdCl 3 in said organic solvent comprising methanol, so that a surface of said substrate is submerged, but accessible by electromagnetic radiation through said solution of B 10 H 14 and said GdCl 3 in said organic solvent which includes at least one selection from the group consisting of: (methanol, THF, hexane, ether, benzene, nitrile and amine);
c. providing a source of electromagnetic radiation and exposing the surface/vicinity of the surface of said substrate to electromagnetic radiation through said solution of B 10 H 14 and said GdCl 3 in said organic solvent comprising methanol, from said provided source of electromagnetic radiation;
such that said GdCl 3 in the vicinity of said substrate surface is fragmented into free chloride and free Gd components, with the result being that said free chlorine fractures said B 10 H 14 , with the further result being that components of said fractured B 10 H 14 combine with Gd to form GdB x +(B 10-x H y Cl+yHCl), which GdB x deposits on said surface of said substrate.
A more general method of depositing rare-earth boride onto the surface of a substrate to form a present invention system, comprises the steps of:
a. dissolving borane and at least one rare-earth halide in an organic solvent;
b. providing and placing a substrate in said solution of borane and at least one rare-earth halide in said organic solvent, so that a surface of said substrate is submerged but accessible by electromagnetic radiation;
c. providing a source of electromagnetic radiation and exposing the vicinity of the surface of said substrate to electromagnetic radiation through said solution of borane and at least one rare earth halide in said organic solvent, from said provided source of electromagnetic radiation;
such that said at least one rare-earth halide deposits on said surface of said substrate.
A present invention system is preferrably formed by, in the method step of dissolving borane and at least one rare-earth halide in an organic solvent, providing an organic solvent which includes at least one selection from the group consisting of:
methanol; THF; hexane; ether; benzene; nitriles and amines;
and the at least one rare-earth halide is selected from the group consisting of:
Sc; Y; La; Ce; Pr; Nd; Pm; Sm; Eu; Gd; Tb; Dy; Ho; Er; Tm; Yb; and Lu.
A preferred, but not limiting substrate utilized in the method of formation of present invention system is made of sodium glass.
As mentioned above, the method step of exposing the the vicinity of the surface of said substrate to electromagnetic radiation, preferrably involves use of a laser, and the method step of exposing the the vicinity of the surface of said substrate to electromagnetic radiation involves use of essentially white light which is passed through filtering means to provide favored wavelengths to provide favored wavelengths are in the visible range where hv is nominally 2.4 eV.
Preferred present invention systems provide for fabrication of patterend rare-earth boride deposition by, in the method step of exposing the surface/vicinity of the surface of said substrate to electromagnetic radiation, providing an electromagnetic radiation mask between the source of electromagnetic radiation and the substrate.
A present invention system is preferably, but not exclusively, formed by, in the method step of dissolving borane and at least one rare-earth halide in an organic solvent, utilizing chloride as the halide.
A preferred present invention system comprises rare-earth hexaborides which deposit(s) on the surface of said substrate.
The present invention will be better understood by reference to the Detailed Description Section of this Disclosure in conjunction with appropriate reference to the Drawings.
SUMMARY OF THE INVENTION
It is therefore a primary objective of the present invention to teach a system made by a method for depositing rare-earth boride onto the surface of a substrate which is submerged in an organic solution of borane and a rare-earth halide, via application of electromagnetic radiation to the surface/vicinity of the surface of the submerged substrate.
It is another objective of the present invention to identify at least one selection from the group consisting of: (methanol, THF, hexane, ether, benzene, nitrile and amine), as an appropriate organic solvent for use in practicing the method of the present invention.
It is yet another objective of the present invention to identify sodium glass as an appropriate substrate for use in practicing the method of the present invention.
It is another objective purpose yet of the present invention to identify appropriate sources of electromagnetic radiation used to expose the surface of said substrate to electromagnetic radiation can be a laser, or a source of essentially white light which is passed through filtering means to provide favored wavelengths, which are in the visible range where hv is nominally 2.4 ev.
It is another objective of the present invention to disclose that favored practice is to deposit rare-earth boride onto the surface of a substrate in patterns which are effected by exposing the surface of said substrate to electromagnetic radiation through an electromagnetic mask placed between said source of electromagnetic radiation and the surface of said substrate.
It is another objective of the present invention to disclose that the method of the present invention can be practiced with any of the rare-earths: (Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu).
It is yet another objective of the present invention to disclose that a preferred halide for use in practice of the present invention is chloride.
It is another objective yet of the present invention to disclose that hexaboride is the preferred boride for deposition on the surface of a substrate.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 demonstrates a system for practicing the present invention.
FIG. 2 demonstrates expected interaction between electromagnetic radiation (EM) and a rare-earth halide, which, in the vicinity of said substrate surface (SS) is fragmented into free halide and free rare-earth (FRE) components, with the result believed to be that said free halide fractures said borane, with the further result that components of said fractured borane (FB) combine with free rare earth (FRE) to form rare-earth boride (REB) which deposits on said surface (SS) of said substrate.
FIG. 3a shows X-ray Diffraction Patterns from Gadolinium Hexaboride (GdB 6 ) deposited onto a glass substrate.
FIG. 3b shows X-ray Diffraction Patterns from Gadolinium sub-borides (GdB 4 ) and (GdB 2 ) on a glass substrate, along with the similar result from the glass substrate prior to deposition.
DETAILED DESCRIPTION
Turning now to the drawings, FIG. 1 demonstrates a system for practicing the present invention. In particular a reservoir of chemicals (RES) with a substrate surface (SS) therein is shown with a source of electromagnetic radiation (EM) positioned to provide "light" through a Mask. Means for entering and recovering waste materials for reuse are demonstrated.
FIG. 2 demonstrates interaction between electromagnetic radiation (EM) and a rare-earth halide in the vicinity of said substrate surface (SS). Said rare-earth halide is functionally shown as being fragmented into free halide and free rare-earth (FRE) components, with the further result believed to be that said free halide fractures said borane, such that components of said fractured borane (FB) combine with free rare earth (FRE) to form rare-earth boride (REB) which deposits on said substrate surface (SS).
Experimental depositions performed to date by the inventors utilized solutions containing various mixtures of methanol, hexane, tetrahydrofuran (THF), ether, benzene, nitrile and amine, and electromagnetic radiation was provided from an Argon Ion Laser (I-90 Coherent) source. Electromagnetic radiation from the Argon Laser provided wavelengths in the ultraviolet, (eg. 300-400 mW, 333 nm-363 nm) and in the visible (5-7 W, 514 nm).
FIG. 3a shows X-ray Diffraction Patterns from Gadolinium Hexaboride (GdB 6 ) deposited onto a glass substrate. The investigated Gadolinium Hexaboride (GdB 6 ) was deposited utilizing gadolinium chloride and decaborane as precursors in a solvent consisting of 10-120 mmol THF (36-48%), 10-100 mmol hexane (36-48%), 2-25 mmol ether (3-28%) and 3-15 mmol (<1%) methanol). The electromagnetic radiation was in the visible range (eg. hv is nominally 2.4 ev). XES measurements show no chlorine in the deposited films and the Diffraction Patterns are clearly associated with the presence of Gadolinium Hexaboride (GdB 6 ). The prominence of the (111) diffraction line, as seen in FIG. 3a, clearly indicates that the films grown from solution are textured. It is noted that films of Gadolinium Hexaboride (GdB 6 ) grown in a vacuum reactor typically show far less texturing. In particular it is noted that FIG. 3a shows an essential absence of an X-ray diffraction (221) peak. This is in direct constrast to, for instance, the significant presence of a (221) X-ray diffraction peak in the plot shown in FIG. 3 of the previously cited Kher et al. paper which describes (GdB 6 ) grown in a vacuum reactor. (Note, the Kher et al. paper is identified in the Background Section of this Specification and is found in Applied Organometallic Chemistry, Vol. 10, P. (297-304), (1996)). It is believed that textured films provide improved electrode fatigue properties. The Gadolinium Hexaboride (GdB 6 ) films were grown on non-crystaline sodium glass, such as used in DC plasma discharge display systems and it is emphasized that no lattice matching between said Gadolinium Hexaboride (GdB 6 ) and the sodium glass was present.
FIG. 3b shows X-ray Diffraction Patterns from Gadolinium sub-borides (GdB4) and (GdB2) on a glass substrate, along with the similar results from the glass substrate prior to deposition. These films showed trace amounts of chlorine present which is consistent with the presence of the identified Gadolinium sub-borides. Similar Lanthanum borides have also been fabricated.
It is again noted that (LISD) deposited films which are deposited utilizing visible range wavelength electromagnetic radiation are typically more uniform that films deposited utilizing more conventional precesses, (eg. CVD).
Additional films were deposited utilizing electromagnetic radiation in the ultraviolet. Where this was done the methanol content of the solution was reduced to less than 1%. The resulting films showed characteristics of nucleation sites. (It is noted that methanol is a necessary solvent component for the dissolution of gadolinium chloride, and that the content of methanol must be reduced where ultraviolet wavelengths are utilized as methanol absorbs uv wavelengths).
The results of the present laser initiated deposition from solution procedure suggests that the deposition chemistry is similar to that associated with use of high temperature vacuum reactor. It is believed that the chemical reaction for the gadolinium borides during deposition from solution can be written as:
GdCl.sub.3 +B.sub.10 H.sub.14 →GdB.sub.x +B.sub.10-x H.sub.y Cl+yHCl.
It is believed that a key chemical intermediate is of the form:
RE.sub.2 (B.sub.10 H.sub.10).sub.3
(where "RE"=Rare Earth), and is a part of the thin film deposition process. The fabrication of the bulk gadolinium borides (and amorphous boron), has been undertaken from the thermolysis of said molecular Gd 2 (B 10 H 10 ) 3 precursor. The dominant gadolinium borides in this pyrolysis reaction are GdB 4 and GdB 6 , as is also the case in the solution deposition reported here.
Laser-induced deposition of gadolinium borides from solution has been shown to be effective and simple. The mechanism of Laser Induced Solution Deposition (LISD) clearly resembles that of Chemical Vapor Deposition (CVD) in the gas phase. However, unlike gas phase deposition, (eg. CVD and PECVD), deposition from solution is compatible with thin film formation on thermally sensitive substrates because of the large thermal sink of the solvent/solute mixture.
It is noted that the mechanism of inducing deposition material reducing electrons at the surface of a substrate onto which a rare-earth boride is to be deposited, such as described in the previously referenced Patent to Inoue, (U.S. Pat. No. 4,511,595), which describes the deposition of a metal onto a substrate from a typically flowing solution, wherein a laser beam is directed onto the substrate over a localized area, to activate an interface between said localized area and said solution, might play a role similar to that in the case where a metal is reduced onto the surface of a substrate.
It should also be appreciated that the (LISD) technique permits one undertake recovery of unused metals and source compounds, and volatility, toxicity and safety issues, common to (CVD) processes, are diminished. Further, the fact that present invention rare-earth boride film deposition occurs best where visible range wavelengths are utilized in the deposition process, means that the present invention process for deposition of rare-earth hexaborides onto substrates can more easily be adapted to industrial scale environments where conventional visible light sources are commonly available.
Having hereby disclosed the subject matter of the present invention, it should be obvious that many modifications, substitutions, and variations of the present invention are possible in view of the teachings. It is therefore to be understood that the invention may be practiced other than as specifically described, and should be limited in its breadth and scope only by the claims.
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Disclosed is a system made by a method for depositing rare-earth boride onto the surface of a substrate which is submerged in an organic solution of borane and a rare-earth halide. Application of electromagnetic radiation, preferably in the visible wavelength range, through a mask near the surface of the submerged substrate, drives the formation and deposition of rare-earth boride onto a substrate in desired patterns.
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CROSS REFERENCES
[0001] This application is a continuation-in-part of co-pending U.S. application Ser. No. 10/629,980 filed Jul. 30, 2003.
TECHNICAL FIELD OF THE INVENTION
[0002] This invention generally relates to fencing products support posts and, more particularly, to a multi-purpose, portable fence incorporating a lay-down or fold-over feature, including a fold-over post for use alone or incorporated into a panel-based fencing system.
DESCRIPTION OF THE RELATED ART
[0003] A number of outdoor and sport-related activities utilize fencing to enhance the playing environment for the activity in question. Baseball and softball are prime examples of such an activity. The construction of fencing to delineate the boundaries of the outfield and the playing field provides a more polished appearance to the field, provides the opportunity for players to hit “real” home runs, and helps limit the amount of playable foul territory surrounding the field. Fencing can also allow larger general purpose fields to be divided into several separate fields to accommodate a number of different games at one time, for example, during tournament play.
[0004] Permanent fencing, while durable and attractive, has a number of shortcomings. First of all, it can be prohibitively expensive. Also, permanent fencing does not allow for adjustments in field dimensions or field arrangements. In addition, because permanent fencing creates a solid vertical surface adjacent to the field, it presents a potential safety issue to athletes who may run into the fence while playing.
[0005] Temporary or portable fencing for athletic fields is also known in the art. Temporary fencing allows for an infinite number of adjustments in how an athletic or general purpose field can be arranged and divided for a number of different athletic events and other activities. For example, it is quite common for high schools, grade schools, or youth athletic associations to utilize a single field for football or soccer in the fall and baseball throughout the spring and summer. Temporary fencing allows these groups to arrange their limited field space in a more efficient and professional looking manner. In addition, these organizations frequently host different sporting events that involve different age groups. Temporary fencing allows an organization to customize a field's dimensions for a particular age group. For instance, a baseball outfield could be set up with smaller dimensions for grade school children than one for high school or college age athletes, allowing each of these different age groups to play on a baseball field properly suited to their size and playing ability while using the same general purpose field.
[0006] The most common form of such temporary fencing utilizes stakes to support a continuous plastic mesh material. The fences are not sturdy and tend to fall over quite easily when struck by a player or ball, requiring that the game be stopped while the fence is repositioned. Further, the stakes are generally inserted rigidly into the ground and may not give way when a player runs into them, creating a safety hazard. In addition, these fences are generally unattractive and are very labor intensive to install. Alternative designs incorporate individual fence panels made of polyvinyl chlorate (“PVC”) or similar material with posts that are rigidly inserted into the ground or connected to wide feet resting perpendicular to the fence panel. Because these designs are rigidly mounted, they present the same safety concerns as permanent fencing. Furthermore, these designs have been priced out of reach of many schools, parks and recreation leagues in the past, which are the very groups that are most in need of the benefits of such fences.
[0007] Therefore, providing a fencing system capable of being installed quickly and manufactured and sold inexpensively, which does not present a significant safety hazard to athletes, would be highly desirable. Furthermore, providing a support post for fences, signs or similar items capable of folding over would also be desirable.
[0008] The present invention is directed to overcoming one or more of the problems set forth above.
SUMMARY OF THE INVENTION
[0009] An aspect of the present invention is to provide an affordable, portable fencing system for athletic fields, crowd control, and general purpose use that is quickly and easily installed.
[0010] Another aspect of the present invention is to provide a portable fencing system that is adapted for use on either outdoor turf or on indoor or hard surfaces.
[0011] Yet another aspect of the present invention is to provide a portable fencing system for athletic fields, crowd control, and general purpose use that is capable of folding over upon impact to minimize the chances for injury to a participant running into the fence and readily returning to an upright position after impact.
[0012] Another aspect of the present invention is to provide a fold-over post for use in a portable fencing system or as a general support post.
[0013] In accordance with the above aspect of the invention, there is provided a portable, fold-over post for use on both outdoor and indoor surfaces that includes a vertical member; a first spring removably connected to the vertical member, said spring having a mounting spike integrally formed therewith for insertion into a soft, outdoor surface, and said spring allowing the post to fold over upon impact; and a foot assembly interchangeable with said spring and suitable for supporting said post on a hard surface.
[0014] These aspects are merely illustrative of the innumerable aspects associated with the present invention and should not be deemed as limiting in any manner. These and other aspects, features and advantages of the present invention will become apparent from the following detailed description when taken in conjunction with the referenced drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] Reference is now made more particularly to the drawings, which illustrate the best presently known mode of carrying out the invention and wherein similar reference characters indicate the same parts throughout the views.
[0016] FIG. 1 is an elevation view of a portable, fold-over fence panel according to one embodiment of the present invention.
[0017] FIG. 2 is an elevation view of a combination spring/mounting spike utilized in the fence panel of FIG. 1 .
[0018] FIG. 2A is a top view of the spring/mounting spike of FIG. 2 .
[0019] FIG. 3 is an elevation view of a portable, fold-over fence composed of separate panels according to another embodiment.
[0020] FIG. 4 is an elevation view of an interconnected spring/mounting spike assembly for a portable, fold-over fence composed of separate panels.
[0021] FIG. 5 is a plan view of a stability plate suitable for use with the embodiment of FIG. 4 .
[0022] FIG. 5A is a side view of the stability plate of FIG. 5 .
[0023] FIG. 6 is a plan view of a connecting clip suitable for interconnecting portable, fold-over fence panels according to another embodiment.
[0024] FIG. 7 is an elevation view of a multi-purpose, portable fence panel according to another embodiment.
[0025] FIG. 7A is a side view of a foot assembly suitable for use with the embodiment of FIG. 7 .
[0026] FIG. 8 is an elevation view of a fold-over post according to another embodiment of the present invention.
[0027] FIG. 9 is an elevation view of a fence panel incorporating an embodiment of a fold-over post.
[0028] FIG. 10 is an elevation view of a fencing system incorporating an embodiment of a fold-over post.
[0029] FIG. 11 is a side view of a foot assembly suitable for use with a fold-over post.
DETAILED DESCRIPTION
[0030] In the following detailed description numerous specific details are set forth in order to provide a thorough understanding of the invention. However, it will be understood by those skilled in the art that the present invention may be practiced without these specific details. For example, the invention is not limited in scope to the particular type of industry application depicted in the figures. In other instances, well-known methods, procedures, and components have not been described in detail so as not to obscure the present invention.
[0031] FIGS. 1-6 illustrate a portable, multi-purpose, fold-over fence panel 10 . The fence panel 10 is well-suited for use in a fencing system for delineating athletic fields, such as baseball and softball outfields, dividing a larger field into several separate athletic fields, and for general crowd control or other general purpose uses. The fence panel 10 is formed by a frame 12 that is composed of two vertical members 14 , 16 and two horizontal members 18 , 20 . In a preferred embodiment, the vertical 14 , 16 and horizontal 18 , 20 members are connected by four rounded comer pieces 22 . The rounded comer pieces 22 help minimize the presence of sharp comers or protrusions in the frame 12 , thereby enhancing the overall safety of the fence panel 12 . Advantageously, the frame 10 , vertical members 14 , 16 , horizontal members 18 , 20 , and comer pieces 22 are all constructed of a tubular, lightweight, plastic material of any suitable cross-section, including round, square, rectangular, etc. In alternative embodiments, these items are constructed from wood, composite, or metal or aluminum piping. In a particularly preferred embodiment, the components of the frame 10 are composed of tubular PVC. The frame may also be constructed as a unitary structure without connecting corner pieces, e.g., a welded aluminum frame or a single aluminum pipe bent to the proper shape.
[0032] The lower horizontal member 18 of the frame 10 may be modified to include a pair of steps 24 . The steps 24 aid in the installation of the fence panel by providing additional leverage for an installer in driving the mounting spikes (discussed in detail below) into the ground.
[0033] The frame 12 supports a panel of flexible material 26 , which completes the fence panel 10 . The panel 26 may be constructed from a number of suitable materials including a wire or plastic mesh, plastic or fabric netting, a solid panel of plastic material, or any other suitable lightweight, flexible material. In a preferred embodiment, the panel 26 is made of a flat laminar mesh made of high density polyethylene. The panel 26 is attached to the frame 12 by an attachment means 28 . Suitable attachment means 28 include hook and loop fastening fabric, e.g., Velcro® strips, wire ties, or pipe. Lower profile attachment means without protrusions are preferred in order to enhance the safety of the fence panels.
[0034] The panel 26 can be personalized in a number of different ways. A particular color of material may be selected for the panel 26 to match a school's or an organization's unique color scheme. The panel 26 may also be adapted to hold a message banner, for example, advertisements of corporate event sponsors, thereby providing an additional source of revenue for an event organizer.
[0035] The two lower corner pieces 22 are advantageously T-shaped connectors 30 . The lower ends of these connectors provide the means for attaching a pair of springs 30 to the frame 12 . An adapter 32 is inserted into the lower end of each T-shaped connector 30 . A spring 34 is then slipped onto the adapter 32 . The spring 34 is a coil spring preferably constructed of ⅜″ diameter wire and is formed with an inside diameter slightly smaller than the outside diameter of the adapter 32 in order to create an interference fit between the spring 34 and the adapter 32 . Each spring 34 terminates in a mounting spike 36 .
[0036] In order to install the fence panel 10 , the two mounting spikes 36 are inserted into the ground to provide a foundation for the fence panel 10 . In a preferred embodiment, each mounting spike 36 is inserted through a plate 38 to provide additional stability to the fence panel 10 . Each plate 38 is provided with a hole 40 having an inside diameter roughly equal or slightly larger than the wire gauge of the spring/mounting spike. The plate 38 rests at the top of the mounting spike 36 adjacent to the spring 34 . Once installed, the plate 38 is sandwiched between the ground surface and the spring 34 . The plate 38 is particularly beneficial when the fence panel 10 is installed on wet, muddy or loose turf. In a preferred embodiment, the plate 38 is also provided with a depression 41 that conforms to the angled bottom of the spring 34 . This arrangement helps support the spring 34 in a more upright position, thereby further enhancing the stability and appearance of the fence panel 10 .
[0037] The arrangement of the springs 34 , mounting spikes 36 and stability plates 38 provide a particularly fast and efficient method of installing temporary fencing. Using this arrangement an entire baseball outfield fence utilizing approximately 150 feet or more of fence panels may be installed by two individuals in less than one hour. This arrangement also speeds removal of the fence panels.
[0038] Once the fence panel 10 is installed, the springs 34 act as a pivot point for the entire fence panel 10 . If a player strikes the fence, for example, when chasing down a fly ball during a baseball or softball game, the springs 34 allow the fence panel 10 to fold flat during impact, thereby reducing the force of the impact on the player and limiting the potential for injury to the player. Advantageously, the coil spring design allows the springs 34 to respond to an impact occurring from almost any angle, including perpendicular to the fence panel or at a very shallow angle, i.e., when a player is running almost parallel to the fence prior to impact. The fence panel 10 will also fold over from an impact initiated from either side of the fence. This feature allows the fence to be used in configurations where play occurs simultaneously on both sides of the fence, for example, where a single fence separates the outfield of one baseball field from the outfield of another field, while producing the same safety advantages to players on both of the fields.
[0039] After impact and once the player has recovered and removed his/her weight from the fence panel 10 , the panel readily returns to its upright position and is ready for further play without the need for repositioning or additional maintenance. This rebound feature is created by the use of a wire gauge in the design of the spring 34 that is capable of producing a spring force sufficient to counterbalance the weight of the frame 12 . The rebound feature eliminates any delay to the game due to an impact between a player and the fence.
[0040] As shown in FIG. 3 , a fence composed of fence panels 10 as described herein is constructed by installing a plurality of fence panels 10 immediately adjacent one another in a desired pattern, e.g., the outline of a baseball or softball outfield or to separate adjacent athletic fields. In installing the fence panels 10 , it is not necessary that the fence panels be interconnected. The fence panels do not require interconnection for stability. Leaving the fence panels unconnected allows each individual fence panel to fold over and rebound on its own without affecting the neighboring panels. However, the panels may be interconnected if necessary with hook and loop fastening fabric, e.g., Velcro® strips, or other releasable means, thereby allowing individual panels to “break away” from adjacent panels upon impact. One alternate means of interconnecting adjacent fence panels, shown in FIG. 6 , includes a connecting clip 52 formed by two open circular clips 54 preferable constructed of a lightweight plastic that are connected by a band 56 . The open sides of the clips 54 allow the connecting clip 52 to “release” from one or both of the adjacent fence panels upon impact. An alternate means of interconnecting adjacent fence panels utilizes a dual stability plate 58 . The plate 58 includes two holes 40 to accommodate mounting spikes 36 and two conforming depressions 41 to accommodate springs 34 . In a particularly preferred version of this embodiment, the springs 34 for the adjacent fence panels 10 are connected together prior to installation on the adjacent fence panels and insertion into the stability plate 58 .
[0041] FIG. 7 illustrates the convertible nature of the above described fencing system. Each fence panel 10 may be quickly and easily adapted for use on any hard outdoor or indoor surface by replacing the adapters 32 and springs 34 with a pair of foot assemblies 42 . Each foot assembly 42 includes a horizontal foot 44 , a vertical leg 46 , which is inserted into the lower end of T-shaped connector 30 , and a T-connector 48 , which connects the horizontal foot 44 and the vertical leg 46 . In a preferred embodiment, the components of the foot assemblies 42 are constructed of tubular PVC. In an alternate embodiment, a spring 50 having a similar construction to spring 34 , but without the mounting spike 36 , is slipped onto the vertical leg 46 and the adapter 32 . This embodiment allows the fence panel 10 to retain its fold-over and rebound features while using the foot assemblies 42 . The ability to convert the fence panels 10 from outdoor to indoor use allows organizations to utilize the fencing system for a larger number of events, thereby enhancing the utility, value, and affordability of the fencing system.
[0042] FIG. 8 illustrates a fold-over post 60 according to another embodiment. The post 60 includes a vertical member 62 . The vertical member may be constructed from any suitable rigid or semi-rigid material, including, as non-limiting examples, PVC pipe, metal pipe, wood, composite, or plastic. While vertical member 62 in the embodiment shown in FIG. 8 is provided with a tubular cross-section, any cross-sectional shape may be used. The lower end of the vertical member 62 is inserted into a spring 64 . The spring 64 is of substantially similar construction to the spring 34 used in the fence panel described previously. The spring 64 is a coil spring preferably constructed of ⅜″ diameter wire and is formed with an inside diameter slightly smaller than the outside diameter of the vertical member 62 in order to create an interference fit between the spring 64 and the vertical member 62 . The spring 64 terminates in a mounting spike 66 .
[0043] In a preferred embodiment, the mounting spike 66 is inserted through a plate 68 to provide additional stability to the vertical member 62 . The plate 68 is substantially similar to plate 38 but including only a single hole having an inside diameter roughly equal or slightly larger than the wire gauge of the spring/mounting spike and a single depression that conforms to the angled bottom of the spring 64 . The plate 68 rests at the top of the mounting spike 66 adjacent to the spring 64 . Once installed, the plate 68 is sandwiched between the ground surface and the spring 64 . This arrangement helps support the spring 64 in a more upright position, thereby further enhancing the stability and appearance of the vertical member 62 .
[0044] As with the springs 34 in the fence panel 10 , the springs 64 on the vertical member 62 acts as a pivot point for the vertical member 62 . If a player or vehicle strikes the post 60 , the spring 64 allows the post 60 to fold over during impact from any angle.
[0045] The fold-over post 60 may utilized with the fence panel 10 , as illustrated in FIG. 9 , to provide additional support for the panel 10 in extreme wind conditions or where it is desired to use a heavier panel 26 that may be more resistant to wind. In this application, the fold-over post 60 is installed immediately adjacent to the downwind side of the fence panel 10 at approximately the midpoint of the fence panel 10 .
[0046] In another application that is illustrated in FIG. 10 , multiple posts 60 are used in combination with flexible fencing material 72 to form a fence. This application results in a fold-over fencing system that is extremely easy to install in a short period of time. The flexible fencing material 72 may be constructed from wire or plastic mesh, plastic or fabric netting, solid plastic or canvas material, or any other suitable lightweight, flexible material. In a preferred embodiment, the flexible material 72 is provided in a continuous length of material that is unwound and connected to each fold-over post 60 by any suitable method. In another preferred embodiment, the post is provided with a cap 74 , that may advantageously be constructed of a cushioned material, such as a foam or a lower density plastic. The cap 74 provides additional protection for players that may impact the top of the post 60 .
[0047] Like the fence panel 10 described above, the fold-over post 60 is adaptable for use on indoor or other hard surfaces. FIG. 11 illustrates the convertible nature of the post 60 . Spring 64 may be removed and replaced with a foot assembly 76 . Each foot assembly 76 includes cross members 78 that are connected with one another by a connecting member 82 . The connecting member 82 includes a vertical portion 84 . The vertical member 62 of the post 60 is inserted into one end of an adapter 86 , while the vertical portion 84 of the connecting member 82 is inserted into the other end of the adapter 86 to complete the conversion. In a preferred embodiment, the components of the foot assembly 76 are constructed of tubular PVC. In an alternate embodiment, a spring 88 having a similar construction to spring 64 , but without the mounting spike 66 , replaces the adapter 86 and is slipped onto the vertical member 62 and the vertical portion 84 of the connecting member 82 . This embodiment allows the post 60 to retain its fold-over and rebound features while using the foot assembly 76 .
[0048] Other objects, features and advantages of the present invention will be apparent to those skilled in the art. While preferred embodiments of the present invention have been illustrated and described, this has been by way of illustration and the invention should not be limited.
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A portable, fold-over post for use on both outdoor and indoor surfaces includes a vertical member; a first spring removably connected to the vertical member, said spring having a mounting spike integrally formed therewith for insertion into a soft, outdoor surface, and said spring allowing the post to fold over upon impact; and a foot assembly interchangeable with said spring and suitable for supporting said post on a hard surface.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a catalyst composition showing a high activity for homopolymerizing or copolymerizing olefins. More particularly, it relates to a catalyst composition and a process for the preparation thereof which catalyst composition provides a highly stereoregular polymer in a high yield when the catalyst composition is used for the polymerization of an α-olefin having at least 3 carbon atoms, and a process for the polymerization of olefins.
2. Description of the Related Art
Many proposals have been made on the process for the preparation of a catalyst component where a solid catalyst component comprising magnesium, titanium and halogen compounds and an electron donor, (i.e., an internal donor) as indispensable ingredients. In most of these proposals, an organic carboxylic acid ester is used as the electron donor, and there is a problem in that an ester smell remains in the formed polymer unless the ester is removed by washing with an organic solvent or the like means. Moreover, these catalyst components have a poor catalytic activity and provide a low stereospecificity. Accordingly, the development of a catalyst having a higher performance is desired.
SUMMARY OF THE INVENTION
A primary object of the present invention to provide a catalyst system having a high catalytic activity and capable of providing a highly stereoregular olefin polymer, which is difficult to obtain by the conventional technique.
In accordance with the present invention, there is provided a process for the preparation of a catalyst component for use in the polymerization of olefins, which comprises, during or after the formation of solid catalyst component derived from a magnesium compound, a titanium compound and a halogen-containing compound as indispensable ingredients, treating the solid catalyst component with at least one member selected from the group consisting of keto-ester compounds represented by the following general formula (I): ##STR2## wherein R 1 and R 2 independently represent a univalent hydrocarbon group having 1 to 20 carbon atoms which may have at least one halogen substituent, and Z represents a divalent hydrocarbon group having 1 to 30 carbon atoms which may have at least one halogen substituent, the R 1 , R 2 , and Z being selected from the group consisting of aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, polycyclic hydrocarbon groups.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
As the magnesium compound used for the preparation of the solid catalyst component in the present invention, there can be mentioned magnesium halides such as magnesium chloride and magnesium bromide, magnesium alkoxides such as magnesium ethoxide and magnesium isopropoxide, magnesium salts of carboxylic acids such as magnesium laurate and magnesium stearate, alkyl magnesium such as butylethyl magnesium, alkyl magnesium halides such as n-butyl magnesium chloride, and alkylalkoxy magnesium compounds such as n-butylethoxy magnesium. These magnesium compounds can be used alone or as a mixture of two or more thereof. A magnesium halide or a compound capable of forming a magnesium halide at the step of preparing the catalyst is preferably used. The compound having chlorine as the halogen is most preferably used.
As the titanium compound used for the preparation of the solid catalyst component in the present invention, there can be mentioned titanium halides such as titanium tetrachloride, titanium trichloride, and titanium tetrabromide, titanium alkoxides such as titanium butoxide and titanium ethoxide, and alkoxytitanium halides such as phenoxytitanium chloride. These titanium compounds can be used alone or as a mixture of two or more thereof. A tetravalent titanium compound containing a halogen is preferably used and titanium tetrachloride is most preferably used.
As the halogen of the halogen-containing compound used for the preparation of the solid catalyst component in the present invention, there can be mentioned fluorine, chlorine, bromine and iodine, and chlorine is preferable. The kind of the halogen-containing compound practically used depends on the catalyst-preparing process, and as typical instances, there can be mentioned titanium halides such as titanium tetrachloride and titanium tetrabromide, silicon halides such as silicon tetrachloride and silicon tetrabromide, and phosphorus halides such as phosphorus trichloride and phosphorus pentachloride. In some preparation processes, halogenated hydrocarbons, halogen molecules and hydrohalogenic acids such as HCl, HBr and HI can be used.
The keto-ester compound used in the present invention is represented by the following general formula: ##STR3##
In the general formula (I), R 1 is a univalent hydrocarbon group having 1 to 20 carbon atoms, which is selected from the group consisting of aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and polycyclic hydrocarbons. As specific examples, there can be mentioned methyl, ethyl, n-propyl, i-propyl, sec-butyl, tert-butyl, tert-amyl, 2-hexenyl, isopropenyl, cyclopentyl, cyclohexyl, tetramethylcyclohexyl, cyclohexenyl, norbornyl, phenyl, tolyl, ethylphenyl, xylyl, cumyl, trimethylphenyl, tetramethylphenyl, pentamethylphenyl, naphthyl, methylnaphthyl, anthranyl, benzyl, diphenylmethyl, and indenyl groups. R 1 may have at least one halogen substituent. Among these groups, a univalent aromatic or polycyclic hydrocarbon group having 6 to 20 carbon atoms is preferably used.
In the general formula (I), Z is a divalent hydrocarbon group having 1 to 30 carbon atoms, which is selected from the group consisting of aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and polycyclic hydrocarbons. As specific examples, there can be mentioned methylene, ethylene, trimethylene, propylene, cyclohexane-diyl, tetramethylcyclohexane-diyl, o-phenylene, m-phenylene, p-phenylene, dimethyl-o-phenylene, 1,2-naphthylene, 2,3-naphthylene, 1,8-naphthylene, biphenylene, binaphthylene, and 1,9-fluorenediyl groups. Z may have at least one halogen substituent. Among these groups, a divalent aromatic or polycyclic hydrocarbon group having 6 to 20 carbon atoms is preferably used.
In the general formula (I), R 2 represents a univalent hydrocarbon group having 1 to 20 carbon atoms, which is selected from the group consisting of aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and polycyclic hydrocarbons. As specific examples, there can be mentioned methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, cyclohexyl, phenyl tolyl, xylyl, and naphthyl groups. R 2 may have at least one halogen substituent. A univalent aliphatic hydrocarbon group having 1 to 12 carbon atoms is preferably used.
As specific examples of the keto-ester compound represented by the general formula (I), there can be mentioned methyl 2-benzoylbenzoate, ethyl 2-benzoylbenzoate, n-butyl 2-(2'-methylbenzoyl)benzoate, ethyl 2-(2',4'-dimethylbenzoyl)benzoate, ethyl 2-(2',4',6'-trimethylbenzoyl)benzoate, propyl 2-(pentamethylbenzoyl)benzoate, ethyl 2-(triethylbenzoyl)benzoate, ethyl 2-(4'-chlorobenzoyl)benzoate, methyl 2-(trimethylbenzoyl)-4,5-dimethylbenzoate, n-propyl 2-(benzoyl-3,6-dimethylbenzoate, ethyl (1'-naphthyl)phenylketone-2-carboxylate, methyl (1'-naphthyl)-4,5-dimethylphenylketone-2-carboxylate, propyl (2'-naphthyl)phenylketone-2-carboxylate butyl phenyl-1-naphthylketone-2-carboxylate ethyl mesityl-2-naphthylketone-3-carboxylate, propyl 8-benzoylnaphthalene-carboxylate, heptyl 8-toluoylnaphtalene-carboxylate, isobutyl 2'-toluoylbiphenyl-2-carboxylate, methyl 2'-benzoylbiphenyl-2-carboxylate, ethyl 2'-benzoylbinaphthyl-2-carboxylate, butyl (5'-indenyl)phenylketone-2-carboxylate, n-butyl 2-benzoylfluorene-carboxylate, ethyl 9-benzoylfluorenecarboxylate, n-butyl 6-(4'-toluoyl)-indene-5-carboxylate, and ethyl 10-benzoylphenanethrene-10-carboxylate.
The process for the preparation of the catalyst used in the present invention is not particularly critical. A method can be adopted in which a magnesium compound such as a magnesium halide, a titanium compound such as a titanium halide and the keto-ester of formula (I) are co-pulverized and the halogenation treatment is then carried out to increase the activity. Alternatively, a method can be adopted in which the magnesium compound is pulverized alone or in combination with a silicon compound or phosphorus compound and the titanium compound treatment and the halogenation treatment are carried out in the presence of the keto-ester of formula (I).
Moreover, a method can be adopted in which a magnesium carboxylate or magnesium alkoxide, the titanium compound, the halogenating agent and the keto-ester of formula (I) are heat-treated to enhance the performances, or a method in which a magnesium halide is dissolved in an organic solvent and the keto-ester of formula (I) is reacted in the presence of the titanium compound during or after the precipitation.
Still further, a catalyst formed by adding the keto-ester of formula (I) and titanium compound when the alkyl magnesium is reacted with the halogenating agent can be used.
Still in addition, a catalyst formed by adding the keto-ester of formula (I) and titanium compound when the halogenated hydrocarbon is reacted with metallic magnesium to form a magnesium halide is the starting material; can be used.
The amount of the keto-ester of formula (I) left in the catalyst differs according to the preparation process, but the titanium/magnesium/keto-ester molar ratio is preferably in the range of 1/(1 to 1,000)/(10 -6 to 100), more preferably 1/(2 to 100)/(10 -4 to 10). If the amount of the keto-ester of formula (I) is too small and below the above-mentioned range, the stereospecificity of the olefin polymer is reduced, but if the amount of the keto-ester of formula (I) is too large, the catalytic activity is reduced.
The polymerization of olefins will now be described.
An olefin can be polymerized by using the thus-obtained solid catalyst component of the present invention in combination with an organic aluminum compound.
As typical examples of the organic aluminum compound used in the present invention, there can be mentioned compounds represented by the following general formulae (II) through (IV):
AlR.sup.3 R.sup.4 R.sup.5 (II)
R.sup.6 R.sup.7 Al--O--AlR.sup.8 R.sup.9 (III)
and ##STR4##
In formulae (II) through (IV), R 3 , R 4 , and R 5 , which may be the same or different, represent a hydrocarbon group having 1 to 12 carbon atoms, a halogen atom or a hydrogen atom, with the proviso that at least one of R 3 , R 4 and R 5 represents a hydrocarbon group. R 6 , R 7 , R 8 , and R 9 , which may be the same or different, represent a hydrocarbon group having 1 to 12 carbon atoms, R 10 represents a hydrocarbon group having 1 to 12 carbon atoms, and l is an integer of at least 1.
As typical examples of the organic aluminum compound represented by formula (II), there can be mentioned trialkylaluminum compounds such as triethylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum and trioctylaluminum, alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride, and alkylaluminum halides such as diethylaluminum chloride, diethylaluminum bromide, and ethylaluminum sesquichloride.
As typical examples of the organic aluminum compound represented by formula (III), there can be mentioned alkyldialumoxanes such as tetraethyldialumoxane and tetrabutyldialumoxane.
Formula (IV) represents an aluminoxane, which is a polymer of an aluminum compound. R 10 includes methyl, ethyl, propyl, butyl, and pentyl groups, but methyl and ethyl groups are preferable. Preferably, l is from 1 to 10.
Among these organic aluminum compounds, trialkylaluminum compounds, alkylaluminum hydrides, and alkylalmoxanes are preferably used, and trialkylaluminum compounds are especially preferably used because they give especially good results.
In the polymerization reaction of α-olefins having at least 3 carbon atoms, to improve the stereoregularity of formed polymers, various compounds having a stereoregularity-improving effect, use of which has been proposed for Ziegler catalysts, can be added to a catalyst system comprising the titanium-containing solid catalyst component of the present invention and a catalyst component comprising an organic aluminum compound. As the compound used for this purpose, there can be mentioned aromatic monocarboxylic acid esters, silicon compounds having an Si--O--C or Si--N--C bond, acetal compounds, germanium compounds having a Ge--O--C bond, and nitrogen- or oxygen-containing heterocyclic compounds having an alkyl substituent.
As specific examples, there can be mentioned ethyl benzoate, butyl benzoate, ethyl p-toluylate, ethyl p-anisate, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, di-n-propyldimethoxysilane, cyclohexylmethyldimethoxysilane, tetraethoxysilane, t-butylmethyldimethoxysilane, benzophenonedimethoxyacetal, benzophenonediethoxyacetal, acetophenonedimethoxyacetal, t-butylmethylketonedimethoxy-acetal, diphenyldimethoxygerman, phenyltriethoxygerman, 2,2,6,6-tetramethylpiperidine, and 2,2,6,6-tetramethylpyrane. Among these compounds, silicon compounds having an Si--O--C or Si--N--C bond and acetal compounds are preferably used, and silicon compounds having an Si--O--C bond are especially preferably used.
In the polymerization of olefins, the amount of the organic aluminum compound in the polymerization system is generally at least 10 -4 millimole/l and preferably at least 10 -2 millimole/l. The molar ratio of the organic aluminum compound to the titanium atom in the solid catalyst component is generally at least 0.5, preferably at least 2 and more preferably at least 10. If the amount of the organic aluminum compound is too small, the polymerization activity is drastically reduced. If the amount of the organic aluminum compound used is larger than 20 millimoles/l and the molar ratio to the titanium atom is higher than 1,000, the catalyst performances are not further increased even by further increasing these values.
When the titanium-containing solid catalyst component of the present invention is used, even if the amount of the above-mentioned stereoregularity-improving agent used for improving the stereoregularity of an α-olefin polymer is very small, the intended object can be attained. This agent is generally used, however, in an amount such that the molar ratio to the organic aluminum compound is 0.001 to 5, preferably 0.01 to 1.
In general, olefins having up to 18 carbon atoms are used. As typical instances, there can be mentioned ethylene, propylene, butene-1, 4-methylpentene-1, hexene-1, and octene-1. These olefins can be homopolymerized, or two or more of these olefins can be copolymerized. A typical example is copolymerization of ethylene with propylene.
In carrying out the polymerization, the solid catalyst component of the present invention, the organic aluminum compound and optionally, the stereoregularity-improving agent can be independently introduced into a polymerization vessel, or two or more of them can be premixed.
The polymerization can be carried out in an inert solvent, a liquid olefin monomer or a gas phase. To obtain a polymer having a practically adoptable melt flow rate, a molecular weight modifier (ordinarily, hydrogen) can be made present in the polymerization system.
The polymerization temperature is preferably -10° to 180° C. and more preferably 20° to 130° C.
The shape of the polymerization vessel, the polymerization controlling procedure and the post-treatment procedure are not particularly limited in the present invention, and known procedures can be adopted.
The present invention will now be described in detail with reference to the following examples that by no means limit the scope of the invention.
In the examples and comparative examples, the heptane index (H.R.) means the amount (%) of the residue obtained when the obtained polymer was extracted with boiling n-heptane for 6-hours. The melt flow rate (MFR) was measured with respect to the polymer powder containing 0.2% of 2,6-di-tert-butyl-4-methylphenol incorporated therein at a temperature of 230° C. under a load of 2.16 kg according to JIS K-6758.
In the examples, all of the compounds (organic solvents, olefins, hydrogen titanium compounds, magnesium compounds, stereoregularity-improving agents) used for the preparation of the solid catalyst component and the polymerization were in the substantially anhydrous state.
The preparation of the solid catalyst component and the polymerization were carried out in a substantially anhydrous nitrogen atmosphere.
EXAMPLE 1
Preparation of Solid Catalyst Component
A stainless steel cylindrical vessel having an inner volume of 1 liter, in which magnetic balls having a diameter of 10 mm were filled in an amount of about 50% based on the apparent volume, was charged with 20 g (0.21 mole) of anhydrous magnesium chloride (obtained by heating to dry commercially available anhydrous magnesium chloride at about 500° C. for 15 hours in a dry hydrogen chloride gas), 12.7 g (0.05 mole) of ethyl 2-benzoylbenzoate 3.3 ml of titanium tetrachloride and 3.0 ml of a silicone oil (TSS-451.20CS supplied by Shin-Etsu Chemical) as the pulverizing assistant in a dry nitrogen current. The vessel was attached to a shaking ball mill having an amplitude of 6 mm and the co-pulverization was carried out for 15 hours to obtain a co-pulverized solid. Then, 15 g of the co-pulverized solid was suspended in 150 ml of 1,2-dichloroethane, and the suspension was stirred at 80° C. for 2 hours. The solid was recovered by filtration and thoroughly washed with hexane until free 1,2-dichloroethane was not detected in the washing liquid. The solid was dried at a low temperature to 30° to 40° C. under a reduced pressure to remove hexane, whereby a solid catalyst component was obtained. The titanium atom content in the solid catalyst component was 2.3% by weight.
Polymerization and Physical Properties of Polymer
A stainless steel autocrave having an inner volume of 3 l was charged with 20 mg of the solid catalyst component prepared by the above-mentioned method, 91 mg of triethylaluminum and 20 mg of diphenyldimethoxysilane, and immediately, 760 g of propylene and 0.1 g of hydrogen were charged into the autocrave. The inner temperature of the autocrave was elevated and maintained at 70° C. After 1 hour, the gas in the autocrave was discharged to stop the polymerization. As the result, 210 g of powdery polypropylene was obtained. The polymerization activity was thus 10,900 g/g of solid catalyst component.hour and 474 kg/g of Ti.hour. The H.R. of the powdery polypropylene was 95.1%, and the MRF was 5.2 g/10 min.
EXAMPLE 2
Using the solid catalyst component prepared in Example 1, the polymerization was carried out in the same manner as described in Example 1 except that the polymerization temperature was changed to 80° C. As the result, 253 g of a powdery polymer was obtained. The polymerization activity was 12,700 g/g of solid catalyst component.hr and 550 kg/g of Ti.hour, the H.R. of the powdery polypropylene was 96.0%, and the MFR was 4.7 g/10 min.
EXAMPLE 3
Using the solid catalyst component used in Example 1, the polymerization was carried out in the same manner as described in Example 1 except that 20 mg of phenyltriethoxysilane was used at the polymerization instead of diphenyldimethoxysilane. The polymerization activity was 11,300 g/g of solid catalyst component.hr and 4.91 kg/g of Ti.hr, the H.R. of the obtained polymer was 94.9%, and the MFR was 11.7 g/10 min.
EXAMPLES 4 THROUGH 7
Using the solid catalyst component used in Example 1, the polymerization was carried out in the same manner as described in Example 1 except that the stereoregularity-improving agent added was changed as shown in Table 1. The results are shown in Table 1.
TABLE 1__________________________________________________________________________ Amount added PolymerizationExampleStereoregularity-improving (molar ratio activity H.R. MFRNo. agent to Al) (g/g · cat* · hr) (%) (g/10 min)__________________________________________________________________________4 Phenyltriethoxysilane 0.3 10,200 95.6 6.75 t-Butylmethyldimethylacetal 0.3 6,900 93.7 4.16 Benzophenonedimethylacetal 0.3 7,100 94.1 1.87 2,2,6,6-Tetramethylpiperidine 0.15 15,400 95.0 2.6__________________________________________________________________________ *solid catalyst component
EXAMPLE 8
In a round-bottom flask, 9.5 g of anhydrous magnesium chloride (treated in the same manner as described in Example 1) was heated and dissolved at 130° C. for 2 hours in 50 ml of decane and 46.8 ml of 2-ethylhexyl alcohol in an N 2 atmosphere. Then, 2.1 g of phthalic anhydride was added to the mixture, and the mixture was heated at 130° C. for 1 hour. The liquid mixture was cooled to room temperature and 20 ml of the liquid mixture was charged in a dropping funnel and dropped into 80 ml of titanium tetrachloride maintained at -20° C. over a period of 30 minutes. The temperature was elevated to 110° C. over a period of 4 hours, and a solution of 3.81 g of ethyl 2-benzoylbenzoate was gradually dropped into the reaction mixture. After termination of the dropwise addition, the reaction was carried out at 110° C. for 2 hours. The supernatant was removed, 80 ml of TiCl 4 was added to the residue, and the mixture was heated at 110° C. for 2 hours. Then, the formed solid was washed with 100 ml of n-decane three times and then with n-hexane to obtain a solid catalyst component in which the amount of Ti supported was 2.3% by weight.
Using the thus-obtained solid catalyst component, the polymerization was carried out in the same manner as described in Example 1. The polymerization activity was 13,700 g/g of solid catalyst.hr and 596 kg/g of Ti.hr, the H.R. was 96.4%, and the MFR was 7.1 g/10 min.
EXAMPLE 9
A round-bottom flask having a capacity of 300 ml, which was sufficiently dried in a nitrogen current, was charged with 100 ml of n-heptane, 9.5 g of MgCl 2 and 68 g of Ti(O-Bu) and the reaction was carried out at 100° C. for 2 hours to form a homogeneous solution. After termination of the reaction, the temperature was lowered to 40° C. and 15 ml of methylhydrogen polysiloxane (20 cSt) was added to the solution, and the reaction was carried out for 3 hours. The formed solid catalyst was washed with n-heptane 150 ml of heptane was added to the solid catalyst, and a solution of 28 g of SiCl 4 in 80 ml of n-heptane was dropped at room temperature over a period of 1 hour. After termination of the dropwise addition, the reaction was further conducted for 30 minutes. The obtained solid component was washed with 200 ml of n-heptane three times and cooled to -10° C. Then, 100 ml of TiCl 4 was introduced into the solid, the resulting mixture was thoroughly stirred, and 3.23 g of ethyl 2-benzoylbenzoate was added dropwise to the mixture. After termination of the dropwise addition, the reaction was carried out at 90° C. for 2 hours. The supernatant was removed, 100 ml of TiCl 4 was introduced, and the reaction was carried out at 90° C. for 2 hours. After the reaction, the formed solid was washed with n-heptane to obtain a solid catalyst. From the results of the analysis, it was found that the amount of Ti supported was 1.7% by weight.
Using the thus-obtained solid catalyst component, the polymerization was carried out in the same manner as described in Example 1. The polymerization activity was 8,630 g/g of solid catalyst.hr and 454 kg/g of Ti.hr, the H.R. was 94.0%, and the MFR was 17.2 g/10 min.
EXAMPLE 10
A round-bottom flask having a capacity of 300 ml, which was sufficiently dried in a nitrogen current, was charged with 5 g of magnesium diethoxide, 1.40 g of ethyl 2-benzoylbenzoate and 25 ml of methylene chloride, and the mixture was stirred under reflux for 1 hour. The formed suspension was introduced under pressure into 200 ml of TiCl 4 maintained at room temperature, the temperature of the mixture was gradually elevated to 110° C., and the reaction was carried out with stirring for 2 hours. After termination of the reaction, the precipitated solid was recovered by filtration and washed with 200 ml of n-decane maintained at 110° C. three times. Then, 200 ml of TiCl 4 was added to the solid and the reaction was carried out at 120° C. for 2 hours. After termination of the reaction, the precipitated solid was recovered by filtration, washed with 200 ml of n-decane maintained at 110° C. three times and then washed with hexane until the chlorine ion was not detected. The content of the titanium atom in the obtained catalyst component was 3.3%.
Using the thus-obtained solid catalyst component, the polymerization was carried out in the same manner as described in Example 1. It was found that the polymerization activity was 20,400 g/g of solid catalyst component.hr and 618 kg/g of Ti.hr, the H.R. was 96.1%, and the MFR was 10.7 g/min.
EXAMPLES 11 through 21
Solid catalyst components were prepared in the same manner as described in Example 10 except that ester compounds shown in Table 2 were used instead of ethyl 2-benzoylbenzoate. Using the thus-prepared solid catalyst components, the polymerization was carried out in the same manner as described in Example 1. The results are shown in Table 2.
TABLE 2__________________________________________________________________________ PolymerizationExample activity H.R. MFRNo. Keto-esters of formula (I) (g/g · cat* · hr) (%) (g/10 min)__________________________________________________________________________11 Ethyl 2-(4'-methylbenzoyl)benzoate 19,300 96.4 7.012 Ethyl 2-(2',4'-dimethylbenzoyl)benzoate 22,100 96.3 15.913 Ethyl 2-benzoyl-4,5-dimethylbenzoate 20,900 96.0 5.414 n-Propyl 2-benzoyl-3,6-dimethylbenzoate 17,300 96.3 2.315 Ethyl 2-(2',4',6'-trimethylbenzoyl)benzoate 22,700 96.9 11.016 Ethyl 2-(4'-chlorobenzoyl)benzoate 21,200 95.1 7.3__________________________________________________________________________ *solid catalyst component
COMPARATIVE EXAMPLE 1
A solid catalyst component was prepared in the same manner as described in Example 10 except that ethyl benzoate was used instead of ethyl 2-benzoylbenzoate used in Example 10. Using the obtained solid catalyst component, the polymerization was carried out in the same manner as described in Example 1. It was found that the polymerization activity was 15,300 g/g of solid catalyst component.hr and 655 kg/g of Ti.hr, the H.R. of the obtained polypropylene powder was 80.1%, and the MFR was 3.2 g/10 min.
When olefins are polymerized by using the catalyst component obtained according to the present invention, since the catalyst has a very high activity, the content of the catalyst residue in the formed polymer can be reduced to a very low level, and therefore, the ash-removing step can be omitted. Furthermore, since the amount (concentration) of the residual halogen is small, the degree of corrosion of a molding machine or the like at the polymer-processing step can be greatly lowered. The residual catalyst causes deterioration and yellowing of the polymer. According to the present invention, the concentration of the residual catalyst is very low, and thus the occurrence of these undesirable phenomena can be controlled.
Moreover, since the obtained polymer has a high stereoregularity, a polymer having a practically sufficient mechanical strength can be obtained without removing an atactic portion.
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Disclosed is a catalyst composition for use in the polymerization of olefins, which is comprised of (a) a catalyst component containing magnesium, titanium, a halogen, and an ingredient derived from a keto-ester compound, and (b) an organic aluminum compound. The catalyst activity and capability of providing a highly stereoregular polymer are enhanced by preparing the catalyst component (a) by a process wherein, during or after the formation of a solid catalyst component containing magnesium, titanium, and a halogen, the solid catalyst component is treated with a keto-ester of the formula: ##STR1## wherein R 1 , R 2 and Z represent a hydrocarbon group.
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FIELD OF THE INVENTION
The present invention relates generally to real time positioning systems and, more particularly, to the use of such systems for the precise monitoring of land masses.
BACKGROUND
In the mining environment, minerals are sometimes excavated through the process of repetitive explosions. These explosions aid in exposing the ore, making it easier to collect and carry out on trucks for further processing at nearby facilities. However, the explosions also have a damaging effect upon the landscape of the mine. Continuous explosion blasts may cause steep slopes around the edges of the mine that are unstable and highly susceptible to avalanche type landslides. These landslides may cause serious injury to workers in the mine, destroy valuable equipment, or leave the ore burried under tons of rubble and, hence, unrecoverable.
Continuous monitoring of the slopes is required while a mine is being operated. Traditional methods of monitoring include stretching a taut wire along the surface of the slope, or using laser-based systems combined with a series of strategically placed prisms. Such methods are inefficient because they either require an inordinate amount of adjustments, or require trained personnel to visit the mine each time an adjustment is necessary.
Modern monitoring methods are able to make use of remote satellite-based positioning systems. The satellite system most commonly used today is the Global Positioning System (GPS). Engineering and monitoring methods which use GPS can be considerably more efficient and accurate than traditional methods. GPS utilizes signals transmitted by a number of in-view satellites to determine the location of a GPS mobile antenna which is connected to a receiver. The exact position of the antenna can then be monitored from a base station to determine whether there has been any movement of the position of the receiver.
Each GPS satellite transmits two coded L-band carrier signals which enable some compensation for propagation delays through the ionosphere. Each GPS receiver contains an almanac of data describing the satellite orbits and uses ephemeris corrections transmitted by the satellites themselves. Satellite to antenna distances may be deduced from time code or carrier phase differences determined by comparing the received signals with locally generated receiver signals. These distances are then used to determine antenna position. Only those satellites which are sufficiently above the horizon can contribute to a position measurement, the accuracy of which depends on various factors including the geometrical arrangement of the satellites at the time when the distances are determined.
Distances measured from an antenna to four or more satellites enable the antenna position to be calculated with reference to the global ellipsoid WGS-84. Local northing, easting and elevation coordinates can then be determined by applying appropriate datum transformation and map projection. By using carrier phase differences in any one of several known base or mobile receiver techniques, the mobile antenna coordinates can be determined to an accuracy on the order of ±1 cm. Using such real time kinematic (RTK) techniques, an operator can obtain position measurements within seconds of placing a mobile antenna on an unknown point. In RTK systems, GPS data is transmitted by a radio or other link between the base and mobile receivers, whether or not there is a dear line of site to ensure that accuracy in the mobile position measurements is maintained and the positioning information is correct.
SUMMARY OF THE INVENTION
According to one embodiment, a slope of a land mass is precisely monitored. Remote sensors are placed in selected positions on the slope. The remote sensors are configured to provide real time position information. A virtual model of the slope is created using positioning information generated by the remote sensors and is stored in a computer memory. The position of each remote sensor is also recorded in the computer memory so that the virtual model accurately reflects the real world situation. A threshold value is set to establish a permissible deviation of each remote sensor location. Real time positioning information produced by the remote sensors is monitored at a base station and is used to update the virtual model. If the position of a remote sensor deviates beyond its associated threshold value, an alarm message is flashed. The information so obtained can also be displayed to a user as a graphical and textual representation of the current state of the slope. Reports can be generated once an alarm message is given.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention is illustrated by way of example and not limitation in the figures of the accompanying drawings in which:
FIG. 1 illustrates a cross section view of the slope of a land mass;
FIG. 2a illustrates a remote sensor of a monitoring system according to one embodiment;
FIG. 2b illustrates a remote sensor of a monitoring system according to a second embodiment;
FIG. 3 illustrates a base station of a monitoring system according to one embodiment;
FIG. 4 illustrates various views of a land mass in three dimensions; and
FIG. 5 is a flow diagram illustrating a method of monitoring slope creep according to one embodiment.
DETAILED DESCRIPTION
Referring to the drawings in detail, wherein like numerals designate like parts and components, the following description sets forth numerous specific details in order to provide a thorough understanding of the present invention. However, after reviewing this specification, it will be apparent to those skilled in the art that the present invention may be practiced without some or all of these specific details. In other instances, well known structures, programming techniques and devices have not been described in detail in order not to unnecessarily obscure the present invention.
FIG. 1 illustrates a cross section view of a slope 15 of a mine or other land mass 10. According to the present invention, remote sensors 100 are strategically positioned along slope 15. Remote sensors 100 determine location coordinates and transmit the coordinates to a base station (not shown) via radio or other communication link. The base station may be located at a site that is in close proximity to the mine 10, or may be positioned at a distant site. Alternatively, remote sensors 100 may transmit raw GPS data received at the sensors 100 to the base station for further processing (e.g., position determination) at the base station.
FIG. 2a illustrates a remote sensor 100 of a slope monitoring system according the present invention. Remote sensor 100 includes a GPS sensor 150 which is coupled to a radio 130. GPS sensor 150 has an associated antenna 120 which is placed in a strategic location on slope 15.
GPS sensor 150 is capable of receiving signals from in-view satellites in order to produce positioning information therefrom. The positioning information is transferred to and modulated by radio 130 and transmitted from antenna 140 to a base station via radio link 300. Although a preferred embodiment uses a remote sensor 100 having a self-contained GPS sensor 150 and radio 130, those skilled in the art will appreciate that multiple GPS sensors 150 placed in different locations may be coupled to one radio 130. Furthermore, those skilled in the art will appreciate that this coupling may be achieved using a hardwired connection, an optical connection or, in some cases, a wireless connection.
Radio 130 receives and demodulates real-time kinematic GPS data transmitted to sensor 100 by a GPS base station. This real-time kinematic GPS data may be transmitted across radio link 300 or separate communication link using techniques well known in the art.
FIG. 2b illustrates an alternative embodiment of remote sensor 100. In this embodiment, remote sensor 100 consists of a GPS sensor 150, a memory 160, and a central processing unit (CPU) 170. Each of these components is linked to a radio 130 via a bus 110. Again, GPS sensor 150 has an associated antenna 120 which is placed in a strategic location on slope 15.
GPS sensor 150 receives positioning information through antenna 120, under the control of CPU 170. As before, radio 130 receives and demodulates real-time kinematic correction information received from a base station via radio link 300. The correction information is transmitted from the radio 130 to the CPU 170 over the bus 110. CPU 170, in turn, makes the appropriate corrections to the positioning information produced by GPS sensor 150. Alternatively, these corrections may be performed by GPS sensor 150 itself. The positioning information so obtained may be updated continuously to produce an updated position. Each updated position may be compared against a previously generated position to determine whether the sensor, i.e., the ground to which the sensor is fixed, has moved. If movement is detected, an alarm message may be generated by CPU 170 and transmitted via radio 130 and radio link 300 to a base station (not shown). It will be appreciated that the control information required to perform these calculations may be stored in memory 160 or other suitable storage medium and executed by CPU 170.
According to another embodiment, remote sensor 100 operates under a variable collection duty cycle. The variable collection duty cycle enables the remote sensor 100 to become active and collect position information at user-defined intervals. Consequently, the variable collection duty cycle enables remote sensor 100 to conserve battery life. The variable collection duty cycle may be implemented as a poll-and-respond system wherein remote sensors 100 are in a low power mode initially, listening for an activation signal from a base station. When a user wishes to obtain positioning information, an activation signal from the base station is transmitted to the remote sensors 100. Upon detecting the activation signal, each remote sensor 100 activates its internal GPS sensor 150 and begins to collect positioning data from in-view satellites. The activation signal may include real-time kinematic GPS data, thereby allowing GPS sensors 150 to derive centimeter level accurate positions for the respective sensor 100. Alternatively, each remote sensor 100 may be configured to provide positioning information updates to a base station at regular intervals (e.g., hourly, daily, etc.), without the need for a polling request from a base station. In such an embodiment, real-time kinematic GPS data may be continually broadcast by a base station for use by remote sensors 100 as appropriate. Other variable duty cycle embodiments will be apparent to those skilled in the art upon review of this specification.
Although described with reference to individual remote sensors 100 having one antenna 120 for each GPS sensor 150, those skilled in the art will appreciate that a single GPS sensor 150 could be used with a number of antennas 120 connected thereto. In such an embodiment, GPS sensor 150 would include an antenna switch for switching between each of the various antennas 120 located at different locations on the slope 15. In this way, monitoring information for each location associated with an antenna 120 could be obtained in a sequential fashion. For those applications where simultaneous, real-time monitoring information from each location associated with an antenna 120 is not required, such an embodiment is sufficient. However, where real-time, simultaneous monitoring information is required, individual GPS sensors 150, each with its own antenna 120, will be required.
FIG. 3 illustrates a base station 200 of a slope monitoring system according the present invention. Base station 200 includes a radio 230, GPS base station 250, memory 260, central processing unit 270, and a display 280. Radio 230 includes antenna 240. Each of these components is coupled by a bus 210.
In order to derive centimeter level accurate positioning information, remote sensors 100 communicate with GPS base station 250 via radio link 300. GPS base station 250 provides real-time kinematic GPS data to allow remote sensors 100 to produce real-time, centimeter level accurate positioning information. The manner in which such calculations are derived are well known in the art. Alternatively GPS base station 250 could produce differential GPS (DGPS) correction information and provide same to remote sensors 100 via radio link 300. Those skilled in the art will appreciate that if DGPS is used, the positioning information derived from remote sensors 100 will be on the order of ±1 meter.
Base station 200 receives positioning information from one or more remote sensors 100 via radio link 300. Alternatively, raw GPS data from the remote sensors may be received at the base station 200 for later processing, as discussed above. Radio signals from radio 130 are received at antenna 240 and demodulated by radio 230 under the control of central processing unit (CPU) 270. This data may be stored in memory 260 or another storage device (not shown) for archiving purposes.
CPU 270 is also provided with a virtual model of slope 15. The virtual model is a three dimensional digital representation of slope 15 and is typically stored in memory 260. FIG. 4 illustrates a slope of a land mass represented in a virtual model. Land mass 500 might represent a mine 10 shown in FIG. 1, or some other land mass that requires monitoring. Using programming techniques well known in the art, land mass 500 is represented in a digital format and stored in a data structure (e.g. a GIS data structure) in memory 260. As remote sensors 100 are positioned on the land mass 500, their locations are received by base station 200 and recorded within the virtual model. For example, remote sensors 100 may be located at positions 510 and 520. These reference points are included in the virtual model with reference to an XYZ coordinate system.
The XYZ coordinate system is based on a WGS-84 coordinate system. This may be translated to a real world coordinate system using transformation techniques well known in the art.
The virtual model so established can be used for accurate monitoring of slope 15 as follows and as illustrated in the flow diagram of FIG. 5. FIG. 5 shows a process 600 for the precise monitoring of slope 15 shown in FIG. 1. At step 605, remote sensors 100 are positioned on slope 15. At step 610, the virtual model of the slope is established using position information gathered by remote sensors 100. The virtual model is stored in memory 260 and represents a network of control points established by the positioning information provided by the remote sensors 100. At step 615, a threshold value is set for each remote sensor 100. The threshold value establishes a permissible range of movement for each remote sensor 100.
At step 620, slope 15 is in the process of being monitored. During the monitoring process, the data provided by the remote sensors 100 is monitored at the base station 200 using radio link 300. Real-time positioning information from each remote sensor 100 is multiplexed on a radio signal by radio 130 and transmitted via antenna 140 across radio link 300 to radio 230 located at base station 200. Radio 230 receives the radio link transmission 300 via antenna 240 and demultiplexes and demodulates the radio signal so as to present each of the individual remote sensor 100 data on bus 210.
At step 625, CPU 270 uses the real-time remote sensor data provided by radio 240 to compare the current position of each remote sensor 100 on slope 15 to the positions stored in memory 260 during step 610. At step 630, a determination is made as to whether any of the remote sensors 100 have changed in position. If there is no position change in any of the remote sensors 100, the process repeats above steps 620 and 625 until there is a change in position of a remote sensor 100.
If any remote sensors 100 change position, step 635 determines whether the change for any displaced sensor is greater or less than the threshold distance set in step 615. If the change for any or all displaced remote sensors 100 is less than the threshold distance, the process proceeds to step 640.
At step 640, CPU 270 uses the real-time sensor data provided by radio 230 to update the virtual model stored in memory. The virtual model is updated to represent the actual location of each remote sensor 100, as well as the original position of each remote sensor 100. In this regard, sensor data from remote sensors 100, aided by GPS data or correction information from GPS base station 250, provide precise positioning information using real-time kinematic or differential GPS techniques.
If the change of any displaced remote sensor 100 is greater than the established threshold distance, the process proceeds to step 645. At step 645, an alarm message is flashed on display 280 signaling significant movement of one or more remote sensors 100, thus indicating possible slope creep. Those skilled in the art will appreciate that any number of possible alarm signals such as warning messages, alarm bells and/or whistles, etc. could be used to indicate potential slope creep conditions.
The process continues to step 640, where the virtual model is updated to represent the actual location of each remote sensor 100, as well as the original position of each remote sensor 100. After step 640, the process repeats above steps 620-630 until there is another change in position of a remote sensor 100.
According to the embodiment described with reference to FIG. 2b, steps 620-630 could be carried out in remote sensor 100. If step 630 indicates that there has been a change in sensor position, the real-time position information is transmitted to base station 200 as described above. Steps 635-645 are then carried out in base station 200.
In an alternative embodiment, after the alarm message has been produced, CPU 270 collects a user defined set of data. This data may include a relatively long record of sensor information, e.g., on the order of 10 min., from remote sensors 100 on slope 15. The data is collected in the manner described above and stored in memory 280 or a similar storage device. The data is averaged to eliminate inaccurate readings (e.g., caused by noise in radio link 300) and mean values and standard deviations are computed. The result of this data collection is a virtual model that accurately reflects the status of slope 15. This information can be used to generate a report, which is a summary of the best estimate of the positions of remote sensors 100 on slope 15 for an engineering report. It will be appreciated that such reports may be continuously generated during the monitoring process as part of a background function and need not only be produced after an alarm condition has occurred.
Thus, a method and apparatus for precisely monitoring a slope of a land mass has been described. In the foregoing specification, the present invention has been described with reference to specific exemplary embodiments thereof. It will, however, be evident that various modifications and changes may be made thereto without departing from the spirit and scope of the invention as set forth in the appended claims. The specification and drawings are, accordingly, to be regarded in an illustrative rather than a restrictive sense.
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According to one embodiment, a slope of a land mass is precisely monitored. Remote sensors are placed in selected positions on the slope. The remote sensors are configured to provide real time position information. A virtual model of the slope is created using positioning information generated by the remote sensors and is stored in a computer memory. The position of each remote sensor is also recorded in the computer memory so that the virtual model accurately reflects the real world situation. A threshold value is set to establish a permissible deviation of each remote sensor location. Real time positioning information produced by the remote sensors is monitored at a base station and is used to update the virtual model. If the position of a remote sensor deviates beyond its associated threshold value, an alarm message is flashed. The information so obtained can also be displayed to a user as a graphical and textual representation of the current state of the slope. Reports can be generated once an alarm message is given.
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FIELD OF THE INVENTION
[0001] The present invention relates to an audio signal processing device for providing a level controlled output signal in response to a selected input signal, the device comprising a selection unit for selecting an input signal, an amplification unit for amplifying the selected input signal, and a gain control unit for controlling the gain of the amplification unit in dependence on an audio signal.
[0002] The present invention further relates to a method of providing a level controlled signal in response to a selected input signal.
[0003] The present invention further relates to a computer program product for carrying out the method according to the second paragraph.
BACKGROUND OF THE INVENTION
[0004] An audio device, such as an audio amplifier or a television set, may be connected to various audio sources. In the case of an amplifier such sources may include a CD player, a DVD player, an MP3 player or a (digital or analog) cassette player, while a television set may for example have a VHS player and/or a DVD player as audio sources. It is well known that the level of the audio signals may vary between audio sources. When switching between broadcast television and a DVD player, for example, a large difference in sound levels may occur, which is very unpleasant for the user. Even between television channels differences in sound levels may be present, which typically requires the user to manually adjust the sound level.
[0005] Some television sets allow the relative gains of the audio sources to be pre-set. Although such an arrangement is useful, it suffers from the disadvantage that it is static and fails to respond to any changes of the sound level of a channel. In addition, user input is required, which some users will find troublesome.
[0006] U.S. Pat. No. 5,784,476 (Bird/Philips) discloses a multiple channel audio signal interface that includes a selector circuit, an automatic gain control unit, and an amplifier. The automatic gain control unit is constituted by an amplitude analyzer and a low-pass filter which produce a control signal that is fed to a control input of the amplifier. The amplitude analyzer is arranged for comparing the input audio signal with two pre-set threshold values and for producing a corresponding control signal, while the low-pass filter is arranged for preventing instantaneous gain changes.
[0007] This known arrangement has the drawback that the gain control is not very accurate. The gain control signal is derived from the input signal of the amplifier and does not take any distortions and/or non-linearities into account that may be introduced by the amplifier.
OBJECT AND SUMMARY OF THE INVENTION
[0008] It is an object of the present invention to overcome these and other problems of the Prior Art and to provide an improved audio signal processing device of the type defined in the first opening paragraph and an improved method of the type defined in the second paragraph and an improved computer program product of the type defined in the third paragraph.
[0009] Accordingly, the present invention provides an audio signal processing device for providing a level controlled output signal in response to a selected input signal, the device comprising:
a selection unit for selecting an input signal from a plurality of input signals, an amplification unit for amplifying the selected input signal so as to produce the output signal, and a gain control unit for controlling the gain of the amplification unit in response to a level signal indicative of the audio signal level,
wherein the device is arranged for deriving the level signal from the output signal.
[0013] By deriving the level signal from the output signal, a signal representative of the actual loudspeaker movements is used, instead of a signal that is passed through an amplifier before being fed to the loudspeaker. As a result, a more accurate gain control is achieved. In addition, a feedback arrangement is obtained, instead of a feed-forward arrangement as in the Prior Art referred to above. This also contributes to a more accurate and stable gain control.
[0014] The level signal may be the output signal itself but preferably is a signal derived from the output signal. Accordingly, the output signal may be analyzed, rectified and/or filtered in order to derive the level signal, or the output signal is fed directly to the gain control unit, in which case the gain control unit suitably processes the output signal to produce a corresponding gain control signal.
[0015] If further amplification units are present in the device or in an audio system including the device of the present invention, it is preferred that the level signal is derived from the signal nearest to the loudspeaker unit(s), but in any case downstream from the controlled amplification unit(s).
[0016] In a first embodiment, the gain control unit is coupled to the output of the amplification unit. The gain control unit may be coupled to the output of the (controlled) amplification unit directly or indirectly, indirect coupling involving an intermediate unit, such as a signal analyzer unit.
[0017] In a second embodiment, the gain control unit is coupled to a transducer arranged at a loudspeaker coupled to the device. In this embodiment, the level signal is derived from the output signal through the loudspeaker and the associated transducer. That is, the loudspeaker and the transducer convert the output signal of the (controlled) amplifier into a level signal. It is noted that the transducer may be a separately produced transducer mounted on the loudspeaker, such as an accelerometer, or an integrated transducer, such as a conductive section of the suspension of the loudspeaker.
[0018] In both embodiment described above, a gain setting unit may be arranged between the signal analyzer unit and the gain control unit. Such a gain setting unit allows the user to adjust the automatically controlled gain, and to manually set an average gain value.
[0019] The device of the present invention may further be provided with suitable filters so as to provide gain control per frequency band. Low frequencies, for example, may require less gain adjustment than medium or high frequencies.
[0020] An audio system according to the present invention comprises a device as defined above. The audio system may additionally comprise at least one loudspeaker unit, and/or at least two audio sources, such as CD players, DVD players, MP3 players, radio tuners, television tuners, etc.
[0021] The present invention also provides a method of providing a level controlled output signal in response to a selected input signal, the method comprising the steps of:
selecting an input signal from a plurality of input signals, amplifying the selected input signal so as to produce the output signal, and controlling the gain of the amplification unit in response to a level signal indicative of the audio signal level,
the method further comprising the step of deriving the level signal from the output signal.
[0025] In a first embodiment, the output signal is the signal fed to a loudspeaker unit, while in a second embodiment, the output signal is the signal produced by a transducer in a loudspeaker unit. Of course the first and the second embodiment may be combined so as to use two level signals or at least a combined level signal.
[0026] The present invention additionally provides a computer program product for carrying out the method as defined above. The computer program product may comprise a computer readable set of instructions stored on a carrier medium, such as a CD (compact disc) or a DVD (digital versatile disc).
[0027] The aspects defined above and further aspects of the invention are apparent from the examples of embodiment to be described hereinafter and are explained with reference to these examples of embodiment.
BRIEF DESCRIPTION OF THE DRAWINGS
[0028] The present invention will further be explained below with reference to exemplary embodiments illustrated in the accompanying drawings to which the invention is not limited, in which:
[0029] FIG. 1 schematically shows a multiple input audio level control device according to the Prior Art.
[0030] FIG. 2 schematically shows a first embodiment of a multiple input audio level control device according to the present invention.
[0031] FIG. 3 schematically shows a second embodiment of a multiple input audio level control device according to the present invention.
[0032] FIG. 4 schematically shows a third embodiment of a multiple input audio level control device according to the present invention.
[0033] FIG. 5 schematically shows a fourth embodiment of a multiple input audio level control device according to the present invention.
DESCRIPTION OF EMBODIMENTS
[0034] The Prior Art device 1 ′ shown in FIG. 1 comprises a selector unit 11 , an amplifier 12 , a signal analyzer 13 and a gain control unit 15 . Multiple audio sources 2 a, 2 b, . . . , 2 n are connected to the selector unit 11 which connects a selected audio source (input signal S I ) to the amplifier 12 , which in turn is coupled to a loudspeaker unit 4 .
[0035] The audio sources 2 a, 2 b, . . . , 2 n may include a CD player, a DVD player, an MP3 player, a television set, a (digital) cassette player, a radio tuner, an Internet terminal and/or any other suitable audio source.
[0036] The amplifier 12 is a controlled amplifier, such as a VCO (voltage controlled amplifier) known per se, whose gain is controlled by a gain control signal S G produced by the gain control unit 15 . The gain control unit 15 derives the gain control signal S G from a level signal S L which represents the audio signal level and which is produced by a signal analyzer 13 . In the Prior Art device shown in FIG. 1 , the level signal S L and the gain signal S G are derived from respectively based on the input signal S I .
[0037] When the selector unit 11 is operated to select another audio source, the level of the input signal S I typically changes, as not all audio sound sources produce the same signal level. The change in the (average) signal level of the input signal S I results in a changed level signal S L and hence in a changed gain control signal S G . Accordingly, a change in the level of the input signal S I will typically result in a change in the gain of the amplifier 12 so as to keep the average level of the output signal S O substantially unaltered.
[0038] Deriving the gain control signal S G from the input signal S I has the disadvantage that any distortions introduced by the amplifier 12 are not taken into account. More specifically, any non-linearities of the amplifier, or any other signal distortions, will result in an incorrect gain adjustment. As a result, the (average) level of the output signal S O may still vary undesirably when another audio sound source is selected. This problem is solved by the device of the present invention.
[0039] The inventive device 1 shown merely by way of non-limiting example in FIG. 2 comprises a selector unit 11 , an amplifier 12 , a signal analyzer 13 and a gain control unit 15 . Multiple audio sources 2 a, 2 b, . . . , 2 n are again coupled to the selector unit 11 while a loudspeaker unit 4 , which may comprise one or more loudspeakers and/or other acoustic transducers, is coupled to the amplifier 12 . It is to mention all or some of the audio sources may be part of the device 1 .
[0040] In contrast to the Prior Art device 1 ′ of FIG. 1 , the level signal S L is in the device 1 of FIG. 2 derived from the output signal S O instead of the input signal S I . As can be seen in FIG. 2 , the signal analyzer 13 is coupled to the output of the amplifier 12 so as to produce a level signal S L that is representative of the actual signal fed to the loudspeaker unit 4 . The gain signal S G is therefore related to the (average) level of the output signal S O , which is the driving signal of the loudspeaker unit 4 . As a result, there is a much more direct relationship between the sound produced by the loudspeaker unit and the gain signal S G , and consequently a better gain adjustment is achieved.
[0041] It is noted that the signal analyzer 13 typically performs an averaging of the output signal S O so as to produce a level signal S G that is not unduly influenced by temporary peaks or troughs in the signal level.
[0042] The embodiment of FIG. 3 is largely identical to the embodiment of FIG. 2 , with the exception of a level setting unit 14 that is inserted between the signal analyzer 13 and the gain control unit 15 . The level setting unit 14 allows the user to set the (average) gain level, on the basis of a gain setting signal V. The gain setting signal V may be derived from a variable resistor or a (remote) control unit.
[0043] In the embodiment of FIG. 5 , the signal analyzer is not coupled to the output of the amplifier 12 but to the loudspeaker unit 4 itself. In this embodiment, at least one transducer (not shown) is mounted in the loudspeaker unit 4 , the transducer being coupled to the signal analyzer 13 . A suitable transducer may be an accelerometer that measures the acceleration of the cone of a loudspeaker, but other transducers may also be utilized, such as a conductive section of the suspension of the loudspeaker. A measuring current may be passed through such a conductive section as to generate a measuring voltage which is substantially proportional to the excursion of the loudspeaker.
[0044] It will be understood that the gain setting unit 14 can be deleted from the embodiment of FIG. 5 without departing from the scope of the present invention. Similarly, additional components, such as a power amplifier and/or filters, may be used in many embodiments of the device of the present invention.
[0045] In the device of the present invention, the signal analyzer 13 may be constituted by a signal averager known per se, or any other suitable circuit. The analyzer 13 , level setting unit 14 and gain control unit 15 could also be implemented in software by means of a digital signal processing unit (e.g. a digital signal processor, DSP), or in hardware by means of a (field) programmable gate array device (FPGA). It will be understood by those skilled in the art that a digital embodiment would require suitable D/A (digital/analog) and/or A/D (analog/digital) converters.
[0046] Accordingly, the gain control unit 15 may be constituted by an operational amplifier or a digital signal processing unit which converts the level signal S L into a suitable gain control signal S G .
[0047] Although the gain of amplifier 12 will typically be greater than one, in all embodiments it is possible for the gain of amplifier 12 to be smaller than 1, thus effectively causing an attenuation. A power amplifier (not shown) may be arranged between the controlled amplifier 12 and the loudspeaker unit(s) 4 . Those skilled in the art will be able to modify the device 1 of FIGS. 2-4 so that it can be used for multi-channel audio, for example stereo or “5.1”.
[0048] In the embodiments shown in FIGS. 1-3 and 5 , the same gain was applied to all frequencies. In further advantageous embodiments, filters may be provided to select frequency bands and to control the gain per frequency band. Low frequencies, for example, may require less gain adjustment (and a different adjustment) than higher frequencies. By providing multiple control loops for multiple frequency bands, an improved audio level control may be achieved.
[0049] This is schematically shown in FIG. 4 , where two filters 17 and 18 each receive the output signal S O . The filtered output signals are both fed to the signal analyzer 13 . Instead of a single signal analyzer 13 , multiple signal analyzers could be provided, each associated with a frequency range. It is also possible to provide separate level setting units 14 and/or gain control units 15 for each frequency range, thus obtaining an even more accurate gain control.
[0050] In the example shown in FIG. 4 , the first filter 17 is a low-pass filter while the second filter 18 is a high-pass filter. This, however, is not essential and filters having substantially any pass-band may be used without departing from the scope of the present invention. Instead of two filters, three or more filters could be provided.
[0051] The embodiment of FIG. 4 has the advantage that a frequency-dependent gain control is achieved, thus allowing, for example, a greater gain adjustment for higher frequencies than for lower frequencies.
[0052] Of course the embodiments of FIGS. 4 and 5 can be combined to provide an embodiment in which at least one loudspeaker transducer is used to derive a frequency dependent gain control signal.
[0053] The present invention is based upon the insight that the actual loudspeaker signal is a better measure for gain control than the input signal.
[0054] It is noted that any terms used in this document should not be construed so as to limit the scope of the present invention. In particular, the words “comprise(s)” and “comprising” are not meant to exclude any elements not specifically stated. Single (circuit) elements may be substituted with multiple (circuit) elements or with their equivalents.
[0055] It will be understood by those skilled in the art that the present invention is not limited to the embodiments illustrated above and that many modifications and additions may be made without departing from the scope of the invention as defined in the appending claims.
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An audio signal processing device ( 1 ) is arranged for providing a level controlled output signal (S o ) in response to a selected input signal (S i ). The device comprises a selection unit ( 11 ) for selecting an input signal (S i ) from a plurality of input signals, an amplification unit ( 12 ) for amplifying the selected input signal so as to produce the output signal (S o ), and a gain control unit ( 15 ) for controlling the gain of the amplification unit ( 12 ) in response to a level signal (S l ) indicative of the audio signal level. The device is arranged for deriving the level signal (S l ) from the output signal (S o ) instead of the input signal (S i ) of the amplifier ( 12 ). As a result, any signal distortions introduced by the amplifier ( 12 ) have no effect on the gain control and a greater precision is achieved.
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BACKGROUND OF THE INVENTION
[0001] This application is a divisional application of and claims the benefit of U.S. patent application Ser. No. 10/323,012 filed on Dec. 18, 2002, and claims the benefit of U.S. Provisional Patent Application Ser. No. 60/345,063 filed Dec. 21, 2001, the complete disclosures of which are hereby expressly incorporated by reference.
[0002] 1. Field of the Invention
[0003] This invention relates to methods and an apparatus for producing decabromodiphenyl alkanes. More specifically, the field of the invention is that of producing decabromodiphenyl ethane.
[0004] 2. Description of the Related Art
[0005] Halogenated aromatic compounds are often employed as flame retardant agents. Flame retardants are substances applied to or incorporated into a combustible material to reduce or eliminate its tendency to ignite when exposed to a low-energy flame, e.g., a match or a cigarette. The incorporation of flame retardants into the manufacture of electronic equipment, upholstered furniture, construction materials, textiles and numerous other products is well known.
[0006] Brominated aromatic compounds are often utilized as flame retardant agents in polymer compositions such as the outer housing of computers, television sets, and other electronic appliances. One group of halogenated flame retardants are decabromodiphenyl alkanes. The manufacture of decabromodiphenyl alkanes is known. Conventionally, decabromodiphenyl alkanes are prepared by reacting a diphenyl alkane with bromine in the presence of a bromination catalyst, such as AlCl 3 or FeCl 3 .
[0007] For example, U.S. Pat. No. 5,030,778 to Ransford discloses a process for producing decabromodiphenyl alkanes in which bromine and a bromination catalyst are charged to a reaction vessel. Liquid diphenyl alkane is fed by a dip tube into the reaction vessel at a point which is beneath the level of the charged liquid bromine and catalyst. The stated advantages of this sub-surface addition method are that (1) a product with a high average bromine number is obtained faster when the diphenyl alkane is fed below the surface of the charged liquid bromine and catalyst; and (2) splattering of the reaction mass associated with the addition of the diphenyl alkane into the vessel is reduced.
[0008] One disadvantage to adding the diphenyl alkane to the vessel at a location below the surface of the charged bromine and catalyst is that the dip tubes used for adding the diphenyl alkane to the vessel are prone to plugging. It is believed that the sub-surface addition dip tubes become plugged when a small amount of diphenyl alkane remains at the tip of the tube and reacts in place, thereby forming insoluble, high melting point material. It is believed that this is more likely to occur at the end of the addition or if the diphenyl alkane addition is interrupted. This susceptibility to plugging prevents the manufacturer from being able to stop and start the diphenyl alkane addition, which is sometimes desirable for controlling the evolution HBr gas.
[0009] It is also believed that the agitation of the reaction mass may create a vortex within the tip of the sub-surface addition dip tube. This vortex may pull solids from the reaction mass into the tube, thereby creating a blockage. Additionally, because some diphenyl alkanes, such diphenylethane (“DPE”), are solids at room temperature and are fed to the reaction vessel as liquids, they may begin to crystallize in an unheated dip tube if the feed is interrupted for any reason. In the event that the sub-surface dip tube does become plugged, regardless of the reason, the diphenyl alkane feed must be stopped and the tube must be pulled out of the reactor in order to remove the blockage. It is desirable to avoid the need to remove the dip tube, as the vapor space of the reaction vessel is filled with toxic and corrosive bromine vapors which may escape during removal.
[0010] The above-surface diphenyl alkane addition technique of the present invention reduces dip tube plugging, thereby providing a more efficient method of adding diphenyl alkane to a reactor charged with bromine and catalyst.
SUMMARY OF THE INVENTION
[0011] The present invention is directed to a method and apparatus for producing decabromodiphenyl alkanes, particularly decabromodiphenylethane. In one embodiment of the invention, a diphenyl alkane, such as diphenylethane, is fed into a reaction vessel containing liquid bromine and a bromination catalyst via a dip tube located above the surface level of the charged liquid bromine and catalyst. The DPE may be fed to the reaction vessel under pressure and at a relatively high velocity from a point above the level of the bromine and catalyst in the reaction vessel.
[0012] Another method for preparing decabromodiphenyl alkanes according to the present invention includes the steps of charging a reaction vessel with bromine and a bromination catalyst, providing a dip tube apparatus having a first end and a second end located in the reaction vessel above the surface level of the bromine and the bromination catalyst, introducing diphenyl alkane through the dip tube apparatus such that the diphenyl alkane flows from the first end, to the second end and enters the reaction vessel at a point above the surface level of the bromine and bromination catalyst in the reaction vessel, reacting the diphenyl alkane with the bromine and the bromination catalyst thereby forming a reaction mass, and recirculating the reaction mass through the dip tube apparatus so as to form a curtain of recirculated reaction mass around the diphenyl alkane being introduced into the reaction vessel. An excess of bromine above that needed to brominate the diphenyl alkane to the desired degree is utilized.
[0013] In accordance with the present invention, the crude decabromodiphenyl alkane, such as decabromodiphenylethane, obtained by the aforementioned process is isolated and purified. Any one of numerous known isolation and purification methods may be utilized. For example, the solid may be isolated through direct removal from the slurry by filtration or centrifugation. The solid decabromodiphenyl alkane could as be removed by combining the reaction mass with water and striping the bromine through the use of heat and/or a vacuum. In one method of the invention, the crude decabromodiphenyl alkane is first made into a water slurry, and is transferred to a another reactor. The slurry is washed with an alkaline solution and the solid decabromodiphenyl alkane is separated and washed with water. The solid decabromodiphenyl alkane is then in the form of a filter cake. The filter cake may be treated in any one of a number of known ways. For example, the cake may first be dried and then fractured and/or heat treated in a number of ways. The wet decabromodiphenyl alkane product may also be treated without first drying, as disclosed in U.S. Pat. No. 4,659,021 to Bark, et al. In one embodiment of the present invention, the filter cake is dried and then ground twice in an air mill using air which is heated to an inlet temperature of approximately 260° C. The ground decabromodiphenyl alkane is then heat-treated at approximately 240° C. for three to four hours in order to release any free bromine which may be present in the product. The release of free bromine improves the purity and the color of the end product. Other known isolation and purification methods may also be utilized, such as those disclosed in U.S. Pat. No. 4,327,227 to Ayres, et al. and U.S. Pat. No. 5,030,778 to Ransford.
[0014] An apparatus for preparing decabromodiphenyl alkanes according to the present invention includes a dip tube apparatus disposed above the surface level of the charged liquid bromine in the reaction vessel and includes an inner tube and an outer tube. The inner tube has a first end and a second end. The first end is adapted to receive a flow of diphenyl alkane. The second end of the inner tube is adapted to receive a plug. The plug includes a hollow portion and an opening. When the inner tube and the plug are engaged, the plug and the inner tube are in fluid communication with one another. The diphenyl alkane flows through the inner tube, through an opening in the plug, and into the reaction vessel at a location which is above the surface level of the charged liquid bromine and the bromination catalyst. Plugs having a variety of opening sizes and configurations may be chosen in order to achieve the desired flow rate diphenyl alkane. Alternatively, the plug can be eliminated and the opening through which the diphenyl alkane flows can be formed in one end of the inner tube.
[0015] The outer tube of the dip tube apparatus extends around the inner tube. The reaction mass within the reaction vessel is pumped out of the reaction vessel, through the outer tube, and then back into the reaction vessel. The outer tube is spaced from the inner tube, such that the recirculated reaction mass re-enters the reaction vessel in the form of a curtain surrounding the diphenyl alkane stream. The curtain of recirculated reaction mass does not come into contact with the stream of diphenyl alkane being simultaneously added to the reaction vessel through the inner tube.
[0016] Other features of the present invention will be apparent to those of skill in the art from the following detailed description and the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] FIG. 1 is a sectional view illustrating the dip tube apparatus according to one embodiment of the present invention disposed in a reaction vessel;
[0018] FIG. 2 is a perspective views of a plug that is a component of the dip tube apparatus of FIG. 1 ; and
[0019] FIG. 3 is an end view of the dip tube apparatus taken along line 3 - 3 of FIG. 1 .
[0020] Corresponding reference characters indicate corresponding parts throughout the several views. The examples set out herein illustrate a preferred embodiment of the invention, in one form, and are not to be construed as limiting the scope of the invention is any manner.
DETAILED DESCRIPTION OF THE INVENTION
[0021] With reference to FIG. 1 , dip tube apparatus 10 is disposed in reaction vessel 11 . Reaction vessel 11 may be any size desired, but for commercial applications, a reactor of at least 3,000 gallons is typically preferred.
[0022] Dip tube apparatus 10 includes inner tube 12 and outer tube 14 . Inner tube 12 may be manufactured out of Teflon or any other suitable material having similar properties, and outer tube 14 may be manufactured of Kynar or any other suitable material having similar properties. Inner tube 12 includes first end 13 a and second end 13 b. First end 13 a is adapted for receiving a flow of a diphenyl alkane, such as, for example, DPE, as indicated by arrow A. Second end 13 b is adapted for receiving plug 18 , as described below.
[0023] Outer tube 14 extends along and surrounds inner tube 12 as shown. Outer tube 14 includes first end 15 a and second end 15 b. FIG. 3 illustrates an end view of dip tube apparatus 10 taken along line 3 - 3 of FIG. 1 . As shown in FIG. 3 , spacers 25 serve to separate inner tube 12 from outer tube 14 . Spacers 25 are may be manufactured from a 15% glass Teflon material or any other suitable material.
[0024] With reference to FIG. 2 , plug 18 , in the embodiment shown, includes a hollow portion 20 and a generally disc-shaped portion 24 . Disc-shaped portion 24 includes a first surface 26 a having an opening 26 b therein. Note that in the embodiment shown, the side of disc-shaped portion 24 is flared. Hollow portion 20 and opening 26 b are in fluid communication such that DPE flowing through hollow portion 20 will exit plug 18 through opening 26 b. The size and shape of opening 26 b may be varied depending upon the desired flow rate of DPE into reaction vessel 11 . Typically, opening 26 b will have a diameter of between about 0.0625″ and about 0.0937″. In the embodiment shown, second end 13 b of inner tube 12 includes a threaded portion 16 which is adapted to receive corresponding threads 16 of plug 18 such that plug 18 is secured within second end 13 b of inner tube 12 . This arrangement allows the size and shape of opening 26 b to be changed by changing plug 18 . Other mechanisms for securing plug 18 to inner tube 12 may also be utilized. When plug 18 is secured within second end 13 b of inner tube 12 , inner tube 12 and plug 18 are in fluid communication such DPE flowing through inner tube 12 will flow into hollow portion 20 and out opening 26 b. Plug 18 may be manufactured from Teflon or any other suitable material.
[0025] Note that plug 18 can be completely eliminated by constructing second end 13 b of inner tube 12 with an appropriately sized and shaped opening for introducing DPE into reaction vessel 11 . Of course, this would mean that the entire inner tube 12 would have to be changed to change the size and shape of the opening.
[0026] In the embodiment shown in FIG. 1 , dip tube apparatus 10 is disposed in reaction vessel 11 such that second end 15 b of outer tube 14 is located at the same level as second end 13 of inner tube 12 . Both second end 15 b of outer tube 14 and second end 13 b of inner tube 12 are located a distance D above surface 26 a of plug 18 . In the embodiment shown, distance D corresponds to the thickness of portion 24 of plug 18 . In one embodiment of the invention, distance D is about 0.5 inches. Note also that it is not necessary that surface 26 a of plug 18 be located below second end 15 b of outer tube 14 . That is, inner tube 12 and plug 18 may be positioned such that surface 26 a is recessed within outer tube 14 and is located further from level L than is second end 15 b of outer tube 14 . As further shown in FIG. 1 , surface 26 a of plug 18 is located a distance X above surface level L of the charged bromine and catalyst. In one embodiment of the invention, distance X is about 4 inches. Typically, distance X will be between about 1 inch and about 12 inches.
[0027] If an inner tube 12 is utilized without a plug 18 , as described above, inner tube 12 and outer tube 14 would be positioned such that second end 13 b of inner tube 12 is located a distance D below second end 15 b of outer tube 14 . Similarly, inner tube 12 would be positioned such that second end 13 b is located a distance X above level L.
[0028] In use, DPE is fed, under pressure, through inner tube 12 and emitted as a stream 36 via opening 26 a into reaction vessel 11 . The DPE preferably has a purity level of about 99.7% or greater, however, DPE of different purity levels can be used depending on the desired characteristics of the final product. The pressure at which the DPE is fed is preferably at least about 20 psig and preferably between about 20 psig and about 60 psig. The DPE stream 36 preferably has a velocity within the range of about 9 meters per second to about 25 meters per second. In one embodiment of the invention, the DPE is fed at about 17.5 meters per second under a pressure of about 30 psig. An agitator (not shown) operating at approximately 47-88 rpm and disposed within reaction vessel 11 mixes the DPE and the bromine reaction medium, thereby facilitating the reaction.
[0029] As the DPE is added to reaction vessel 11 , the reaction mass 38 is recirculated to first end 15 a of outer tube 14 and allowed to flow through outer tube 14 (shown in FIG. 1 by arrows B), along inner tube 12 and back into reaction vessel 11 . Preferably, reaction mass 38 is recirculated at a rate of between about 45 gallons per minute to 250 gallons per minute. In this manner, a curtain 34 of reaction mass 38 is formed around DPE stream 36 . The distance Y between curtain 34 and DPE stream 26 is preferably at least about 0.5 inches. In one embodiment of the invention, distance Y is about 0.867″. Note that DPE stream 26 does not come into contact with curtain 34 . The flared sides of portion 24 of plug 18 assists in keeping the DPE stream 26 and the curtain 34 separated. Note that any portion of reaction mass 38 that splashes as a result of the DPE feed will be contained by curtain 34 and carried back into the remainder of the reaction mass 38 .
[0030] Decabromodiphenylethane may be obtained according to the present invention by reacting DPE in the presence of an excess of bromine and a bromination catalyst. The molar ratio of bromine to DPE is between about 18:1 and about 50:1. Preferably, the ratio is between about 18:1 to about 39:1. Appropriate bromination catalysts include aluminum halides, such as aluminum chloride and aluminum bromide, as well as iron powder. Other catalysts may also be used.
[0031] During the DPE addition, the temperature of the reaction mass is preferably in the range of about 50° C. to about 60° C. Preferably the temperature of the reaction mass is maintained at 55° C. until the DPE feed is complete. The temperature is then increased to approximately 60° C. and held constant for the duration of the reaction time. The reaction time will vary depending upon the amount of DPE being added, and upon the rate at which the DPE is added. For commercial production, reaction times will likely be between three and six hours.
[0032] As noted above, isolation and purification of the resulting decabromodiphenylethane may be carried out in a variety of ways. In one method, the decabromodiphenylethane slurry is placed in a pressurized vessel charged with water which has been heated to approximately 70° C. Once the slurry addition is complete, the temperature within the vessel is increased to approximately 100° C. to facilitate the removal of any remaining free bromine. The water slurry is transferred to a tank which is charged with a solution which is 25% alkaline. The resulting slurry is then fed to a centrifuge where the solid decabromodiphenylethane product is separated and washed with water. The solid is in the form of a filter cake. The filter cake of decabromodiphenylethane is then dried and ground twice in an air mill using air heated to an inlet temperature of approximately 260° C. The resulting material is heat-treated at approximately 240° C. for 3-4 hours. The final product preferably has a yellowness index of below about 10, and more preferably below about 9.
EXAMPLE
[0033] A 3000 gallon glass lined Pfaudler reactor was equipped with a vertical H-type baffle, condenser system, 41″ Pfaudler Cryo-lock reverse curve agitator, temperature sensor, and the dip tube apparatus described above. 21,210 kg (132,278.41 moles) of liquid bromine and 63.5 kg (476.26 moles) of aluminum chloride were charged to the reaction vessel. The agitator was then turned on and ranged in speed from 47 to 88 rpm. The reactor was heated to 55° C. 618 kg (3395.6 moles) of DPE was then charged through the dip tube, as described above, at a rate of 4-8.5 lbs./min. The DPE addition ranged from 3.5 to 5 hours. Once the feed was completed, the reaction temperature was increase to 60° C. and held at that temperature for thirty minutes.
[0034] A 4000 gallon glass lined Pfaudler reactor was equipped with a vertical H-type baffle, condenser system, 41 ″ Pfaudler Cryo-lock reverse curve agitator, and temperature sensor. The vessel was charged with 1850 gallons of water. The water was then heated to 70° C. The bromine slurry from the reactor was fed into the vessel over a 2.5 to 3 hour period, while maintaining 5 to 5.5 lbs. of pressure within the vessel. Once the slurry addition was complete, the temperature within the vessel was raised to 100° C. to complete the bromine removal.
[0035] The water slurry was transferred to a 5000 gallon tank equipped with an agitator. The tank was charged with 475 gallons of a 25% caustic (alkaline) solution. The resulting slurry was then fed to a centrifuge where the solid was separated and washed with water. The filter cake was then dried. The resulting material was then ground twice by passing it through a Fluid Energy Aljet air mill using air heated to 260° C. The product was then heat treated in a Wyssmont drier at 240° C. for 3 to 4 hours.
[0036] The conditions and results of the reactions run are illustrated in the following table. Note that some of the reactions were run without utilizing the curtain of recirculated reaction mass. In these runs, the DPE was simply fed under pressure to the reaction vessel at a point above the level of the bromine and bromination catalyst.
Bromine Bromine Bromine Bromine DPE DPE Agitation Hole Weight Weight temp temp DPE Weight Linear Rate Diameter (rcyl) (vir) initial final DPE Rate total Feed Rate Wet cake Run # RPM (inches) lbs. lbs. ° C. ° C. Assay % lbs/min lbs. m/sec GC Assay % Above Surface 20 88 0.0625 23360 23360 56.7 54.2 98.7 4.62 1363 17.7 99.07 21 88 0.0937 47510 0 53.3 53.3 98.7 5.4 1363 9.2 98.93 22 88 0.07813 37360 9340 58.3 51.7 98.7 4.4 767 10.8 98.82 23 88 0.07813 46700 0 57.8 53.3 98.7 10 640 24.5 98.7 24 88 0.07813 46710 0 57.2 57.2 98.7 4.3 741 10.5 25 0.07813 46710 0 56.7 98.7 463 0.0 Above surface curtain 26 75 0.07813 46710 0 56.7 55.6 98.7 5 1363 12.2 99.102 27 75 0.07813 46720 0 55.0 56.1 98.7 5.05 1363 12.4 99.05 28 75 0.07813 43280 0 56.7 58.3 98.7 4.99 1263 12.2 99.24 29 46 0.07813 43340 0 59.2 57.3 98.7 5.3 1263 13.0 99.14 30 46 0.07813 43321 0 98.7 1263 0.0 98.83 31 47 0.07813 46710 0 98.7 1338 0.0 99.18 32 47 0.07813 45110 0 59.2 56.4 98.7 5.4 1315 13.2 98.98 33 47 0.07813 45100 0 56.1 56.7 98.7 4.7 326 11.5 98.8 34 47 0.07813 45100 0 56.1 57.8 98.7 5.89 1315 14.4 99.01 35 47 0.0625 45120 0 55.9 56.6 98.7 5 1315 19.1 99.08 36 47 0.07813 46660 0 58.9 57.8 98.7 5.37 1315 13.1 99.2 37 47 0.07813 46730 0 56.5 98.7 1773 0.0 98.6 38 47 0.07813 98.7 0.0 99.27
[0037] While this invention has been described with reference to specific embodiments, the present invention may be further modified within the spirit and scope of the disclosure. This application covers such departures from the present disclosure as come within the known or customary practice in the art to which the invention pertains and which fall within the limits of the appended claims.
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A method of producing decabromodiphenyl alkanes includes the steps of charging a reaction vessel with bromine and a bromination catalyst and introducing a diphenyl alkane into the vessel at a location above the level of the charge bromine and catalyst. A dip tube apparatus for introducing the diphenyl alkane includes an inner tube and an outer tube, each of which are disposed above the surface of the bromine reaction vessel. The inner tube is fitted with a plug having an opening. Diphenyl alkane flows through the inner tube, out the opening in the plug, and into the reactor. The outer tube is disposed around and along the inner tube. Reaction mass from the vessel is recirculated from the vessel, through the outer tube and back to the vessel so as to form a curtain of reaction mass around the stream of diphenyl alkane being simultaneously fed into the reaction vessel.
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RELATED APPLICATIONS
This application is a continuation of U.S. patent application Ser. No. 09/840,624 filed on Apr. 23, 2001, which issued as U.S. Pat. No. 6,863,801 on Mar. 8, 2005, which is a continuation of U.S. application Ser. No. 09/709,968, filed Nov. 10, 2000, which issued as U.S. Pat. No. 6,521,110 on Feb. 18, 2003, which is a continuation of U.S. application Ser. No. 09/314,251, filed May 18, 1999, which issued as U.S. Pat. No. 6,174,420 on Jan. 16, 2001, which is a continuation-in-part of U.S. application Ser. No. 09/068,828, filed on Mar. 15, 1999, which issued as U.S. Pat. No. 6,179,979 on Jan. 30, 2001, and is also a continuation-in-part of U.S. application Ser. No. 08/852,804, filed on May 7, 1997, which issued as U.S. Pat. No. 5,942,102 on Aug. 24, 1999, the contents of which are incorporated herein by reference in their entirety.
FIELD OF THE INVENTION
This invention relates to an electrochemical cell for determining the concentration of an analyte in a carrier.
BACKGROUND OF THE INVENTION
The invention herein described is an improvement in or modification of the invention described in our co-pending U.S. application Ser. No. 08/981,385, entitled ELECTROCHEMICAL CELL, filed on Dec. 18, 1997, the contents of which are incorporated herein by reference in its entirety.
The invention will herein be described with particular reference to a biosensor adapted to measure the concentration of glucose in blood, but it will be understood not to be limited to that particular use and is applicable to other analytic determinations.
It is known to measure the concentration of a component to be analysed in an aqueous liquid sample by placing the sample into a reaction zone in an electrochemical cell comprising two electrodes having an impedance which renders them suitable for amperometric measurement. The component to be analysed is allowed to react directly or indirectly with a redox reagent whereby to form an oxidisable (or reducible) substance in an amount corresponding to the concentration of the component to be analysed. The quantity of the oxidisable (or reducible) substance present is then estimated electrochemically. Generally this method requires sufficient separation of the electrodes so that electrolysis products at one electrode cannot reach the other electrode and interfere with the processes at the other electrode during the period of measurement.
In our co-pending application we described a novel method for determining the concentration of the reduced (or oxidised) form of a redox species in an electrochemical cell of the kind comprising a working electrode and a counter (or counter/reference) electrode spaced from the working electrode by a predetermined distance. The method involves applying an electric potential difference between the electrodes and selecting the potential of the working electrode such that the rate of electro-oxidation of the reduced form of the species (or of electro-reduction of the oxidised form) is diffusion controlled. The spacing between the working electrode and the counter electrode is selected so that reaction products from the counter electrode arrive at the working electrode. By determining the current as a function of time after application of the potential and prior to achievement of a steady state current and then estimating the magnitude of the steady state current, the method previously described allows the diffusion coefficient and/or the concentration of the reduced (or oxidised) form of the species to be estimated.
Our co-pending application exemplifies this method with reference to use of a “thin layer electrochemical cell” employing a GOD/Ferrocyanide system. As herein used, the term “thin layer electrochemical cell” refers to a cell having closely spaced electrodes such that reaction product from the counter electrode arrives at the working electrode. In practice, the separation of electrodes in such a cell for measuring glucose in blood will be less than 500 microns, and preferably less than 200 microns.
The chemistry used in the exemplified electrochemical cell is as follows:
where GOD is the enzyme glucose oxidase, and GOD* is the ‘activated’ enzyme. Ferricyanide ([Fe(CN) 6 ] 3− ) is the ‘mediator’ which returns the GOD* to its catalytic state. GOD, an enzyme catalyst, is not consumed during the reaction so long as excess mediator is present. Ferrocyanide ([Fe(CN) 6 ] 4− ) is the product of the total reaction. Ideally there is initially no ferrocyanide, although in practice there is often a small quantity. After reaction is complete the concentration of ferrocyanide (measured electrochemically) indicates the initial concentration of glucose. The total reaction is the sum of reactions 1 and 2:
“Glucose” refers specifically to β-D-glucose.
The prior art suffers from a number of disadvantages. Firstly, sample size required is greater than desirable. It would be generally preferable to be able to make measurements on samples of reduced volume since this in turn enables use of less invasive methods to obtain samples.
Secondly, it would be generally desirable to improve the accuracy of measurement and to eliminate or reduce variations due, for example, to cell asymmetry or other factors introduced during mass production of microcells. Likewise, it would be desirable to reduce electrode “edge” effects.
Thirdly, since the cells are disposable after use, it is desirable that they be capable of mass production at relatively low cost.
SUMMARY OF THE INVENTION
In a first embodiment of the present invention, a biosensor for use in determining a concentration of a component in an aqueous liquid sample is provided, the biosensor including: (a) an electrochemical cell, the electrochemical cell including a first electrically resistive substrate having a first thin layer of a first electrically conductive material on a first face, a second electrically resistive substrate having a second thin layer of a second electrically conductive material on a second face, the substrates being disposed with the first electrically conductive material facing the second electrically conductive material and being separated by a sheet including an aperture, the wall of which aperture cooperates with the electrically conductive materials to define a cell wall, and wherein the aperture defines a working electrode area in the cell, the cell further including a sample introduction aperture whereby the aqueous liquid sample may be introduced into the cell; and (b) a measuring circuit.
In one aspect of the first embodiment, the electrochemical cell further includes a socket region having a first contact area in electrical communication with the first thin layer of the first electrically conductive material and a second contact area in electrical communication with the second thin layer of the second electrically conductive material, whereby the electrochemical cell may be electrically connected with the measuring circuit.
In another aspect of the first embodiment, the measuring circuit includes a tongue plug.
In a further aspect of the first embodiment, at least one of the first electrically conductive material and the second electrically conductive material includes a metal. The metal may further include a sputter coated metal.
In still other aspects of the first embodiment, the aqueous liquid sample includes blood, and the component includes glucose.
In yet another aspect of the first embodiment, the measuring circuit includes an automated instrument for detecting an electrical signal from the electrochemical cell and relating the electrical signal to the concentration of the component in the aqueous liquid sample.
In a further aspect of the first embodiment, the electrochemical cell includes a substantially flat strip having a thickness, the strip having at least two lateral edges, and wherein the sample introduction aperture includes a notch through the entire thickness of the strip in at least one of the lateral edges thereof.
In a second embodiment of the present invention, a biosensor for use in determining a concentration of a component in an aqueous liquid sample is provided, the biosensor including: (a) a thin layer electrochemical cell, the cell including: (i) an electrically resistive sheet including an aperture wherein the aperture defines a working electrode area in the cell; (ii) a first electrode layer covering the aperture on a first side of the sheet; (iii) a second electrode layer covering the aperture on a second side of the sheet; and (iv) a passage for admission into the aperture of the aqueous liquid sample; and (b) a measuring circuit.
In one aspect of the second embodiment, the electrochemical cell further includes a socket region having a first contact area in electrical communication with the first electrode layer and a second contact area in electrical communication with the second electrode layer, whereby the electrochemical cell may be electrically connected with the measuring circuit.
In another aspect of the second embodiment, the measuring circuit includes a tongue plug.
In still other aspects of the second embodiment, the aqueous liquid sample includes blood, and the component includes glucose.
In a further aspect of the second embodiment, the measuring circuit includes an automated instrument for detecting an electrical signal from the electrochemical cell and relating the electrical signal to the concentration of the component in the aqueous liquid sample.
In yet another aspect of the second embodiment, the cell includes a substantially flat strip having a thickness, the strip having at least two lateral edges, and wherein the passage for admission into the aperture includes a notch through the entire thickness of the strip in at least one of the lateral edges thereof.
In a third embodiment of the present invention, an apparatus for determining a concentration of a reduced form or an oxidized form of a redox species in a liquid sample is provided, the apparatus including: (a) a hollow electrochemical cell having a working electrode and a counter or counter/reference electrode wherein the working electrode is spaced from the counter or counter/reference electrode by less than 500 μm; (b) means for applying an electric potential difference between the electrodes; and (c) means for electrochemically determining the concentration of the reduced form or the oxidized form of the redox species in the liquid sample.
In one aspect of the third embodiment, means for electrochemically determining the concentration of the reduced form or the oxidized form of the redox species includes: (i) means for determining a change in current with time after application of the electric potential difference and prior to achievement of a steady state current; (ii) means for estimating a magnitude of the steady state current; and (iii) means for obtaining from the change in current with time and the magnitude of the steady state current, a value indicative of the concentration of the reduced form or the oxidized form of the redox species.
In another aspect of the third embodiment, the cell further includes a socket region having a first contact area in electrical communication with the working electrode and a second contact area in electrical communication with the counter or counter/reference electrode, whereby the cell may be electrically connected with at least one of the means for applying an electric potential difference between the electrodes and the means for electrochemically-determining the concentration of the reduced form or the oxidized form of the redox species in the liquid sample.
In a further aspect of the third embodiment, at least one of the means for applying an electric potential difference between the electrodes and the means for electrochemically determining the concentration of the reduced form or the oxidized form of the redox species in the liquid sample includes a tongue plug.
In yet another aspect of the third embodiment, at least one of the means for applying an electric potential difference between the electrodes and the means for electrochemically determining the concentration of the reduced form or the oxidized form of the redox species in the liquid sample includes an automated instrument for detecting an electrical signal from the electrochemical cell and relating the electrical signal to the concentration of the reduced form or the oxidized form of the redox species in the liquid sample.
In a further aspect of the third embodiment, the cell includes a substantially flat strip having a thickness, the strip having at least two lateral edges, and wherein a notch extends through a wall of the electrochemical cell and through the entire thickness of the strip in at least one of the lateral edges thereof, whereby the liquid sample may be introduced into the cell.
In still other aspects of the third embodiment, the liquid sample includes blood, and the redox species includes glucose.
In a fourth embodiment of the present invention, a method for determining a concentration of a reduced form or an oxidized form of a redox species in a liquid sample is provided, the method including: (a) providing a hollow electrochemical cell having a working electrode and a counter or counter/reference electrode wherein the working electrode is spaced from the counter or counter/reference electrode by less than 500 μm; (b) applying an electric potential difference between the electrodes; and (c) electrochemically determining the concentration of the reduced form or the oxidized form of the redox species in the liquid sample.
In one aspect of the fourth embodiment, step (c) includes: (i) determining a change in current with time after application of the electric potential difference and prior to achievement of a steady state current; (ii) estimating a magnitude of the steady state current; and (iii) obtaining from the change in current with time and the magnitude of the steady state current, a value indicative of the concentration of the reduced form or the oxidized form of the redox species.
In another aspect of the fourth embodiment, the cell further includes a socket region having a first contact area in electrical communication with the working electrode and a second contact area in electrical communication with the counter or counter/reference electrode.
In a further aspect of the fourth embodiment, step (b) further includes the step of: providing an automated instrument for applying an electric potential difference between the electrodes.
In yet another aspect of the fourth embodiment, step (c) includes the steps of: (i) providing an automated instrument for detecting an electrical signal from the electrochemical cell; and (ii) relating the electrical signal to the concentration of the reduced form or the oxidized form of the redox species in the liquid sample.
In a further aspect of the fourth embodiment, the cell includes a substantially flat strip having a thickness, the strip having at least two lateral edges, and wherein a notch extends through a wall of the electrochemical cell and through the entire thickness of the strip in at least one of the lateral edges thereof, whereby the liquid sample may be introduced into the cell.
In still other aspects of the fourth embodiment, the liquid sample includes blood and the redox species includes glucose.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will now be particularly described by way of example only with reference to the accompanying schematic drawings wherein:
FIG. 1 shows the product of manufacturing step 2 in plan.
FIG. 2 shows the product of FIG. 1 in side elevation.
FIG. 3 shows the product of FIG. 1 in end elevation.
FIG. 4 shows the product of manufacturing step 3 in plan.
FIG. 5 shows the product of FIG. 4 in cross-section on line 5 - 5 of FIG. 4 .
FIG. 6 shows the product of manufacturing step 5 in plan.
FIG. 7 shows the product of FIG. 6 in side elevation.
FIG. 8 shows the product of FIG. 6 in end elevation.
FIG. 9 shows the product of manufacturing step 7 in plan.
FIG. 10 is a cross-section of FIG. 9 on line 10 - 10 .
FIG. 11 shows the product of FIG. 9 in end elevation.
FIG. 12 shows a cell according to the invention in plan.
FIG. 13 shows the call of FIG. 12 in side elevation.
FIG. 14 shows the cell of FIG. 12 in end elevation.
FIG. 15 shows a scrap portion of a second embodiment of the invention in enlarged section.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The construction of a thin layer electrochemical cell will now be described by way of example of the improved method of manufacture.
Step 1: A sheet 1 of Melinex® (a chemically inert, and electrically resistive Polyethylene Terephthalate [“PET”]) approximately 13 cm×30 cm and 100 micron thick was laid flat on a sheet of release paper 2 and coated using a Number 2 MYAR bar to a thickness of 12 microns wet (approximately 2-5 microns dry) with a water-based heat activated adhesive 3 (ICI Novacoat system using catalyst:adhesive). The water was then evaporated by means of a hot air dryer leaving a contact adhesive surface. The sheet was then turned over on a release paper and the reverse side was similarly coated with the same adhesive 4 , dried, and a protective release paper 5 applied to the exposed adhesive surface. The edges were trimmed to obtain a sheet uniformly coated on both sides with tacky contact adhesive protected by release paper.
Step 2: The sheet with protective release papers was cut into strips 7 , each about 18 mm×210 mm ( FIGS. 1-3 ).
Step 3: A strip 7 of adhesive-coated PET from step 2 with release paper 2 , 5 on respective sides, was placed in a die assembly (not shown) and clamped. The die assembly was adapted to punch the strip with a locating hole 10 at each end and with for example 37 circular holes 11 each of 3.4 mm diameter at 5 mm centres equi-spaced along a line between locating holes 10 . The area of each hole 11 is approximately 9 square mm.
Step 4: A sheet 12 of Mylar® PET approximately 21 cm square and 135 microns thick was placed in a sputter coating chamber for palladium coating 13 . The sputter coating took place under a vacuum of between 4 and 6 millibars and in an atmosphere of argon gas. Palladium was coated on the PET to a thickness of 100-1000 angstroms. There is thus formed a sheet 14 having a palladium sputter coating 13 .
Step 5: The palladium coated PET sheet 14 from Step 4 was then cut into strips 14 and 15 and a die was used to punch two location holes 16 in each strip, at one end ( FIGS. 6 , 7 and 8 ). Strips 14 and 15 differ only in dimension strips 14 being 25 mm×210 mm and strips 15 being 23 mm×210 mm.
Step 6: A spacer strip 7 prepared as in step 3 was then placed in a jig (not shown) having two locating pins (one corresponding to each locating hole 10 of strip 7 ) and the upper release paper 2 was removed. A strip 14 of palladium coated PET prepared as in step 5 was then laid over the adhesive layer, palladium surface downwards, using the jig pins to align the locating holes 16 with the underlying PET strip 7 . This combination was then passed through a laminator comprising a set of pinch rollers, one of which was adapted to heat the side bearing a palladium coated PET strip 14 . The roller on the opposite side of the strip 7 was cooled. By this means, only the adhesive between the palladium of strip 14 and PET strip 7 was activated.
Step 7: PET strip 7 was then turned over and located in the jig with the release coating uppermost. The release coating was peeled off and second palladium coated strip 15 was placed palladium side down on the exposed adhesive surface using the locating pins to align the strips. this assembly was now passed again through the laminator of step 6, this time with the hot roll adjacent the palladium coated Mylar® added in step 7 so as to activate the intervening adhesive ( FIGS. 9 , 10 and 11 ).
Step 8: The assembly from step 7 was returned to the die assembly and notches 17 punched in locations so as to extend between the circular holes 11 previously punched in the Melinex® PET and the strip edge 17 . Notches 16 extend so as to intercept the circumference of each circular cell. The strip was then guillotined to give 37 individual “sensor strips”, each strip being about 5 mm wide and each having one thin layer cavity cell ( FIGS. 12 , 13 and 14 ).
There is thus produced a cell as shown in FIG. 12 , 13 or 14 . The cell comprises a first electrode consisting of PET layer 12 , a palladium layer 13 , an adhesive layer 3 , a PET sheet 1 , a second adhesive layer 4 , a second electrode comprising palladium layer 13 , and a PET layer 12 . Sheet 1 defines a cylindrical cell 11 having a thickness in the cell axial direction corresponding to the thickness of the Melinex® PET sheet layer 1 together with the thickness of adhesive layers 3 and 4 . The cell has circular palladium end walls. Access to the cell is provided at the side edge of the cell where notches 16 intersect cell 11 .
In preferred embodiments of the invention, a sample to be analysed is introduced to the cell by capillary action. The sample is placed on contact with notch 16 and is spontaneously drawn by capillary action into the cell, displaced air from the cell venting from the opposite notch 16 . A surfactant may be included in the capillary space to assist in drawing in the sample.
The sensors are provided with connection means for example edge connectors whereby the sensors may be placed into a measuring circuit. In a preferred embodiment this is achieved by making spacer 1 shorter than palladium supporting sheets 14 , 15 and by making one sheet 15 of shorter length than the other 14 . This forms a socket region 20 having contact areas 21 , 22 electrically connected with the working and counter electrodes respectively. A simple tongue plug having corresponding engaging conduct surfaces can then be used for electrical connection. Connectors of other form may be devised.
Chemicals for use in the cell may be supported on the cell electrodes or walls, may be supported on an independent support contained within the cell or may be self-supporting.
In one embodiment, chemicals for use in the cell are printed onto the palladium surface of the electrode immediately after step 1 at which stage the freshly-deposited palladium is more hydrophilic. For example, a solution containing 0.2 molar potassium ferricyanide and 1% by weight of glucose oxidase dehydrogenase may be printed on to the palladium surface. Desirably, the chemicals are printed only in the areas which will form a wall of the cell and for preference the chemicals are printed on the surface by means of an ink jet printer. In this manner, the deposition of chemicals may be precisely controlled. If desired, chemicals which are desirably separated until required for use may be printed respectively on the first and second electrodes. For example, a GOD/ferrocyanide composition can be printed on one electrode and a buffer on the other. Although it is highly preferred to apply the chemicals to the electrodes prior to assembly into a cell, chemicals may also be introduced into the cell as a solution after step 6 or step 8 by pipette in the traditional manner and the solvent subsequently is removed by evaporation or drying. Chemicals need not be printed on the cell wall or the electrodes and may instead be impregnated into a gauze, membrane, non-woven fabric or the like contained within, or filling, the cavity (eg inserted in cell 11 prior to steps 6 or 7). In another embodiment the chemicals are formed into a porous mass which may be introduced into the cell as a pellet or granules. Alternatively, the chemicals maybe introduced as a gel.
In a second embodiment of the invention a laminate 21 is first made from a strip 14 as obtained in step 5 adhesively sandwiched between two strips 7 as obtained from step 3. Laminate 20 is substituted for sheet 1 in step 5 and assembled with electrodes as in steps 6 and 7.
There is thus obtained a cell as shown in FIG. 15 which differs from that of FIGS. 9 to 11 in that the cell has an annular electrode disposed between the first and second electrode. This electrode can for example be used as a reference electrode.
It will be understood that in mass production of the cell, the parts may be assembled as a laminate on a continuous line. For example, a continuous sheet 1 of PET could be first punched and then adhesive could be applied continuously by printing on the remaining sheet. Electrodes (pre-printed with chemical solution and dried) could be fed directly as a laminate onto the adhesive coated side. Adhesive could then be applied to the other side of the punched core sheet and then the electrode could be fed as a laminate onto the second side.
The adhesive could be applied as a hot melt interleaving film. Alternatively, the core sheet could first be adhesive coated and then punched.
By drying chemicals on each electrode prior to the gluing step the electrode surface is protected from contamination.
Although the cell has been described with reference to Mylar® and Melinex® PET, other chemically inert and electrically resistive materials may be utilised and other dimensions chosen. The materials used for spacer sheet 1 and-for supporting the reference and counter electrodes may be the same or may differ one from the other. Although the invention has been described with reference to palladium electrodes, other metals such as platinum, silver, gold, copper or the like may be used and silver may be reacted with a chloride to form a silver/silver chloride electrode or with other halides. The electrodes need not be of the same metal.
Although the use of heat activated adhesives has been described, the parts may be assembled by use of hot melt adhesives, fusible laminates and other methods.
The dimensions of the sensor may readily be varied according to requirements.
While it is greatly preferred that the electrodes cover the cell end openings, in other embodiments (not illustrated) the electrodes do not entirely cover the cell end openings. In that case it is desirable that the electrodes be in substantial overlying registration.
Preferred forms of the invention in which the electrodes cover the apertures of cell 11 have the advantages that the electrode area is precisely defined simply by punching hole 11 . Furthermore the electrodes so provided are parallel, overlying, of substantially the same area, and are substantially or entirely devoid of “edge” effects.
Although in the embodiments described each sensor has one cell cavity, sensors may be provided with two or more cavities. For example, a second cavity may be provided with a predetermined quantity of the analyte and may function as a reference cell.
As will be apparent to those skilled in the art from the teaching herein contained, a feature of one embodiment herein described may be combined with features of other embodiments herein described or with other embodiments described in our co-pending application. Although the sensor has been described with reference to palladium electrodes and a GOD/ferrocyanide chemistry, it will be apparent to those skilled in the art that other chemistries, and other materials of construction may be employed without departing from the principles herein taught.
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A biosensor for use in determining a concentration of a component in an aqueous liquid sample is provided including: an electrochemical cell having a first electrically resistive substrate having a thin layer of electrically conductive material, a second electrically resistive substrate having a thin layer of electrically conductive material, the substrates being disposed with the electrically conductive materials facing each other and being separated by a sheet including an aperture, the wall of which aperture defines a cell wall and a sample introduction aperture whereby the aqueous liquid sample may be introduced into the cell; and a measuring circuit.
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[0001] This application claims foreign priority benefits to Russian Patent Application No. 2007105188, filed on Feb. 13, 2007.
BACKGROUND
[0002] The statements in this section merely provide background information related to the present disclosure and may not constitute prior art.
[0003] This invention relates to the oil and gas industry, and in particular, to methods of oil and gas production, and can be applied to improve hydrocarbon recovery from a fractured subterranean reservoir due to fracture clean up.
[0004] The method of hydraulic fracturing of oil-bearing formation is an efficient method for stimulation of oil/gas production from a well. The goal of hydraulic fracturing is to pump a fluid under the pressure and rate sufficient for cracking the formation of the reservoir; this creates two fractures on opposite sides of wellbore traveling in opposite directions. These large-scale fractures are required as conduits for draining of hydrocarbon fluids into the borehole; these conduits have a higher fluid conductivity than the formation itself. To prevent the fracture closing when the fluid pumping has ended, propping agents are delivered with the fluid into the fractures. This proppant particulate is carried into the formation by fracturing fluid with a required certain density and viscosity. The preferable variant of fracturing fluid is viscous solution of viscoelastic polymers (guar or hydroxypropylcellulose).
[0005] The disadvantage of traditional fracturing methods is damaging the fracture with polymers and products of their decomposition. The residue of undamaged polymer stays in pores and considerably reduces fracture permeability. Research data shows that 45 to 75% of polymer remains in the fracture after an initial flowback period. To counteract this damage breakers are used to reduce gel viscosity and help remove concentrated polymer residues.
[0006] Some methods are known where low-molecular oxidizers (persulfates/peroxides of metals or ammonium) or organic peroxides are applied as gel breaker. These oxidizers and peroxides are effective up to 120° C. Sometimes these breakers are poorly compatible with the fracturing fluid or with resin coated proppant.
[0007] Some methods describe treatment of near-wellbore zone with hydrochloric acid pumped. This method is not adapted for removal of gel and filter cake damage from propped fractures.
[0008] Other methods a method for acid treatment of the near-wellbore zone. A mixture of polyvinylchloride and ammonium bifluoride is thermally decomposed (due to in-situ ignition or impact of formation temperature) and produces acid. The resulting mixture of acids is used to break apart the colloidal sediments of ferrous oxide. This method has not been adapted for removal of gel and filter cake damage from propped fractures because is only used to treat the near-wellbore zone.
[0009] Also known is a method of using acid to dissolve filter cake via a proppant with coating made of organic acid precursor (e.g., polylactic acid). This method may also be applied to aid with gel cleanup in gravel packs. The solid acid precursor can make up to 10% by weight of the total proppant mass. This invention is the most similar to the disclosed invention.
[0010] There are many known methods for production improvement after stimulation, by removal of concentrated gel and filter cake from a propped fracture. Removal of gel damage is achieved by using of polymers that are capable to produce organic or nonorganic acids under subterranean conditions.
DESCRIPTION OF THE INVENTION
[0011] At the outset, it should be noted that in the development of any such actual embodiment, numerous implementation-specific decisions must be made to achieve the developer's specific goals, such as compliance with system related and business related constraints, which will vary from one implementation to another. Moreover, it will be appreciated that such a development effort might be complex and time consuming but would nevertheless be a routine undertaking for those of ordinary skill in the art having the benefit of this disclosure.
[0012] The description and examples are presented solely for the purpose of illustrating the preferred embodiments of the invention and should not be construed as a limitation to the scope and applicability of the invention. While the compositions of the present invention are described herein as comprising certain materials, it should be understood that the composition could optionally comprise two or more chemically different materials. In addition, the composition can also comprise some components other than the ones already cited. In the summary of the invention and this detailed description, each numerical value should be read once as modified by the term “about” (unless already expressly so modified), and then read again as not so modified unless otherwise indicated in context. Also, in the summary of the invention and this detailed description, it should be understood that a concentration range listed or described as being useful, suitable, or the like, is intended that any and every concentration within the range, including the end points, is to be considered as having been stated. For example, “a range of from 1 to 10” is to be read as indicating each and every possible number along the continuum between about 1 and about 10. Thus, even if specific data points within the range, or even no data points within the range, are explicitly identified or refer to only a few specific, it is to be understood that inventors appreciate and understand that any and all data points within the range are to be considered to have been specified, and that inventors possession of the entire range and all points within the range.
[0013] The current invention describes a method for cleaning up a propped fracture by aiding the breakdown and removal of gel and gel residue from the fracture.
[0014] The technical benefit of this method is the improved fluid mobility into and inside the propped fracture and therefore enhancement of hydrocarbon production from the fracture.
[0015] The said technical result is achieved by the following means: the fracturing fluid carries proppant and particulate into the propped fracture; the said particulate under formation temperature releases a substance that reacts with the formation fluid and produces hydrochloric or etching acid. The preferable embodiment of this patent uses the particles of polyvinyl chloride or polyvinylden chloride or their copolymers comprising monomers of vinyl chloride or vinylden chloride, as well as their chlorinate analogs. Another variant is the use of material granulated and encapsulated into oil-dissolving coating; the said material is ammonium chloride or fluoride, ammonium difluoride, pyridine fluoride, and fluoride-bearing polymers, e.g., fluoride of polyvinylpyridine. The usual size of polymer particulate varies from 0.1 microns to 10 mm. The preferable amount of vinyl chloride is from 0.1% to 99.9% wt., and the content of chloride in the polymer is from 0.01% to 85% wt. The proportion of polymeric particulate as a percentage of proppant mass varies from 0.1% to 99.9%.
[0016] The method is based on using the substances which release hydrochloride under conditions of the formation temperature and in a water-oil medium; the produced hydrogen chloride destroys the polymer gel and dissolves the gel residue, typically filter cake. The disclosed method is based on using a new material for this technique (preferably, polyvinylchloride or co-polymers).
BRIEF DESCRIPTION OF THE DRAWING
[0017] FIG. 1 shows the diagram that illustrate a loss of polymer mass over the time of the thermal treatment.
[0018] These new substances enable efficient cleanup of polymers typically used in hydraulic fracturing fluid by removal of concentrated gel and gel residues, such as filter cake. The advantages of using a polymer based on vinylchloride monomer in contrast to other methods of destruction the polymer gel in propped fractures are the following:
[0019] 1. It is possible to reduce the concentration of costly gel breakers or abandon their use completely.
[0020] 2. The yield of hydrogen chloride from the said polymeric material is a long-term process (tens of days). A long time interval facilitates more uniform distribution of produced hydrochloric acid over the fracture volume and ensures more complete breaking of polymer gel.
[0021] 3. The particulate of polymer based on vinylchloride monomer releases hydrogen chloride at elevated temperatures (130 . . . 200° C.), where most commercially available peroxide breakers lose effectiveness (e.g., peroxide and persulfate of metal or ammonium).
[0022] 4. Unlike common peroxide breakers, the polymer particles with vinylchloride monomers do not react with resin coated proppant (RCP) or reduce the strength of the proppant packing that can lead to a reduction of fracture width.
[0023] 5. Unlike peroxide-type (persulfate-type) gel breakers, the polymer particles with vinylchloride monomers are non-reactive with the fracturing fluid during the fracturing process and fracture closure; the particulate does not affect the rheology of fracturing fluids or solids transport properties.
[0024] 6. Hydrogen chloride released from particulates with vinylchloride monomers can dissolve a carbonate rock and create microchannels in the formation. This creates a divaricated system of drainage and improves the hydrocarbon flow towards the wellbore.
[0025] 7. Hydrogen chloride released from polymer particulates can dissolve the filter cake formed during filtration on gel by the rock matrix.
[0026] If other types of substances meet the conditions formulated in the independent claim of the invention formula, the advantages must be the same.
[0027] A new method of conducting of hydraulic fracturing is disclosed in the following claims; according to this method, proppant is delivered to the fracture with a mixture polymer particles (polyvinylchloride or copolymers of vinylchloride), wherein the main proppant and polymeric particulate can be mixed before the job or on-the-fly and then delivered to the subterranean formation. Under the conditions of high subterranean temperature the polymeric material produces hydrogen chloride that destroys the network of intermolecular cross-links in the polymer gel; the said cross-linked network is formed due to intermolecular bonds between hydroxyl groups of polymer gel and ions of multivalent metals (the cross-linking agents). The produced hydrogen chloride breaks the gel and improves the water solubility of polymer components suspended in the fracturing fluid; this reduces the viscosity of fracturing solution. In general, the said factors facilitate a more complete cleanup of polymer gel from the fracture and improve the fracture permeability. In addition, the method ensures dissolving of the filer cake and formation of micro channels in the formation; the later creates a divaricated system of drainage and facilitates the flow of hydrocarbons towards the wellbore.
[0028] The molar concentration of vinylchloride monomer units in a copolymer varies from about 0.1% to about 99.9%.
[0029] The copolymer may include plasticizers, thermostability agents, and organic and inorganic compounds.
[0030] Other organic or inorganic compounds can be used for the same purpose if they produce hydrogen chloride or hydrogen fluoride under formation conditions; the released hydrogen chloride or hydrogen fluoride combine in water to form hydrochloric acid or etching acid.
[0031] In the method disclosed, the particles of polymeric material can be employed during the entire operation of hydrofracturing or at the final stages.
EXAMPLES
[0032] The application feasibility of the method disclosed was proven by example using a polymer with vinylchloride monomers placed under conditions imitating the conditions of a producing oil well.
[0033] The release of hydrogen chloride by polyvinylchloride was proven by the following experiment. A sample of polyvinylchloride was stored for several days at a high temperature (110° C.) in crude oil. The polyvinylchloride sample initially had a glass transition temperature of 56° C. and crystalline degree equal to 12%. There was no plasticizer in the composition.
[0034] The evolution of sample weight during 1-32 days (showed on the abscissa axis) is plotted in the FIG. 1 (the sample mass is on the left ordinate axis). It is apparent in this diagram that over the time of the thermal treatment there is loss of polymer mass showed on the left ordinate axis. The data of elementary analysis (carbon, hydrogen, chlorine) for initial sample and current state of degraded sample demonstrated that the mass loss of the polyvinylchloride correlates with the production of hydrogen chloride, showed on the right ordinate axis in gram
[0035] For example, a sample of polyvinylchloride with the initial mass of 0.100 kg was stored for the period of 19 days at temperature of 110° C. and produced 0.029 kg of hydrogen chloride, which is equivalent to 0.193 kg of hydrochloric acid with concentration 15%. This quantity of acid is enough to dissolve of 0.042 kg calcite rock, a typical component of carbonate formations.
[0036] Advantages of the disclosed method in comparison to known at the art are the following:
[0037] 1. It is possible to reduce the concentration or abandon completely the costly gel breakers.
[0038] 2. The yield of hydrogen chloride from the said polymeric material is a long-run process (tens of days). A long time interval facilitates more uniform distribution of produced hydrochloric acid over the fracture volume and ensures more complete breaking of polymer gel.
[0039] 3. The particulate of polymer based on vinylchloride monomer effectively releases hydrogen chloride at elevated temperature of formation (130 . . . 200° C.), when most of commercially available peroxide gel breakers (e.g., peroxide and persulfate of metal or ammonium) fail.
[0040] 4. Unlike common peroxide-type gel breakers, the polymer particles with vinylchloride monomers does not react with components of resin coated proppant and therefore should not damage the proppant pack strength which can lead to a reduction of fracture width.
[0041] 5. Unlike peroxide-type (persulfate-type) gel breakers, the polymer particles with vinylchloride monomers do not react with fracturing fluids during any stage of the fracturing process or during fracture closure; the particulate will not affect the rheology of fracturing fluid or proppant transport properties.
[0042] 6. Hydrogen chloride or hydrogen fluoride released from particulates can dissolve a carbonate rock and create micro channels in the formation. This creates a divaricated system of drainage and facilitates the flow of hydrocarbons towards the wellbore.
[0043] 7. Hydrogen chloride or hydrogen fluoride released from polymer particulates is capable of filter cake removal because these particles will be trapped inside the fracture, near the fracture surface.
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Methods including the pumping of fracturing fluid carrying proppant. Simultaneously particulate is pumped made of substance that under subterranean temperature releases hydrochloric or etching acid precursor, wherein the said acid precursor reacts with the formation water and produces acid. The methods stimulate the inflow of formation fluid towards the well due to cleaning of the surface of hydrofracture and due to growth of its area.
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BACKGROUND OF THE INVENTION
The history of slot machines as amusement devices dates back to 1897 when Charlie Fey, a car mechanic from San Francisco, invented “Liberty Bell”. He used it to entertain his customers while they were waiting for their cars being repaired at his shop. Several new companies, by making mechanical slot machines with similar design, gave the birth of a new fast growing industry. But the gambling aspect of these gambling primates was limited due to the physical limitation on the number of symbols and fairly easiness to cheat, therefore the rather small jackpots.
In 1964 the slot machines turned into a business device also. By replacing the mechanical parts of the slot machine with electronic parts Bally Manufacturing added two more dimensions to slot machines: the coins in and coins out. Unlike their mechanical counterparts the computers were no subject to wear and tear. The results from their operation became highly reliable and predictable. From fringe pastime offering placed around the edges of the casinos for the companions of the gamblers while they were playing at the tables, the slot machines were moved to the center of the casino. By the mid 70's they dominated the casinos by generating about three quarters of the casino revenue.
Video poker became very popular as a slot game in the late 70's. The dimension of the optimal play was added. Players were able to make decisions and chose among different alternative strategies. Its popularity grew so much in the early 90's that earned it the name the “America's National Game of Chance”.
The progressive systems in the 80's added another dimension to the slot machines by virtually linking many slot machines very often in different casinos and physical areas into one common pool. By playing at any one of these slot machines the players were contributing a dismal portion of their bet into a jackpot with unperceivable before size and were competing for it. The technological innovations in the computer science elevated the physical restriction in the size of the reels and provided analyses on the outcomes by computer simulation.
The design of the multi-game in the early 90's gave the player the ability to choose among different games at the same slot machines and added multiple dimensions to the slot machines. Now the same slot machine was also a poker machine, a keno machine, you name it. The slot machine was turned into a virtual multidimensional gaming device.
By linking two consecutive games into one game the bonus games added yet another equation to the problem. Now the slot machines are linked both in space and time.
The Indian gaming expanded the social dimension to the slot machines on a national scale. Now not just Nevada but the whole nation uses the slot machine as tool to aggregate disposable income and allocates it to solve community issues.
SUMMARY OF THE INVENTION
The novelty of the approach in this new game design is, that in contrast to the traditional casino slot games the player is offered a series of betting rounds in a slot game based on the computer evaluation or processing of precompiled data in real time to the dynamically changing real probabilities of the game outcomes and associating awards to them. Also considering some established paradigms in the gaming industry, at any time during the game the player can engage into the betting round, skip and proceed to the next betting round, or be able to exit the game without any penalty.
The 21st century marked an explosion in technological innovation and information. This created a challenging environment for every one of us in making decisions every day of our lives in imperfect information. As information changes throughout the course of an execution, we have to reevaluate our initial decision and take appropriate actions to improve our performance.
The current invention is aimed to provide a method for designing casino slot game that will match our environment. The current innovative game design links together more than one game through their bets and their outcomes. If we arrange the bets of more than 2 games in the rows of a table and the outcomes in the columns of the table, we will obtain a multidimensional matrix as far as the games have some common bets and some common outcomes (In this invention we are not going to discuss the subclass of diagonal matrixes as they don't present any interest to us). Next with a computer we calculate the probabilities of all bets and outcomes in the table in real time. By real time we mean that the computer is either dynamically solving the so formed matrix with methods of the mathematical optimization, or simply retrieving the data from previously created and statically stored tables. In both case we can derive and use parameterized approximation functions in well-behaved subsections of the matrix, either to speed up the calculations, or reduce the size of the tables, hence increase the speed also. As the player is receiving additional information in the course of the game, he has to make decision in each betting round based on future events that will be revealed later in the game, which is defined as insufficient information.
For better illustration of the idea we will use a basic example. A player tosses a dollar coin in a casino. If he gets tails, he loses his dollar, if he gets heads, the casino pays him $0.95. Let's now try to improve the game. The player can toss two $1 coins. If both are tails, he loses them, if 1 is heads, he gets $0.95, if both are heads, he gets $1.90. We can describe the so designed game in the following table:
0 0.95 0.95 1.9 1st coin T (0.25) H (0.25) T (0.25) H (0.25) 2nd coin T (0.25) T (0.25) H (0.25) H (0.25) Legend: T = tails H = heads
And the probabilities will look like:
Probabilities
Pays
Percent
0.5 × 0.5 = 0.25
0
0.00%
0.5 × 0.5 = 0.25
0.95
23.75%
0.5 × 0.5 = 0.25
0.95
23.75%
0.5 × 0.5 = 0.25
1.9
47.50%
95.00%
With a little effort this game can be promoted to making decision in insufficient information for the player. The player tosses a $1 coin. If it is tails, he may toss a second $1 coin and win $0.96 or lose all. If he gets heads on the first, he can take $0.95 or toss a second coin and either win $1.92 or lose a $1.
As the entertainment value of tossing the first coin is equal to the entertainment value of tossing a second coin, we had to pay the player a penny to lure him to toss the second coin instead of starting a new game. But in more complex games this is not necessary. Just the opposite, we can as well charge the player a penny or more if the entertainment value of “tossing a second coin” is greater than that of “tossing a first coin”. Also in more complex games the probabilities will not be that obvious, so we will need to use more sophisticated mathematical algorithms and computers.
FIG. 1 gives the general idea of a casino game in which the player makes a decision based on insufficient information. The player starts the game at step 25 placing a bet for the first betting round (step 27 ). The computer displays the bet and the possible game awards for the current betting round at step 29 . The player evaluates the information at step 39 . He decides if he wants to raise his bet at step 41 . If not, he has to decide if he will play more betting rounds at 43 . If not he ends the game at this betting round and the computer pays any unpaid winnings accumulated at 47 and the game ends at step 49 .
If the player chooses to play more betting rounds either by raising the bet at 41 or staying with his bet at step 43 , the computer may pay or may not pay the win from the betting round at step 45 . This is determined by the game designer, who will chose if the computer will pay the bet round win immediately after the completion of the betting round at step 45 a, or the computer will accumulate the win from the bet rounds in a separate win meter at step 45 b. The computer may also allocate the total bet (the bet accumulated in the previous betting rounds plus the bet raise for the current betting round) in respect to the probabilities of the current bet round outcomes. In each particular case this will be dictated by the entertainment value of the underlying game and its perception by the game designer but will not affect the general logic flow in the game design.
At step 31 and 35 the computer either dynamically or statically, or as a combination of both methods, evaluates the probabilities and allocates awards for the outcomes in the next betting round (in step 33 or 37 alternatively). Then the total bet and the contract for the next betting round are displayed again at step 29 . This circular routine may last either until the player decides to end the game, or until a certain resource that regulates its recurrence has been reached. This may be based on a decision that the casino may not want further increases in the payout percentage due to generating excessive losses to the casino, or substantially increasing the game volatility, or a diminishing entertainment value, or encouraging compulsive gaming behavior, etc. The utilization of multiple input/output quantitative models of the game allows any set of different specification requirements to be explicitly defined as a limiting resource in the optimization model. Upon exhausting this resource the optimization algorithm will force the computer to exit the recurring game loop.
The price that the player is willing to pay in every betting round to gain access to perfect information is defined as the Expected Value of Perfect Information (EVPI) in the decision theory as set forth in Douglas Hubbard “How to Measure Anything: Finding the Value of Intangibles in Business” pg. 46, John Wiley & Sons, 2007. The problem is modeled with a payoff matrix R ij in which the row index i describes a choice that must be made by the player, while the column index j describes the random game outcomes of each round the player does not yet have knowledge of, determined by the probability p j of winning j. If the player is to choose i without knowing the value of j, his best choice is the one that maximizes the Expected Monetary Value (EMV):
E M V = max i ∑ j p j R ij .
Here ∑ j p j R ij .
is the expected payoff for action i, and
E M V = max i
denotes choosing the maximum of these expectations for all available actions. With perfect knowledge of j, the player may choose a value of i that optimizes the expectation for that specific j. Therefore, given perfect information, the expected value is given in
EV ❘ PI = ∑ j p j ( max i R ij ) ,
where p j is the probability that the system is in state j, and R ij is the pay-off if one follows action i while the system is in state j. Here
( max i R ij ) ,
indicates the best choice of action i for each state j.
The expected value of perfect information is the difference between these two quantities,
EVPI=EV|PI−EMV.
This difference describes, in expectation, how much larger a value the player can hope to obtain by knowing j and picking the best i for that j, as compared to picking a value of i before j is known. Note that EV|PI is necessarily greater than or equal to EMV. That is, EVPI is always non-negative.
The first computational algorithm for the above model, the simplex method, was created by George Dantzig in 1947. Many other algorithms were developed later on with different success on speed and accuracy, but for the first time the linear programming became feasible for practical problems only in the late 80's, with the invention of the PC computers and the development of many optimization software packages like LINDA, GAMS, LP —solve etc.
The general form of the linear programming looks like:
∑ j = 1 n c j x j -> max
Subject to:
x j ≥ 0 , j = 1 , 2 , … , n .
∑ j = 1 n a ij x j ≤ b i , i = 1 , 2 , … , m .
Where
j stands for the pay categories to be rewarded depending on the played game, i.e. poker, slot, keno, black jack etc. i represents the players choices, that is the betting options in every round, the hold strategies in poker, the play cards in keno and bingo, etc.; c j represents the constant total number of outcomes in all betting rounds of the game, normally these are finite sets, but they as well could be the limit of any converging infinite mathematical function; x j represents the unknown prizes for each betting round to be determined; a ij is the matrix of probabilities for each player choice j and each possible game outcome; b i are genuine restrictions on the players choices, for example one easily identifiable i is the players disposable income (or the bankroll as they like to call it), another one is the casino margin (obviously if the game is not profitable for the casino it will take it off the floor), in poker we can easily identify the next 32 constraints with all possible combination for 5 cards, etc.
The third major element in the game design is the physical limitation in human beings. There is an absolute time limit for us to push buttons, absorb information, react to a change and make a decision. Today's technological advances in computer hardware have made it possible for Electronic Gaming Machines (“EGM”) to calculate the probabilities for multiple players choices and game outcomes faster than human limitations and the traditional duration of slot games. Using the advances in decision theory to design complex scenarios, in mathematical programming to solve them and in computer hardware and software to implement them, EGM manufacturer can design more entertaining games for the players.
The distinguished features of the present invention are described as
(a) Entertainment value—players will have more choices and make decision in insufficient information. (b) Monetary value—the player's bets and game awards in the slot game can be measured in multiple dimensions and may span over multiple consecutive games. (c) Business value—the profit margin for the casino operator can be reliably secured by computers and mathematical algorithms. (d) Fiscal value—the business taxes on the casino operators can be reliable assessed in complex slot games by computers and mathematical algorithms.
In a final note we will try to summarize the difference of the current invention in regard to any previous slot games. The new game design links multiple consecutive casino games in a single game through their bets and outcomes in real time. The significance of the real time is that the player can interactively build the slot game story.
We can link any kind of games, like the homogeneous games True Odds Texas Hold'Em and True Odds Razor Poker that are discussed in more detail later on, or keno and bingo. They can very well be heterogeneous if we link poker with slot and keno. The only necessary condition is that a subset of their bets and outcomes overlay. Otherwise the matrix will become diagonal and we will find ourselves playing the well known multigame EGM.
The new game design is not a mere bet change in the series of bet rounds, like the double up in poker games, the split and the insurance in Black Jack, the rescind of the initial bet in Let it Ride, the buying of reels or features in slot games, the additional bet to draw a sixth card in Second Chance Poker, etc. It is an interaction between the bets and the game outcomes in a sequence of game states. And it is interaction in real time, which implies the player chooses among the bets and the outcomes in imperfect information. This also implies that at any time the player upon his sole discretion can make a bet, skip a bet or end the game without any penalty.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a flow chart of the new wagering casino slot game system.
FIG. 2 is a display of the video screen after the player places his or her wager to initiate the True Odds Texas Hold'Em game.
FIG. 3 is a display of the video screen after the Hole cards are dealt and displayed face up.
FIG. 4 is a display of the video screen after the Flop cards are displayed face up.
FIG. 5 is a display of the video screen after the Turn card is displayed face up.
FIG. 6 is a display of the video screen after the River card is displayed face up.
FIG. 7 is a detailed flow chart of the True Odds Texas Hold'Em game.
FIG. 8 is a display of the video screen after player places his or her wager to initiate the True Odds Razor Poker game.
FIG. 9 is a display of the video screen after 5 randomly selected cards are turned faced up And the computer has evaluated and displayed the contracts for the bet raise.
FIG. 10 is a display of the video screen after the player has chosen to raise his bet by 5 credits to 10 credits.
FIG. 11 is a display of the video screen after the player has chosen to raise his bet by 10 credits to a total of 15 credits.
FIG. 12 is a display of the video screen of the final hand after the player has chosen to deal and replace the unheld cards with random cards from the deck.
FIG. 13 is a detailed flow chart of the True Odds Razor Poker game.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The exemplary embodiment of the current invention is presented by two prominent representative games in the casino slot industry, epitomizing two very distinctive classes of the casino games: skilled and non-skilled games of chance.
The first exemplary case according to this invention details the implementation in non-skilled slot games. Texas Hold 'Em surged in popularity worldwide thanks to the popularity of online poker, the promotion on television through the World Series of Poker championship and the release of major movie blockbusters by Hollywood sporting the game. But yet it had not found its match on the casino floors as an EGM. The game herein and after described is called True Odds Texas Hold'Em (TOTH'Em). It is designed to be played on a computerized slot gaming device by a single player.
One standard fifty-two card deck is used with the traditionally established poker rankings. Clearly displayed contracts (payoff schedules) are presented to the player before he places his wager. After two cards are revealed to the player, his is offered another contract with better or equal odds to wager on. The player may raise his bet, proceed to the next betting round or finish the game without raising the wager and qualifying for the awards from the contract he had bet on. Three more cards are displayed and another contract with improved odds and optional round of betting are displayed. Again, the player may raise his bet, skip to the next betting round with the placed wager and corresponding contract or simply finish the game (the showdown option). The “Turn card” is displayed and the last round of betting is offered to the play. He may raise or keep his bet with the respective contract being enforced and finish the game by displaying the last (“The River”) card.
For better illustration of a player playing the game, reference will be made to the screen displays in combination with the flow chart illustrated in FIG. 7 . A video screen 18 initially appears to the player as seen in FIG. 2 . The game clears and begins at step 55 . At step 57 the player places his wager on a poker hand 20 . It is assumed, that the player wagers the required 5 credits called a blind bet in area 38 and displayed in area 44 for a first contract 36 to take effect. The first contract 36 is comprised of area 40 displaying the winning hands, an area 46 displaying the prizes for the winning hands, a window 42 displaying “Blind Odds” and a window 48 displaying the real odds or pay back percentage. A bet meter 96 displays the amount of the player's wager. Seven cards, 22 , 24 , 26 , 28 , 30 , 32 and 34 representing a typical Texas Hold'Em Hand 20 are dealt to the player face down. At this point as there are no cards revealed and therefore there is no information on the cards value, all contracts 36 , 50 , 64 and 78 look exactly the same. At step 59 the game computer (not illustrated) deals the hole cards 22 and 24 face up from a randomly shuffled standard deck of cards as illustrated in FIG. 3
At step 61 the computer evaluates the probabilities of winning any of the awarded categories for the remaining 50 cards in the deck. Then it optimizes the initial bet and the required raise among all the possible prizes. It applies the general rule of the gaming industry that only the highest win pays and aims at a predetermined targeted return to the player, which is higher than the one in the first contract 36 . In the optimization process the computer may employ additional criteria to generate prizes which will be attractive to the player. The second contract 50 is comprised of area 54 displaying the winning hands, an area 60 displaying the prizes for the winning hands, a window 52 displaying “Flop Bet”, a window 56 displaying “Flop Odds”, and a window 62 displaying the real odds or pay back percentage. The required raise of the bet is displayed in area 58 . The player can depress a “Call Flop” button 104 to raise his bet and qualify for contract 50 , depress a “Check” button 98 to reveal the flop cards 26 - 30 without raising the bet and accepting the contract 50 , or simply depress a “Showdown” button 100 and reveal all cards 26 - 34 . In the last case the amount won, if any according to the first contract 36 , is displayed on a win meter 92 (shown in FIG. 6 ) and added to a credit meter 94 .
As seen in FIG. 4 and as described in FIG. 7 , at step 75 , as soon as the first round of betting is completed, the computer displays the flop cards 26 - 30 and evaluates the odds for the next betting round. It evaluates the probabilities of winning any of the awarded categories for the remaining 47 cards in the deck. Then it optimizes the current bet of the player and the required raise for the player to qualify for the next contract 64 . All possible prizes are allocated based on the general rule in the gaming industry that only the highest win pays, and a predetermined targeted return for this betting round. This targeted return percentage is chosen to be higher than the return of the active contract to attract the player's participation in the betting process. In the optimization process the computer may employ additional criteria to generate enticing prizes to the player. The third contract 64 is comprised of area 68 displaying the winning hands, an area 74 displaying the prizes for the winning hands, a window 66 displaying “Turn Bet”, a window 70 displaying “Turn Odds”, and a window 76 displaying the real odds or pay back percentage. The required raise of the bet for contract 64 is displayed in area 72 . The player can depress a “Call Turn” button 106 to raise his bet and qualify for contract 64 , depress the “Check” button 98 to reveal the turn card 32 without raising the bet and declining contract 64 or simply depress the “Showdown” button 100 and reveal all remaining cards 32 - 34 . The amount won, if any, according to the contract that the player qualified for, is displayed on the win meter 92 (shown in FIG. 6 ) and added to the credit meter 94 .
On the next betting round as seen in FIG. 5 and as described in FIG. 7 at step 89 , as soon as the second round of betting is completed, the computer displays the turn card 32 face up and evaluates the odds for the next betting round. It evaluates the probabilities of all possible winning categories for the remaining 46 cards in the deck. Then it optimizes the current bet of the player and the required raise for the player to qualify for the next contract 78 . All possible prizes are allocated based on the general rule of the gaming industry that only the highest win pays and a predetermined targeted return for this betting round. This targeted return percentage is again set to be higher than the return of the active contract to further involve the player into participating in the betting process. In the optimization process the computer may employ additional criteria to generate attractive prizes to the player. The forth contract 78 is comprised of area 82 displaying the winning hands, an area 88 displaying the prizes for the winning hands, a window 80 displaying “River Bet”, a window 84 displaying “River Odds”, and a window 86 displaying the real odds or pay back percentage. The required raise of the bet for contract 78 is displayed in area 90 . The player can depress a “Call River” button 108 to raise his bet and qualify for contract 78 , depress either the “Check” button 98 or the “Showdown” button 100 , which in this case is equivalent, to reveal the river card 34 without raising the bet and declining contract 78 .
FIG. 6 displays the end of the game. All cards 22 - 34 are displayed face up. Assuming that the player has participated in all betting rounds he has “Two pairs” and has won 12 credits as displayed in area 88 according to contract 78 . His prize is also displayed on the win meter 92 and added to the credit meter 94 . Had the player skipped the raise for the last betting round by either depressing the “Check” button 98 or the “Showdown” button 100 , the bet meter 96 would have shown 20 credits and the win meter 92 would've shown 9 credits according to contract 64 .
If the player had hit the “Showdown” button 100 in the second betting round his win would be displayed as 6 credits in win meter 92 according to contract 50 , but the bet meter 96 would also show only 10 credits.
Finally if the player had hit the “Showdown” button 100 in the first betting round his win would be displayed as only 2 credits in win meter 92 according to contract 36 , but the bet meter 96 would also show only 5 credits.
In the described embodiment of the invention only one pocket was dealt to the player. This has been chosen for practical reasons: due to the novelty of the game the simplicity improves the clarity. But obviously there are no limits to offer more pockets to the player. It is strongly emphasized that in the general case neither the number of pockets dealt to the player, nor the offered betting schemes need to be always the same in different implementation of the game. It could very well be played with different poker categories in the contracts. The overall framework is flexible enough also to utilize different kind of decks including one or more jokers and/or different wild cards like in other currently played video poker games in the casinos.
Yet in other embodiments of TOTH'Em the player may be offered to keep any number of the initial pockets concealed and reveal them at any round with different betting schemes. In this case the entertainment aspect will be expanded by providing the player with the opportunity of evaluating different subsets of poker hands and applying different betting strategies. Such embodiments will be possible only in gaming jurisdictions which allow games of skills, but they are subject and will be discussed in more depth in the next preferred embodiment.
Turning to FIG. 8 , there is illustrated the second preferred embodiment of the current invention applied to skilled games. By skilled game it is implied that the ability of the player influences the final results of the game by his actions. The exemplary game hereinafter described is called True Odds Razor (TOR). The resemblance to its next to kin, the video draw poker is unmistaken.
Video monitor 118 displays a typical Video Draw Poker Hand 119 that is comprised of five cards 120 , 122 , 124 , 126 and 128 . Initially only the backs of the cards 120 - 128 are displayed. A genuine Jacks or Better contract 129 (Pay Table) is displayed above the Poker Hand 119 . A first column 130 in contract 129 displays the names of the winning categories of the contract 129 . A second column 132 displays the awards for 1 credit bet by the player, and columns three through six, 134 - 140 , display respectively the awards for 2, 3, 4 and 5 credits bet by the player. Generally the cards are dealt from “standard” fifty-two card decks which may also include jokers.
There is also displayed an area 148 which provides genuine instruction to the player during the course of the game to facilitate his actions, an area 146 to display the players win, an area 142 to show his credits and an area 144 to display the wager. All the available controls to the player 150 - 168 are displayed below. Control 150 allows the player to cash out his credits. Control 152 allows the player to bet one credit. Controls 154 - 162 allow the player to hold or discard respectively cards 120 - 128 . Control 164 allows the player to bet the maximum allowable wager. Control 168 instructs the game to deal the cards.
For better illustration of game flow a reference will be made to the screen displays in combination with the flow chart illustrated in FIG. 13 . The video screen 118 initially appears to the player after he places his wager as seen in FIG. 8 . The game starts at step 155 in FIG. 13 . At step 157 the player places his wager on the poker hand 119 . It is assumed, that the player wagers 5 credits which is displayed in area 144 of FIG. 8 . At step 159 the game computer (not illustrated) deals the five cards 120 - 128 face up from a randomly shuffled standard deck of cards as illustrated in FIG. 9 .
As described in FIG. 13 , at step 159 , as soon as the poker hand 119 is determined, the computer starts evaluating all possible 2,598,960 combinations in all possible permutations of the remaining 47 cards in the deck and all possible 32 combinations, in which the initial five cards 120 - 128 can be held, to calculate the probabilities of the winning categories as seen at step 173 . Utilizing a powerful central processing unit (“CPU”) and fast poker evaluation algorithms the CPU allocates awards to the winning categories at step 175 . In step 177 and 179 is shown an alternative approach, in which the computer had pre-calculated and stored all contracts in a lookup table for faster retrieval. At step 161 the computer displays the two or more raising options and their contracts and the maximum pay back percentages achievable through an optimal play of the initially dealt five cards 120 - 128 . At step 163 , the player holds any of the originally displayed five cards 120 - 128 face up by depressing hold buttons 154 , 156 , 158 , 160 , and 162 . In FIG. 9 the video screen 118 displays in areas 176 and 178 an overlay of columns 132 - 138 of FIG. 8 exemplary contracts to the player if he opts to raise his bet.
At steps 165 and 167 the player can raise his initial bet by 5 or 10 as shown in FIG. 10 and FIG. 11 . His total wager is not committed yet and is displayed in area 144 , therefore it is not subtracted from his credits as displayed in area 142 until he makes his final decision. Evaluating his option as displayed by the original contract in area 140 or the raised bet contracts in areas 176 and 178 , he can change the hold of the originally dealt cards 120 - 128 , or defaults to his original contract. Below the columns are clearly displayed the required raise amounts in area 170 and 172 and the maximum pay back percentage achievable through an optimal play of the initially dealt poker hand by these contracts. The player can activate those contracts either by controls 152 or 164 on FIG. 10 or by touching areas 170 or 172 on a touch screen. Area 174 provides to the player an option to revoke his raise and return to his initial wager and default contract by touching it, which corresponds to step 169 in FIG. 13 . Once the player has decided which cards he wants to hold and which contract he wants to play, he can then depresses the draw button 168 at step 171 . Then the computer commits the wager and proceeds by replacing the cards that are not held with new cards from the randomly shuffled deck as seen in FIG. 12 .
Assuming that the player has raised his wager by 10 credits, his bet is 15 as displayed in area 144 in FIG. 12 . His total credits had been reduced from 990 to 980 (not shown) by the amount of his additional raise. The unheld cards 122 - 126 had been replaced by new cards. At step 181 the computer evaluates that the player has Two Pair in his final hand. In this particular case the amount won is 37 credits according to contract 178 . It is displayed in payout window 146 and is added to the player's credits in the amount of 1027 as shown in window 142 (990−10+37=1017). Should the player have risen by 5 credits, the bet in area 144 would've shown 10 credits. Then contract 176 would take effect and the computer would pay 24 credits. Finally, if the player had chosen to forfeit any raise option the bet in area 144 would've shown at the original value of 5 and the computer would've paid 10 credits according to the original contract 140 .
As described above, the specific application was described as a form of poker. However, other games can be played such as keno, blackjack, slots or other games which are generally found at casinos.
Thus there has been provided a casino game and wagering system that fully satisfies the objects and advantages set forth herein. While the invention has been described in conjunction with a specific embodiment, it is evident that many alternatives, modifications and variations will be apparent to those skilled in the art in light of the foregoing description. Accordingly, it is intended to embrace all such alternatives, modifications and variations as fall within the spirit and scope of the appended claims.
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A new concept for designing casino slot games The game links together more than one game through their bets and their outcomes. All the bets and outcomes form a multidimensional matrix. A computer calculates the probabilities of all bets and outcomes during the betting rounds in real time. As a result of the so chained slot games the player makes decisions in multiple betting rounds in insufficient information about the game outcomes. At any time during the game play the player can evaluate the game outcomes as presented to him by the computer and raise his bet, proceed to the next betting round without changing the bet, or simply finish the game with no penalty.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to certain 2,3,6 substituted quinazolinone compounds which have demonstrated activity as angiotensin II (AII) antagonists and are therefore useful in alleviating angiotensin induced hypertension and for treating congestive heart failure.
SUMMARY OF THE INVENTION
According to the present invention, there are provided novel compounds of Formula I which have angiotensin II antagonizing properties and are useful as hypertensives: ##STR2## wherein:
R is ##STR3##
X is lower alkyl of 3 to 5 carbon atoms;
R 6 is: ##STR4##
A is --(CH 2 ) n --;
n is 1, 2, 3, or 4;
W is --CH 2 -- or ##STR5## or A and W are each ##STR6## and are connected by a --(CH 2 ) s -- bridge, wherein S=1, 2 or 3;
Q is --O--, --CH 2 -- or ##STR7##
D is --(CH 2 ) m --;
m is 3 or 4;
R 1 is H, lower alkyl of 1 to 4 carbon atoms (optionally substituted with --OR 5 , --CO 2 R 5 , --CN, phenyl, substituted phenyl (substitution selected from mono-lower alkyl of 1 to 3 carbon atoms, trifluoromethyl, nitro, O-alkyl of 1 to 3 carbon atoms, F, Cl, or Br)), pyridine, thiophene, furan, --CHO, --CO 2 R 5 , --CN, ##STR8##
R 2 is H, lower alkyl of 1 to 4 carbon atoms, (optionally substituted with --OR 5 , --CO 2 R 5 , --CN, phenyl, substituted phenyl (substitution selected from mono-lower alkyl of 1 to 3 carbon atoms, trifluoromethyl, nitro, O-alkyl of 1 to 3 carbon atoms, F, Cl, or Br)), pyridine, thiophene, furan, --CHO, --CO 2 R 5 , --CN, ##STR9##
R 3 is H, lower alkyl of 1 to 4 carbon atoms, phenyl, substituted phenyl (substitution selected from mono-lower alkyl of 1 to 3 carbon atoms, trifluoromethyl, nitro, O-alkyl of 1 to 3 carbon atoms, F, Cl, or Br), pyridine, thiophene, furan, --OR 5 , --N(R 5 )(R 7 ), --CO 2 R 5 , --CH 2 OR 5 , --CN, --CHO, ##STR10##
R 5 is H, lower alkyl of 1 to 4 carbon atoms;
R 11 is H, lower alkyl of 1 to 4 carbon atoms, cycloalkyl of 5 or 6 carbon atoms, phenyl, substituted phenyl (substitution selected from mono-lower alkyl of 1 to 3 carbon atoms, trifluoromethyl, nitro, O-alkyl of 1 to 3 carbon atoms, P, Cl, or Br), pyridine, thiophene, furan, benzyl, substituted benzyl (substitution selected from mono-lower alkyl of 1 to 3 carbon atoms, trifluoromethyl, nitro, O-alkyl of 1 to 3 carbon atoms, P, Cl, or Br), --CO 2 R 5 , --SO 2 R 10 , ##STR11##
R 7 is H, lower alkyl of 1 to 4 carbon atoms;
R 8 is H, --CO 2 R 5 , --SO 2 R 10 , ##STR12##
R 10 is lower alkyl of 1 to 4 carbon atoms, phenyl, substituted phenyl (substitution selected from mono-lower alkyl of 1 to 3 carbon atoms, trifluoromethyl, nitro, O-alkyl of 1 to 3 carbon atoms, F, Cl, or Br); and pharmaceutically acceptable salts thereof.
The present invention also provides novel intermediate compounds, methods for making the novel 2,3,6 substituted quinazolinone angiotensin II antagonizing compounds, methods of using the novel quinazolinone angiotensin II antagonizing compounds to treat hypertension, congestive heart failure and to antagonize the effects of angiotensin II.
DETAILED DESCRIPTION OF THE INVENTION
The novel compounds of the present invention are prepared according to the following reaction schemes.
Referring to Scheme I, the corresponding anthranilic acid 2 wherein R 9 is I, Br or CH 3 , are heated to reflux in alkyl acid anhydride 3 wherein X is lower alkyl of 3 to 5 carbon atoms to provide the 4H-3,1-benzoxazin-4-ones 4 which are isolated by concentrating the reaction mixtures and used without further purification. When the 4H-3,1-benzoxazin-4-ones 4 are refluxed in ethyl alcohol containing ammonia, or ammonium hydroxide solution, the quinazolinone intermediates 5 are obtained. ##STR13##
The quinazolinone intermediates 5 are modified according to the following reaction schemes to obtain the novel quinazolinone angiotensin II antagonizing compounds of the present invention.
In Scheme II, 6-methylquinazolinone 6, as prepared by Scheme I, is brominated with N-bromosuccinimide to give the bromomethyl compound 7. Hydrolysis of the bromide with aqueous potassium carbonate in dimethylsulfoxide yields the primary alcohol 8. The alcohol 8 is oxidized with pyridinium dichromate in N,N-dimethylformamide to afford aldehyde 9. The aldehyde 9 is reacted with a variety of Grignard Reagents R 1 MgBr or lithium reagents R 1 Li in tetrahydrofuran where R 1 is hereinbefore defined, with the proviso that for this reaction scheme R 1 cannot contain a carbonyl group or be H, --CO 2 R 5 , or ##STR14## to give the desired secondary alcohol 10. Alcohol 10 is oxidized with pyridinium dichromate in N,N-dimethylformamide to afford ketone 11. ##STR15##
In an alternate route to 9, as shown in Scheme III, 2-alkylsubstituted-6-iodo-4(1H)-quinazolinone 12 is reacted via a palladium catalyzed formylation to give aldehyde 9. Additionally, 12 is converted to ester 13 by palladium (II) catalyzed coupling in the presence of carbon monoxide and methanol. Reduction of 13 with lithium aluminum hydride in tetrahydrofuran gives alcohol 8. Alcohol 8 is oxidized with pyridinium dichromate to yield aldehyde 9. ##STR16##
As shown in Scheme IV, the palladium (II) catalyzed coupling of (trimethylsilyl)acetylene with 2-alkylsubstituted-6-iodo-4(1H)-quinazolinone 12 yields the acetylenic quinazolinone 14. Desilylation of the acetylene with sodium hydroxide in water-methanol gives the terminal acetylene 15. Hydration of acetylene is with catalytic mercuric sulfate-sulfuric acid in acetic acid affords methyl ketone 16. The palladium (II) catalyzed coupling of substituted acetylenes where R 17 is defined as lower alkyl of 1 to 4 carbon atoms with 2-alkylsubstituted-6-iodo-4(1H)- quinazolinone 12 yields the acetylenic quinazolinone 17. Hydration of 17 with catalytic mercuric sulfate-sulfuric acid in acetic acid gives ketone 18. ##STR17##
As described in EP 0,497,150, biphenyl 19 is attached to quinazolinone intermediate 11 by initially alkylating the quinazolinone with a para-substituted benzyl bromide and subsequently attaching a second phenyl moiety containing a trityl protected tetrazole or a cyano via a transition metal catalyzed coupling at the para position of the first phenyl ring. Quinazolinone intermediates 16 and 18 are similarly reacted. Alternatively, the coupling of quinazolinone intermediate 11 where X and R 1 are hereinbefore defined with biphenyl 19 where R 18 is a trityl protected tetrazole prepared by the methods of N. B. Mantlo, J. Chem., 34, 2919-2922 (1991) or cyano prepared by the methods outlined in D. J. Carini, J. Med. Chem. 34, 2525-2547 (1991) is illustrated in Scheme V and gives coupled product 20 by dissolving 11 and 19 in acetone or another suitable solvent such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidinone, methanol, ethanol, t-butanol, tetrahydrofuran, dioxane or dimethylsulfoxide, in the presence of excess potassium carbonate or another suitable base such as sodium carbonate, cesium carbonate, sodium hydride, potassium hydride, sodium methoxide, sodium ethoxide, lithium methoxide, sodium t-butoxide, potassium t-butoxide, lithium diisopropylamide (LDA) or lithium hexamethyldisilazide for 2-48 hours, at 20°-60° C. The obtained alkylated quinazolinone 20 may be purified by chromatography or used as is in further transformations and/or deprotection. Quinazolinone intermediates 16 and 18 are similarly reacted. ##STR18##
As shown in Scheme VI, aldehyde or ketone 20, where R 1 and x are hereinbefore defined, is reacted with an N-substitutedhydroxylamine 21, where R 2 , R 3 , W, Q and A are hereinbefore defined prepared by the method of W. Oppolzer et al., Tetrahedron, 41, #17, 3497-3509(1985), at room temperature in chloroform in the presence of molecular sieves to give a nitrone 22. Heating the nitrone 22 at reflux in toluene gives a mixture of bicyclic-substituted quinazolinone 23 and bicyclic-substituted quinazolinone 24.
Reaction of 23 or 24 where R 18 is cyano with sodium azide in the presence of tri-n-butyltin chloride in refluxing xylene affords the desired tetrazole 25 or 26. Contemplated equivalents to tri-n-butyltin chloride include tri-(loweralkyl C 1 -C 4 ) tin chlorides and bromides. Contemplated equivalents to sodium azide include potassium azide, and lithium azide. Hydrolysis of 23 or 24 where R 18 is a trityl protected tetrazole with methanol-tetrahydrofuran at room temperature to reflux or with an aqueous solution containing a catalytic amount of hydrochloric acid or other suitable acid such as sulfuric, trifluoroacetic or hydrogen chloride for 10 minutes to 24 hours at room temperature affords the free tetrazole 25 or 26.
As shown in Scheme VII, aldehyde or ketone 11, where R 1 and X are hereinbefore defined is reacted with an N-substitutedhydroxylamine 27 where R 11 is hereinbefore defined to give nitrone 28. Reaction of 28 with olefin 29 where A, Q, W, R 2 and R 3 are as defined hereinbefore gives quinazolinone 30. ##STR19##
Quinazolinone intermediate 30 wherein X, A, Q, W, R 1 , R 2 , R 3 and R 11 , are hereinbefore defined is coupled with with biphenyl 19 by the methods described hereinabove for scheme V to give coupled product 33. The obtained alkylated quinazolinone 33 may be purified by chromatography or used as is in further transformations and/or deprotection.
Reaction of 33 where R 18 is cyano with sodium azide in the presence of tri-n-butyltin chloride in refluxing xylene affords the desired tetrazole 35. Contemplated equivalents to tri-n-butyltin chloride include tri-(loweralkyl C 1 -C 4 ) tin chlorides and bromides. Contemplated equivalents to sodium azide include potassium azide, and lithium azide. Hydrolysis of 33 where R 18 is a trityl protected tetrazole with methanol-tetrahydrofuran at room temperature to reflux or with an aqueous solution containing a catalytic amount of hydrochloric acid or other suitable acid such as sulfuric, trifluoroacetic or hydrogen chloride for 10 minutes to 24 hours at room temperature affords the free tetrazole 35. ##STR20##
As shown in Scheme VIII, aldehyde or ketone 20, where R 1 , R 18 and X are hereinbefore defined is reacted with amine 37 where R 2 , R 3 and D are hereinbefore defined to give quinazolinone intermediate 38. Aza-allyl anion cyclization of 38 with LDA using the method of W. H. Pearson, J. Am. Chem. Soc. 108, 2769-2771 (1986) gives 39 which is converted to substituted intermediate 40 where R 11 is hereinbefore defined. Reaction of 40 where R 18 is cyano with sodium azide in the presence of tri-n-butyltin chloride in refluxing xylene affords the desired tetrazole 41. Contemplated equivalents to sodium azide included potassium azide and lithium azide. Hydrolysis of 40 where R 18 is a trityl protected tetrazole with methanol-tetrahydrofuran at room temperature to reflux or with an aqueous solution containing a catalytic amount of hydrochloric acid or other suitabled acid such as sulfuric, trifluoroacetic or hydrogen chloride for 10 minutes to 24 hours at room temperature affords the free tetrazole 41. ##STR21##
As outlined in Scheme IX, aldehyde or ketone 20, where R 1 , R 18 and X are hereinbefore defined is reacted with amine 42, where R 2 , R 3 , R 11 , W, Q and A are hereinbefore defined and cyclized using the method of W. Oppolzer et al., Tet. Lett 17, 1707-1710 (1972) to give quinazolinone intermediate 43. Reaction of 43 where R 18 is cyano with sodium azide in the presence of tri-n-butyltin chloride in refluxing xylene affords the desired tetrazole 44. Contemplated equivalents to sodium azide include potassium azide and lithium azide. Hydrolysis of 43 where R 18 is a trityl protected tetrazole with methanol-tetrahydrofuran at room temperature to reflux or with an aqueous solution containing a catalytic amount of hydrochloric acid or other suitable acid such as sulfuric, trifluoroacetic or hydrogen chloride for 10 minutes to 24 hours at room temperature affords the free tetrazole 44.
Reactions are performed in a solvent appropriate to the reagents and materials employed and suitable for the transformation being effected. It is understood by those skilled in the art of organic synthesis that the various functionalities present on the molecule must be consistent with the chemical transformations proposed. This may necessitate judgement as to the order of synthetic steps, protecting groups, if required, and deprotection conditions. Substituents on the starting materials may be incompatible with some of the reaction conditions. Such restrictions to the substituents which are compatible with the reaction conditions will be apparent to one skilled in the art.
Pharmaceutically suitable salts include both the metallic (inorganic) salts and organic salts; a list of which is given in Remington's Pharmaceutical Sciences, 17th Edition, pg. 1418 (1985). It is well known to one skilled in the art that an appropriate salt form is chosen based on physical and chemical stability, flowability, hydroseopicity and solubility. Preferred salts of this invention for the reasons cited above include potassium, sodium, calcium, magnesium and ammonium salts.
Some of the compounds of the hereinbefore described schemes have centers of asymmetry. The compounds may, therefore, exist in at least two and often more stereoisomeric forms. The present invention encompasses all stereoisomers of the compounds whether free from other stereoisomers or admixed with other stereoisomers in any proportion and thus includes, for instance, racemic mixture of enantiomers as well as the diastereomeric mixture of isomers. The absolute configuration of any compound may be determined by conventional X-ray crystallography.
While the invention has been illustrated using the trityl protecting group on the tetrazole, it will be apparent to those skilled in the art that other nitrogen protecting groups may be utilized. Contemplated equivalent protecting groups include, benzyl, p-nitrobenzyl, propionitrile or any other protecting group suitable for protecting the tetrazole nitrogen. Additionally, it will be apparent to those skilled in the art that removal of the various nitrogen protecting groups, other than trityl, may require methods other than dilute acid.
The compounds of this invention and their preparation are illustrated by the following non-limiting examples.
EXAMPLE 1
2-Butyl-6-(methyl)-4(1H)-quinazolinone
To 20.0 g of 2-amino-5-methylbenzoic acid is added 60 ml of valeric anhydride. The mixture is heated at reflux for 18 hours and then concentrated under reduced pressure. The resulting brown solid residue is dissolved in a mixture of 200 ml of 30% of ammonium hydroxide solution and 300 ml of ethyl alcohol. This mixture is heated at reflux for 5 hours and then allowed to cool to room temperature. After cooling, the precipitate is collected by filtration. The cake is washed with ethanol and water, then dried under vacuum to give 8.92 g of the quinazolinone as a white solid.
CI MASS SPEC MH + =217.
EXAMPLE 2
2-Butyl-6-iodo-4(1H)-quinazolinone
The method of Example 1 is used with 2-amino-5-iodobenzoic acid to prepare the desired product, m.p. 257°-258° C.
EXAMPLE 3
2-Butyl-6-(bromomethyl)-4(1H)-quinazolinone
To a suspension of 3.50 g of 6-methylquinazolone in 100 ml of chloroform is added 3.39 g of N-bromosuccinimide and 0.25 g of benzoyl peroxide. The reaction mixture is heated at reflux for 18 hours and then filtered hot. A precipitate of 2.21 g of an inseparable mixture of the desired bromide and starting 6-methyl-quinazolinone is obtained and used in Example 4 without further purification.
EXAMPLE 4
2-Butyl-6-(hydroxymethyl)-4(1H)-quinazolinone
To a suspension of 2.0 g of impure 2-butyl-6-(bromomethyl)-4(1H)-quinazolinone (Example 3) in 35 ml of dimethylsulfoxide and 20 ml of water is added 1.0 g of potassium carbonate. The reaction mixture is heated at reflux for 6 hours, resulting in a complete solution. Upon cooling slowly to room temperature a white precipitate forms and is collected by filtration. The filter cake is purified by flash chromatography on silica gel, eluting with 9:1 chloroform-methanol to give 0.67 g of the desired product as a white solid.
CI MASS SPEC 233(M+H).
EXAMPLE 5
2-Butyl-1,4-dihydro-4-oxo-6-quinazolinecarboxaldehyde
To a solution of 0.3 g of 2-butyl-6-(hydroxymethyl)-4(1H)-quinazolinone in 3.5 ml of dry N,N-dimethylformamide is added 1.7 g of pyridinium dichromate. The reaction mixture is stirred at room temperature for 16 hours and then poured into 125 ml of water. The resulting precipitate is removed by filtration and the filtrate extracted with 9:1 chloroform-methanol. The combined organic extracts are dried over magnesium sulfate, filtered and concentrated in vacuo and combined with the precipitate above. The combined solids are purified by flash chromatography on silica gel by eluting with 1:1 ethyl acetate-hexanes to give 0.27 g of the desired product.
CI MASS SPEC 231(M+H).
EXAMPLE 6
2-Butyl-6-(l-hydroxyethyl)-4(1H)-quinazolinone
To a solution of 0.60 g of 2-butyl-1,4-dihydro-4-oxo-6-quinazolinecarboxaldehyde in 30 ml of dry tetrahydrofuran, cooled to 0° C. is added dropwise, 2.61 ml of a 3.0M solution of methylmagnesium bromide in diethyl ether. The reaction is stirred at 0° C. for 30 minutes and then quenched with 10 ml of aqueous ammonium chloride. After diluting with 10 ml of water, the reaction mixture is extracted with 9:1 chloroform-methanol. The combined extracts are dried with magnesium sulfate, filtered and concentrated to yield 0.64 g of the desired product.
CI MASS SPEC 247(MH + ).
EXAMPLE 7
2-Butyl-6-(l-hydroxypropyl)-4(1H)-quinazolinone
To a solution of 0.25 g of 2-butyl-1,4-dihydro-4-oxo-6-quinazolinecarboxaldehyde in 10 ml of dry tetrahydrofuran, cooled to a0° C., is added 1.63 ml of 2.0M ethyl magnesium bromide in tetrahydrofuran. The reaction mixture is stirred for 30 minutes at 0° C. and quenched with 20 ml of saturated ammonium chloride solution and 20 ml of water. The reaction mixture is extracted with 9:1 chloroform-methanol, dried over magnesium sulfate, filtered and evaporated in vacuo to give 0.26 g of the desired product.
CI MASS SPEC 261(MH + ).
EXAMPLE 8
2-Butyl-1,4-dihydro-4-oxo-6-quinazolinecarboxaldehyde
To a solution of 1.0 g of 2-butyl-6-iodo-4(1H)-quinazolinone and 0.355 g of tetrakis(triphenylphosphine)palladium in 15 ml of tetrahydrofuran and 5 ml of N,N-dimethylformamide, heated to 55° C. under an atmosphere of carbon monoxide is added a solution of 1.40 g of tri-n-butyltin hydride in 2.5 ml of toluene over 6 hours via a syringe pump. After the addition is complete the reaction is allowed to cool to room temperature, diluted with brine and extracted with chloroform. The combined organics are concentrated in vacuo and the resulting residue triturated with ether. The precipitate is collected by filtration and purified by flash chromatography on silica gel, eluting with 1:1 ethyl acetate-hexanes to give 0.35 g of the desired product, m.p. 242°-244° C.
EXAMPLE 9
2-Butyl-6-[(trimethylsilyl)ethylnyl]-4(1H)-quinazolinone
To a solution of 1.0 g of 2-butyl-6-iodo-4(1H)-quinazolinone 0.043 g of bis(triphenylphosphine) palladium (II) chloride and 5.8 mg of copper (I) iodide in 5.0 ml of N,N-dimethylformamide and 5.0 ml of triethylamine is added 0.36 g of (trimethylsilyl) acetylene. The resulting reaction mixture is heated at 45° C. for 1 hour and then 65° C. for 5 hours. Upon cooling, the reaction mixture is concentrated in vacuo and the residue purified by flash chromatography on silica gel, eluting with 1:3 ethyl acetate-hexane to yield 0.75 g of the desired product as a white solid.
CI MASS SPEC 299(MH + ).
EXAMPLE 10
2-Butyl-6-ethylnyl-4(1H)-quinazolinone
To a solution of 0.70 g of 2-butyl-6-[(trimethylsilyl)ethynyl]-4(1H)-quinazolinone in 20 ml of methanol and 20 ml of tetrahydrofuran is added 10.0 ml of 1.0N sodium hydroxide solution. The reaction is stirred at room temperature for 2 hours and then diluted with 5% hydrochloric acid solution until the pH is 2. The resulting tan precipitate is collected by filtration and dried in vacuo to yield 0.50 g of the desired product.
CI MASS SPEC 227(MH + ).
EXAMPLE 11
6-Acetyl-2-butyl-4(1H)-quinazolinone
To a solution of 1.20 g of 2-butyl-6-ethynyl-4(1H)-quinazolinone in 90 ml of acetic acid is added 0.45 g of mercuric sulfate, 0.9 ml of water and 0.3 ml of sulfuric acid. The reaction mixture is heated at reflux for 5 hours, cooled to room temperature and quenched with 150 ml of water. The resulting mixture is concentrated in vacuo, diluted with 150 ml of water and extracted with 6:1 chloroform-methanol. The combined organics are dried over magnesium sulfate, filtered and concentrated in vacuo. The residue is purified by flash chromatography on silica gel, eluting with 1:1 ethyl acetate-hexanes to give 0.67 g of the desired product as a white solid.
CI MASS SPEC 245(MH + ).
EXAMPLE 12
2-Butyl-6-(hydroxyphenylmethyl)-4(1H)-quinazolinone
To a stirred solution of 2.00 g of 2-butyl-1,4-dihydro-4-oxo-6-quinazolinecarboxaldehyde in 100 ml of tetrahydrofuran, cooled at 0° C., is added 13.0 ml of 2.0M phenyllithium and stirring continued is for 1 hour. The cooling is removed and the reaction allowed to reach room-temperature followed by an additional 30 minutes at room temperature. The reaction is diluted with saturated ammonium chloride solution and extracted with ethyl acetate. The organic layer is dried, evaporated to a residue, which is purified by chromatography on silica gel by elution with 0.25:100 methanol-chloroform to give 0.932 g of the desired product.
CI MASS SPEC 309(MH + ).
EXAMPLE 13
Methyl 2-butyl-1,4-dihydro-4-oxo-6-quinazolinecarboxylate
To a solution of 1.00 g of 2-butyl-6-iodo-4(1H)-quinazolinone and 6.0 ml of triethylamine in 25 ml of methanol and 5 ml of N,N-dimethylformamide is added 0.275 g of bis-(triphenylphosphine)palladium (II) chloride. The reaction mixture is heated at reflux under an atmosphere of carbon monoxide for 16 hours, then allowed to cool and concentrated in vacuo. The residue is purified by flash chromatography on silica gel, eluting with 1:1 ethyl acetate-hexanes to give 0.389 g of the desired product as a white solid.
CI MASS SPEC 261(MH + ).
EXAMPLE 14
2-Butyl-6-(hydroxymethyl)-4(1H)-quinazolinone
To a suspension of 0.013 g of lithium aluminum hydride in 5.0 ml of tetrahydrofuran is added 0.100 g of methyl 2-butyl-1,4-dihydro-4-oxo-6-quinazolinecarboxylate followed by stirring at room temperature for 5 hours. An additional 20 mg of lithium aluminum hydride is added and stirring continued for 18 hours. An additional 20 mg of lithium aluminum hydride is added and stirring continued for an additional 8 hours. The reaction mixture is poured into 75 ml of water and extracted with ethyl acetate. The extract is evaporated in vacuo to a residue which is stirred with acetone and filtered to give 0.040 g of the desired product as a white solid.
CI MASS SPEC 233 (MH + ).
EXAMPLE 15
2-Butyl-6-(hydroxymethyl)-3-[[2'-[1-(triphenylmethyl)-1H-tetrazol-5-yl][1,1'-biphenyl]-4-yl]methyl-4(3H)-quinazolinone
A mixture of 0.198 g of 2-butyl-6-(hydroxymethyl)-4(1H)-quinazolinone, 0.477 g of 5-[4'-(bromomethyl)[1,1'-biphenyl]-2-yl]-1-(triphenylmethyl)-1H-tetrazole and 0.500 g of potassium carbonate in 15.0 ml of dry acetone is heated at reflux for 18 hours. The reaction mixture is allowed to cool to room temperature and evaporated to a residue. The residue is diluted with water and extracted with chloroform. The organic layer is washed with brine, dried with Na 2 SO 4 and evaporated in vacuo to a residue which is purified on thick layer silica gel chromatography plates using 1:1 ethyl acetate-hexanes to give 0.14 g of the desired product. FAB MASS SPEC 709 (M+H).
EXAMPLE 16
2-Butyl-3,4-dihydro-4-oxo-3-[[2'-[1-(triphenylmethyl)-1H-tetrazol-5-yl][1,1'-biphenyl]-4-yl]methyl]-6-quinazolinecarboxaldehyde
A mixture of 6.48 g of 2-Butyl-6-(hydroxymethyl)-3-[[2'-[1-(triphenylmethyl)-1H-tetrazol-5-yl][1,1'-biphenyl]-4-yl]methyl-4(3H)quinazolinone and 5.16 g of pyridinium dichromate in 20 ml of methylene chloride is stirred at room temperature for 18 hours. The reaction mixture is diluted with 100 ml of ether and filtered through a short pad of MGSO 4 . The filtrate is concentrated in vacuo to give the desired product as a residue. FAB MASS SPEC 729 (M+Na).
EXAMPLE 17
2-Butyl-6-(9-oxa-1-azabicyclo[4.2.1]non-8-yl)-3-[[2'-[1-(triphenylmethyl)-1H-tetrazol-5-yl][1,1'-biphenyl]-4-yl]methyl-4(3H)-quinazolinone
A mixture of 0.198 g of 2-Butyl-3,4-dihydro-4-oxo-3-[[2'-[1-(triphenylmethyl)-1H-tetrazol-5-yl][1,1'-biphenyl]-4-yl]methyl]-6-quinazolinecarboxaldehyde and 0.034 g of N-(5-hexenyl)hydroxylamine in 5.0 ml of toluene is heated at reflux for 18 hours then concentrated in vacuo to a residue. The residue is purified by column chromatography on silica gel using 1:1 ethyl acetate-hexanes to give 47 mg of the desired product.
EXAMPLE 18
cis-2-Butyl-6-(9-oxa-1-azabicyclo[4.2.1]non-8-yl)-3-[[2'-(1H-tetrazol-5-yl)[1,1'-biphenyl]-4-yl-methyl-4(3H)-quinazolinone
A mixture of 0.154 g of 2-Butyl-6-(9-oxa-1-azabicyclo[4.2.1]non-8-yl)-3-[[2'-[1-(triphenylmethyl)-1H-tetrazol-5-yl][1,1'-biphenyl]-4-yl]methyl-4(3H)-quinazolinone in 5.0 ml of methanol and 1.0 ml of tetrahydrofuran is heated at reflux for 18 hours. The volatiles are evaporated in vacuo to give 0.053 g of the desired product. FAB MASS SPEC 562 (M+H).
EXAMPLE 19
2-Butyl-6-(7-oxa-1-azabicyclo[3.2.1]-oct-8-yl)-3-[[2'-[1-(triphenylmethyl))-1H-tetrazol-5-yl][1,1'-biphenyl]-4-yl]methyl]-4(3H)-quinazolinone
EXAMPLE 20
2-Butyl-6-(8-oxa-1-azabicyclo[3.2.1]oct-7-yl)-3-[[2'-[1-(triphenylmethyl)-1H-tetrazol-5-yl][1,1'-biphenyl]-4-yl]methyl]-4(3H)-quinazolinone
A mixture of 0.487 g of N-(4-pentenyl)hydroxylamine oxalate and 20 ml of 6N KOH is stirred and extracted with ether. The organic layer is separated and dried with solid NAOH. The organic layer is separated and combined with 0.900 g of 2-butyl-3,4-dihydro-4-oxo-3-[[2'-[1-(triphenylmethyl)-1H-tetrazol-5-yl][1,1'-biphenyl]-4-yl]methyl]-6-quinazolinecarboxaldehyde and the volatiles concentrated in vacuo to a residue which is dissolved in CHCl 3 and 4A molecular sieves added. The reaction mixture is stirred overnight at room temperature and filtered. The filtrate is evaporated in vacuo to a residue which is purified by column chromatography on silica gel using 1:1 ethyl acetate-hexanes to all ethyl acetate to afford 0.716 g of residue which is dissolved in 30 ml of toluene and heated at reflux for 12 hours. The volatiles are evaporated in vacuo to afford a residue which is purified by high pressure liquid chromatography on silica gel using 1:2 ethyl acetate-hexanes to give 0.134 g of the first desired product as a pale yellow foam and 2 mg of the second desired product as a yellow glass. FAB MASS SPEC 812 (M+Na).
EXAMPLE 21
2-Butyl-6-(7-oxa-1-azabicyclo[3.2.1]oct-8-yl)-3-[[2'-(1H-tetrazol-5-yl)[1,1'-biphenyl]-4-yl]-methyl-4(3H)-quinazolinone
A mixture of 0.124 g of 2-butyl-6-(7-oxa-1-azabicyclo[3.2.1]oct-8-yl)-3-[[2'-[1-(triphenylmethyl)-1H-tetrazol-5-yl][1,1'-biphenyl]-4-yl]methyl-4(3H)-quinazolinone in 5.0 ml of methanol and 1.0 ml of tetrahydrofuran is heated at reflux for 16 hours, cooled and concentrated in vacuo to a residue which is purified by column chromatography on silica gel using 9:1 chloroform-methanol to give 0.073 g of the desired product as a white solid. FAB MASS SPEC 548 (M+H).
EXAMPLE 22
2-Butyl-6-[(methylimino)methyl]-4(1H)-quinazolinone N 6 -oxide
To a stirred solution of 2.7 g of sodium methoxide in 50 ml of ethyl alcohol, cooled to 0° C. is added 4.1 g of N-methylhydroxylamine hydrochloride. After stirring for 10 minutes, 2.3 g of 2-butyl-1,4-dihydro-4-oxo-6-quinazolinecarboxaldehyde is rapidly added. The cooling bath is removed and the reaction mixture stirred at room temperature for 18 hours. The volatiles are evaporated in vauco to a yellow solid residue which is stirred with water, filtered, the cake washed with water and air dried to afford 2.3 g of the desired product as a yellow solid, m.p. 206° C.
EXAMPLE 23
2-Butyl-6-[[(phenylmethyl)imino]methyl]-4(1H)-quinazolinone N 6 -oxide
This reaction is performed under the same conditions as Example 22 using 2.3 g of 2-butyl-1,4-dihydro-4-oxo-6-quinazolinecarboxaldehyde, 1.2 g of sodium methoxide, 25 ml of ethyl alcohol and 3.18 g of N-benzylhydroxylamine hydrochloride to give 2.9 g of the desired product as a yellow solid, m.p. 180° C.
EXAMPLE 24
2-Butyl-6-[(cyclohexylimino)methyl]-4(1H)-quinazolinone N 6 -oxide
This reaction is performed under the same conditions as Example 22 using 4.0 g of 2-butyl-1,4-dihydro-4-oxo-6-quinazoline carboxaldehyde, 2.65 g of sodium methoxide, 150 ml of ethyl alcohol and 7.55 g of N-cyclohexylhydroxylamine hydrochloride to give 4.2 g of the desired product as a yellow solid. Mass Spec (EI) 327.
EXAMPLE 25
(3α,3aα,6aα) -2-butyl-6- (hexahydro-2-methyl-4-oxo-2H-cyclopent[d]isoxazol-3-yl-4(1H)-quinazolinone
A mixture of 1.0 g of 2-butyl-6-[(methylimino)methyl]-4(1H)-quinazolinone N 6 -oxide and 2 ml of 2-cyclopenten-3-one in 15 ml of toluene is heated at reflux for 8 hours then allowed to cool. The volatiles are evaporated in vacuo to give a residue which is purified by chromatography on silica gel using 60% ethyl acetate-hexanes to give 1.1 g of the desired product as a yellow solid, m.p. 182° C.
Examples 26-36 in Table I are prepared under substantially the same conditions as Example 25 from the appropriately substituted hydroxylamine, quinazolinone N 6 -oxide and olefin starting materials.
TABLE I__________________________________________________________________________ ##STR22## Starting m.p. °C.Ex. Starting RNHOH.HCl Reaction or MassNo. R.sup.6 X Olefin R Time (Hours) Spec.__________________________________________________________________________26 ##STR23## (CH.sub.2).sub.3 CH.sub.3 Cis-cyclo- octene CH.sub.3 48 167°27 ##STR24## (CH.sub.2).sub.3 CH.sub.3 Cis-cyclo- octene CH.sub.3 48 176-180°28 ##STR25## (CH.sub.2).sub.3 CH.sub.3 2(5H)-- furanone CH.sub.3 24 190-193°29 ##STR26## (CH.sub.2).sub.3 CH.sub.3 Norbor- nylene CH.sub.3 24 166°30 ##STR27## (CH.sub.2).sub.3 CH.sub.3 1-cyclohex- ene-3-one CH.sub.3 48 186°31 ##STR28## (CH.sub.2 ).sub.3 CH.sub.3 cyclo- pentene CH.sub.3 48 147-149°32 ##STR29## (CH.sub.2).sub.3 CH.sub.3 1-cyclopen- tene-3-one CH.sub.3 8 182°33 ##STR30## (CH.sub.2).sub.3 CH.sub.3 1-cyclopen- tene-3-one PhCH.sub.2 24 418(M + H)34 ##STR31## (CH.sub.2).sub.3 CH.sub.3 1-cyclopen- tene-3-one PhCH.sub.2 24 418(M + H)35 ##STR32## (CH.sub.2).sub.3 CH.sub.3 2(5H)- furanone PhCH.sub.2 24 176°36 ##STR33## (CH.sub.2).sub.3 CH.sub.3 2(5H)- furanone PhCH.sub.2 24 151°__________________________________________________________________________
EXAMPLES 37 AND 38
(3α,3aα,6aα)-2-butyl-6-(hexahydro-2-methyl-4-oxofuro[3,4-d]isoxazol-3-yl)-3-[[2'-[1-(triphenylmethyl)-1H-tetrazol-5-yl][1,1'-biphenyl]-4-yl]methyl]-4(3H)-quinazolinone and
(3α,3aα,6aα) -2-butyl-6-(hexahydro-2-methyl-4-oxofuro[3,4-d]isoxazol-3-yl)-3-[[2'-[1-(triphenylmethyl)-1H-tetrazol-5-yl][1,1'-biphenyl]-4-yl]methyl]-4(3H)-quinazolinone isomer 2
A mixture of 343 mg of (3α,3aα,6aα)-2-butyl-6-(hexahydro-2-methyl-4-oxofuro[3,4-d]isoxazol-3-yl)-4(1H)-quinazolinone, 552 mg of 5-[4'-(bromomethyl)[1,1'-biphenyl]-2-yl]-1-(triphenylmethyl)-1H-tetrazole and 2 g of K 2 CO 3 in 200 ml of acetone is heated at reflux for 24 hours. The reaction mixture is filtered and the filtrate evaporated in vacuo to a residue which is purified by column chromatography on silica gel by elution with 30% ethyl acetate-hexanes to give 400 mg of the first desired product as a solid and 250 mg of the second desired product as a solid.
Examples 39-47 in Table II are prepared under substantially the same conditions as Examples 37 and 38 from the appropriately substituted quinazolinone starting materials.
TABLE II______________________________________ ##STR34## Ex. No. m.p. °C.Ex. S. or MassNo. R.sup.6 X Material Spec.______________________________________39 ##STR35## (CH.sub.2).sub.3 CH.sub.3 31 803 (M + H)40 ##STR36## (CH.sub.2).sub.3 CH.sub.3 29 829 (M + H)41 ##STR37## (CH.sub.2).sub.3 CH.sub.3 30 831 (M + H)42 ##STR38## (CH.sub.2).sub.3 CH.sub.3 27 846 (M + H)43 ##STR39## (CH.sub.2).sub.3 CH.sub.3 32 893 (M + H)44 ##STR40## (CH.sub.2).sub.3 CH.sub.3 33 894 (M + H)45 ##STR41## (CH.sub.2).sub.3 CH.sub.3 36 895 (M + H)46 ##STR42## (CH.sub.2).sub.3 CH.sub.3 35 895 (M + H)47 ##STR43## (CH.sub.2).sub.3 CH.sub.3 34 893 (M + H)______________________________________
EXAMPLE 48
(3α,3aα,6aα)-2-butyl-6-(hexahydro-2-methyl-4-oxo-2H-cyclopent[d]-isoxazol-3-yl)-3-[[2'-(1H-tetrazol-5-yl)[1,1'-biphenyl]-4-yl]methyl-4(3H)-quinazolinone
A mixture of 250 mg of (3α,3aα,6aα)-2-butyl-6-(hexahydro-2-methyl-2H-cyclopent[d]-isoxazol-3-yl)-3-[[2'-[1-(triphenylmethyl)-1H-tetrazol-5-yl][1,1'-biphenyl]-4-yl]methyl]-4(3H)-quinazolinone in 50 ml of 1:1 tetrahydrofuran-methanol is heated at reflux for 18 hours. The volatiles are evaporated in vacuo and the residue is purified by chromatography on silica gel thick layer plates using a solvent system of 60:20:20:5 ethyl acetate-hexanes-chloroform-methanol to give 110 mg of the desired product. m.p. 118° C.
Examples 49-57 in Table III are prepared under substantially the same conditions as Example 48 from the appropriately substituted quinazolinone starting materials.
TABLE III______________________________________ ##STR44## Ex. No. m.p. °C.Ex. S.. or MassNo. R.sup.6 X Material Spec.______________________________________49 ##STR45## (CH.sub.2).sub.3 CH.sub.3 41 126°50 ##STR46## (CH.sub.2).sub.3 CH.sub.3 39 562 (M + H)51 ##STR47## (CH.sub.2).sub.3 CH.sub.3 40 86°52 ##STR48## (CH.sub.2).sub.3 CH.sub.3 42 603 (M + H)53 ##STR49## (CH.sub.2).sub.3 CH.sub.3 38 160- 165°54 ##STR50## (CH.sub.2).sub.3 CH.sub.3 37 150°55 ##STR51## (CH.sub.2).sub.3 CH.sub.3 47 99°56 ##STR52## (CH.sub.2).sub.3 CH.sub.3 46 138°57 ##STR53## (CH.sub.2).sub.3 CH.sub.3 45 149°______________________________________
Angiotensin II Antagonists In Vitro Tests
Materials and Methods
Beef adrenals are obtained from a local slaughter house (maxwell-Cohen). [ 125 I](Sar 1 ,Ile 8 )AngII, S.A. 2200 Ci/mmole, is purchased from Dupont (NEN®, Boston, Mass.). All unlabeled AngII analogs, Dimethylsulfoxide (DMSO), nucleotides, bovine serum albumin (BSA) are purchased from Sigma Chemical Co., St. Louis, Mo. U.S.A.
Preparation of Membranes
Approximately sixteen (16) to twenty (20) beef adrenal glands are processed as follows: fresh adrenal glands received on crushed ice are cleaned of fatty tissues and the tough membranes encapsulating the glands are removed and discarded. The brownish tissue forming the adrenal cortex is scraped off and finely minced with scissors before homogenization. Care is taken to avoid contamination with medullary tissue during dissection. The scraped cortices are suspended in twenty volumes of an ice-cold buffer medium consisting of 10 mM Tris.HCl (pH 7.4 at 22° C.) and containing 1.0 mM EDTA and 0.2M sucrose. Unless otherwise indicated, all subsequent operations are done at 4° C. The tissue is homogenized in a glass homogenizer with a motor-driven teflon pestle with a clearance of 1.0 mm. The homogenate is centrifuged first at low speed (3,000× g) for 10 min. The resulting pellet is discarded and the supernatant fluid recentrifuged at 10,000× g for 15 minutes to give a P 2 pellet. This P 2 pellet is discarded and the liquid phase is carefully decanted off in clean centrifuge tubes and recentrifuged at high speed (100,000× g) for 60 min. The translucent final pellet is harvested and combined in a small volume (20-50.0 ml) of 50.0 mM Tris.HCl buffer, pH 7.2. A 100 ul aliquot is withdrawn and the protein content of the preparation is determined by the Lowry's method (Lowry, O. H., Rosebrough, N. F., Parr, A. L. and Randall, R. J., Protein measurement with Folin phenol reagent. J. Biol. Chem., 48, 265-275; 1951). The pelleted membrane is reconstituted in 50.0 mM Tris.HCl buffer containing 0.1 mM of phenylmethylsulfonyl fluoride (PMSF) to give approximately a protein concentration of 2.5 mg per ml of tissue suspension. The membrane preparation is finally aliquoted in 1.0 ml volumes and stored at -70° C. until use in the binding assays.
Receptor Binding Assay
Binding of [ 125 I](Sar 1 ,Ile 8 )AngII
The binding of [ 125 I](Sar 1 ,Ile 8 )AngII to microsomal membranes is initiated by the addition of reconstituted membranes (1:10 vols.) in freshly made 50.0 mM Tris.HCl buffer, pH 7.4 containing 0.25% heat inactivated bovine serum albumin (BSA): 80 ul membrane protein (10 to 20 ug/assay) to wells already containing 100 ul of incubation buffer (as described above) and 20 ul [ 125 I](Sar 1 ,ILE 8 )AngII (Specific Activity, 2200 Ci/mmole). Non-specific binding is measured in the presence of 1.0 uM unlabeled (Sar 1 ,ILE 8 )AngII, added in 20 ul volume. Specific binding for [ 125 I](Sar 1 ,Ile 8 ) AngII is greater than 90%. In competition studies, experimental compounds are diluted in dimethylsulfoxide (DMSO) and added in 20 ul to wells before the introduction of tissue membranes. This concentration of DMSO is found to have no negative effects on the binding of [ 125 I] (Sar 1 ,Ile 8 ) AngII to the membranes. Assays are performed in triplicate. The wells are left undisturbed for 60 min. at room temperature. Following incubation, all wells are harvested at once with a Brandel® Harvester especially designed for a 96 well plate (Brandel® Biomedical Research & Development Labs. Inc., Gaithersburg, Md., U.S.A.). The filter discs are washed with 10×1.0 ml of cold 0.9% NaCl to remove unbound ligand. Presoaking the filter sheet in 0.1% polyethyleneimine in normal saline (PEI/Saline) greatly reduces the radioactivity retained by the filter blanks. This method is routinely used. The filters are removed from the filter grid and counted in a Parkard® Cobra Gamma Counter for 1 min. (Packard Instrument Co., Downers Grove, Ill., U.S.A.). The binding data are analyzed by the non-linear interactive "LUNDON-1" program (LUNDON SOFTWARE Inc., Cleveland, Ohio U.S.A.). Compounds that displace 50% of the labelled angiotensin II at the screening dose of 50 μM are considered active compounds and are then evaluated in concentration-response experiments to determine their IC 50 values. The results are shown in Table IV.
TABLE IV______________________________________ ##STR54## Angiotensin IIEx. ReceptorNo. R.sup.6 X Binding IC.sub.50 (M)______________________________________18 ##STR55## (CH.sub.2).sub.3 CH.sub.3 4.2 × 10.sup.-821 ##STR56## (CH.sub.2).sub.3 CH.sub.3 1.6 × 10.sup.-848 ##STR57## (CH.sub.2).sub.3 CH.sub.3 5.7 × 10.sup.-849 ##STR58## (CH.sub.2).sub.3 CH.sub.3 88.0 × 10.sup.-850 ##STR59## (CH.sub.2).sub.3 CH.sub.3 9.9 × 10.sup.-851 ##STR60## (CH.sub.2).sub.3 CH.sub.3 15.0 × 10.sup.-852 ##STR61## (CH.sub.2).sub.3 CH.sub.3 18.0 × 10.sup.-853 ##STR62## (CH.sub.2).sub.3 CH.sub.3 7.1 × 10.sup.-854 ##STR63## (CH.sub.2).sub.3 CH.sub.3 16.0 × 10.sup.-855 ##STR64## (CH.sub.2).sub.3 CH.sub.3 7.8 × 10.sup.-856 ##STR65## (CH.sub.2).sub.3 CH.sub.3 9.4 × 10.sup.-857 ##STR66## (CH.sub.2).sub.3 CH.sub.3 18.0 × 10.sup.-8______________________________________
As can be seen from Table IV, the compounds demonstrate excellent Angiotensin II Receptor Binding activity.
The enzyme renin acts on a blood plasma α 2 -globulin, angiotensinogen, to produce angiotensin I, which is then converted by angiotensin converting enzyme to AII. The substance AII is a powerful vasopressor agent which is implicated as a causative agent for producing high blood pressure in mammals. Therefore, compounds which inhibit the action of the hormone angiotensin II (AII) are useful in alleviating angiotensin induced hypertension.
The compounds of this invention inhibit the action of AII. By administering a compound of this invention to a rat, and then challenging with angiotensin II, a blockage of the vasopressor response is realized. The results of this test on representative compounds of this invention are shown in Table II.
AII Challenge
Conscious Male okamoto-Aoki SHR, 16-20 weeks old, weighing approximately 330 g are purchased from Charles River Labs (Wilmington, Mass.). Conscious rats are restrained in a supine position with elastic tape. The area at the base of the tail is locally anesthetized by subcutaneous infiltration with 2% procaine. The ventral caudal artery and vein are isolated, and a cannula made of polyethylene (PE) 10-20 tubing (fused together by heat) is passed into the lower abdominal aorta and vena cava, respectively. The cannula is secured, heparinized (1,000 I.U./ml), sealed and the wound is closed. The animals are placed in plastic restraining cages in an upright position. The cannula is attached to a Statham P23Db pressure transducer, and pulsatile blood pressure is recorded to 10-15 minutes with a Gould Brush recorder. (Chan et al., (Drug Development Res., 18:75-94, 1989). Angiotensin II (human sequence, Sigma Chem. Co., St. Louis, Mo.) of 0.05 and 0.1 ug/kg i.v. is injected into all rats (predosing response). Then a test compound, vehicle or a known angiotensin II antagonist is administered i.v., i.p. or orally to each set of rats. The two doses of angiotensin II are given to each rat again at 30, 60, 90, 120, 180, 240 and 300 minutes post dosing the compound or vehicle. The vasopressor response of angiotensin II is measured for the increase in systolic blood pressure in mmHg. The percentage of antagonism or blockade of the vasopressor response of angiotensin II by a compound is calculated using the vasopressor response (increase in systolic blood pressure) of angiotensin II of each rat predosing the compound as 100%. A compound is considered active if at 30 mg/kg i.v. it antagonized at least 50% of the response.
__________________________________________________________________________ANGIOTENSIN II (AII) VASOPRESSOR RESPONSE Dose AII Dose Min Post Control Response Average & (mg/kg) mcg/kg IV Dose Before AII After AII Change Change Inhibition__________________________________________________________________________SPONTANEOUSLY HYPERTENSIVE RATS n = 2 Body Weight(s): 355, 340 gramsCONTROL 0.05 0 220 275 55 47.5 190 230 40 0.1 215 275 60 50 190 230 40Ex. No. 3 I.V. 0.05 30 185 210 25 15 6818 230 235 5 0.1 230 245 15 12.5 75 190 200 10 0.05 60 220 250 30 22.5 53 190 205 15 0.1 220 250 30 20 60 190 200 10 0.05 90 230 260 30 25 47 190 210 20 0.1 250 280 30 27.5 45 190 215 25 0.05 120 200 220 20 45 5 190 260 70 0.1 200 225 25 50 0 190 265 75 0.05 180 230 255 25 20 58 180 195 15 0.1 230 260 30 25 50 220 240 20SPONTANEOUSLY HYPERTENSIVE RATS n = 2 Body weight(s): 330, 340 grams 0.05 240 220 240 20 17.5 63 185 200 15 0.1 220 270 50 45 10 180 220 40 0.05 300 210 250 40 42.5 11 165 210 45 0.1 230 270 40 27.5 45 180 195 15CONTROL 0.05 0 255 315 60 47.5 230 265 35 0.1 260 322 62 57Ex. No. 1 I.V. 0.05 30 250 270 20 22.5 5321 200 225 25 0.1 260 290 30 27 53 220 244 24 0.05 60 250 265 15 15 68 220 235 15 0.1 250 285 35 25 56 225 240 15 0.05 90 260 285 25 17.5 63 225 235 10 0.1 255 295 40 27.5 52 225 240 15SPONTANEOUSLY HYPERTENSIVE RATS n = 2 Body weight(s): 360, 330 grams 0.05 120 255 275 20 17.5 63 215 230 15 0.1 250 270 20 22.5 61 220 245 25 0.05 180 245 265 20 17.5 63 215 230 15 0.1 240 275 35 30 47 215 240 25 0.05 240 240 270 30 27.5 42 225 250 25 0.1 245 270 25 22.5 61 225 245 20 0.05 300 235 265 30 30 37 215 245 30 0.1 245 280 35 37.5 34 220 260 40CONTROL 0.05 0 200 245 45 37.5 180 210 30 0.1 205 250 45 42.5 175 215 40Ex. No. 3 I.V. 0.05 30 200 205 5 2.5 9348 170 170 0 0.1 205 210 5 2.5 94 160 160 0SPONTANEOUSLY HYPERTENSIVE RATS n = 2 Body weight(s): 360, 330 grams 0.05 60 200 200 0 0 100 165 165 0 0.1 195 202 7 6 86 160 165 5 0.05 90 190 195 5 5 87 165 170 5 0.1 190 205 15 10 76 180 185 5 0.05 120 210 215 5 4 89 170 173 3 0.1 205 215 10 7.5 82 170 175 5 0.05 180 190 205 15 15 60 160 175 15 0.1 185 215 30 22.5 47 170 185 15 0.05 240 195 210 15 15 60 170 185 15 0.1 200 215 15 22.5 47 160 190 30 0.05 300 185 210 25 20 47 165 180 15 0.1 200 215 15 27.5 35 150 190 40SPONTANEOUSLY HYPERTENSIVE RATS n = 2 Body weight(s): 270, 280 gramsCONTROL 0.05 0 205 242 37 41 190 235 45 0.1 210 255 45 47.5 190 240 50Ex. No. 5 P.O. 0.05 30 205 210 5 10 7648 195 210 15 0.1 195 210 15 16 66 190 207 17 0.05 60 200 205 5 10 76 185 200 15 0.1 195 205 10 12.5 74 185 200 15 0.05 90 185 202 17 8.5 79 195 195 0 0.1 190 202 12 7 85 195 197 2 0.05 120 205 205 0 4 90 190 198 8 0.1 207 207 0 5 89 185 195 10 0.05 180 185 185 0 7.5 82 185 200 15 0.1 185 190 5 12.5 74 180 200 20SPONTANEOUSLY HYPERTENSIVE RATS n = 2 Body weight(s): 280, 290 grams 0.05 240 185 185 0 2.5 94 180 185 5 0.1 180 190 10 10 79 180 190 10 0.05 300 200 205 5 3 93 175 176 1 0.1 190 200 10 10 79 175 185 10CONTROL 0.05 0 152 200 48 44 190 230 40 0.1 160 215 55 52.5 190 240 50Ex. No. 1 I.V. 0.05 30 165 180 15 15 6648 195 210 15 0.1 165 190 25 25 52 190 215 25 0.05 60 160 180 20 20 55 190 210 20 0.1 170 185 15 15 71 195 210 15 0.05 90 157 185 28 26.5 40 190 215 25 0.1 175 195 20 25 52 195 225 30SPONTANEOUSLY HYPERTENSIVE RATS n = 2 Body weight(s): 350, 330 grams 0.05 120 170 195 25 22.5 49 195 215 20 0.1 175 205 30 36 31 183 225 42 0.05 180 165 200 35 27.5 38 175 195 20 0.1 175 215 40 32.5 38 175 200 25 0.05 240 175 215 40 32.5 26 175 200 25 0.1 175 218 43 35.5 32 175 203 28 0.05 300 170 217 47 36 18 175 200 25 0.1 172 210 38 36.5 30 175 210 35CONTROL 0.05 0 196 232 36 38 195 235 40 0.1 182 235 53 54 170 225 55Ex. No. 10 I.V. 0.05 30 200 200 0 0 10049 155 155 0 0.1 192 205 13 6.5 88 160 160 0 0.05 60 185 185 0 1 97 175 177 2 0.01 175 185 10 7.5 86 165 170 5 0.05 90 170 175 5 5 87 160 165 5 0.1 170 175 5 7.5 86 150 160 10 0.05 120 174 180 6 5.5 86 175 180 5 170 180 10 10 81 165 175 10 0.05 180 180 190 10 12.5 67 165 180 15 0.1 175 195 20 20 63 170 190 20SPONTANEOUSLY HYPERTENSIVE RATS n = 2 Body weight(s): 330, 330 gramsCONTROL 0.05 0 207 250 43 34 205 230 25 0.1 200 250 50 42.5 205 250 35Ex. No. 5 P.O. 0.05 30 200 233 33 21.5 3749 200 210 10 0.1 203 236 33 26.5 38 195 215 20 0.05 60 195 215 20 14 59 202 210 8 0.1 195 235 40 30 29 195 215 20 0.05 90 195 210 15 15 56 190 205 15 0.1 190 205 15 17.5 59 200 220 20 0.05 120 185 210 25 20 41 190 205 15 0.1 195 218 23 19 55 195 210 15 0.05 180 200 215 15 12.5 63 200 210 10 0.1 195 235 40 27.5 35 195 210 15SPONTANEOUSLY HYPERTENSIVE RATS n = 2 Body weight(s): 310, 305 grams 0.05 240 200 230 30 22.5 34 185 200 15 0.1 200 235 35 27 36 186 205 19CONTROL 0.05 0 200 270 70 55 240 280 40 0.1 200 265 65 55 235 280 45Ex. No. 3 I.V. 0.05 30 200 235 35 20 6450 225 230 5 0.1 210 235 25 18.5 66 218 230 12 0.05 60 195 218 23 16.5 70 210 220 10 0.1 200 225 25 19 65 220 233 13 0.05 90 190 202 12 11 80 215 225 10 0.1 190 225 35 26.5 52 220 238 18 0.05 120 185 207 22 18.5 66 210 225 15 0.1 185 210 25 14 75 210 213 3 0.05 180 200 225 25 22.5 59 200 220 20 0.1 190 220 30 17.5 68 220 225 5SPONTANEOUSLY HYPERTENSIVE RATS n = 2 Body weight(s): 315, 370 gramsCONTROL 0.05 0 195 235 40 42.5 185 230 45 0.1 200 240 40 42.5 190 235 45Ex. No. 5 P.O. 0.05 30 200 215 15 22.5 4750 195 225 30 0.1 198 227 29 32 25 185 220 35 0.05 60 205 225 20 22.5 47 185 210 25 0.1 210 228 18 29 32 185 225 40 0.05 90 200 230 30 20 53 180 190 10 0.1 200 230 30 20.5 52 185 196 11 0.05 120 203 220 17 13.5 68 190 200 10 0.1 205 240 35 22.5 185 195 10 0.05 180 185 220 35 27.5 35 160 180 20 0.1 205 240 35 35 18 160 195 35SPONTANEOUSLY HYPERTENSIVE RATS n = 2 Body weight(s): 300, 320 gramsCONTROL 0.05 0 215 240 25 30 200 235 35 0.1 205 237 32 41Ex. No. 1 I.V. 0.05 30 190 220 30 25 1750 190 210 20 0.1 185 215 30 25 39 190 210 20 0.05 60 190 220 30 25 17 180 200 20 0.1 185 220 35 30 27 185 210 25 0.05 990 190 225 35 24 20 180 193 13 0.1 190 230 40 37.5 9 180 215 35 0.05 120 190 225 35 25 17 180 195 15 0.1 207 240 33 26.5 35 180 200 20 0.05 180 220 245 25 22.5 25 195 215 20 0.1 225 250 25 27.5 33 185 215 30SPONTANEOUSLY HYPERTENSIVE RATS n = 2 Body weight(s): 340, 340 grams 0.05 240 185 230 45 32.5 -8 185 205 20 0.1 195 250 55 47.5 -16 175 215 40 0.05 300 185 240 55 37.5 -25 190 210 20 0.1 191 244 53 45.5 -11 180 218 38CONTROL 0.05 0 160 198 38 45 170 222 52 0.1 165 232 67 61 185 240 55Ex. No. 3 I.V. 0.05 30 185 185 0 5 8951 175 185 10 0.1 170 183 13 8 87 180 183 3 0.05 60 165 195 30 16.5 63 170 173 3 0.1 175 195 20 11 82 175 177 2 0.05 90 165 177 12 10 78 175 183 8 0.1 185 205 20 12.5 80 180 185 5SPONTANEOUSLY HYPERTENSIVE RATS n = 2 Body weight(s): 300, 290 grams 0.05 120 165 175 10 7.5 83 165 170 5 0.1 165 186 21 15.5 75 180 190 10 0.05 180 165 180 15 15 67 170 185 15 0.1 165 190 25 22.5 63 165 185 20CONTROL 0.05 0 220 265 45 37.5 210 240 30 0.1 220 265 45 42.5 200 240 40Ex. No. 3 I.V. 0.05 30 220 225 5 4 8952 200 203 3 0.1 220 230 10 10 76 195 205 10 0.05 60 220 225 5 7.5 80 190 200 10 0.1 205 225 20 17.5 59 185 200 15 0.05 90 200 242 42 28.5 24 190 205 15 0.1 210 240 30 20 53 185 195 10SPONTANEOUSLY HYPERTENSIVE RATS n = 2 Body weight(s): 300, 330 grams 0.05 120 225 250 25 14 63 190 193 3 0.1 225 250 24 17.5 59 195 205 10 0.05 180 200 230 30 30 20 190 220 30 0.1 225 265 40 37.5 12 190 225 35 0.05 240 225 255 30 27.5 27 180 205 25 0.1 235 260 25 22.5 47 180 200 20 0.05 300 225 250 25 33 180 205 25 0.1 225 260 35 36 15 183 220 37CONTROL 0.05 0 195 232 37 40 192 235 43 0.1 185 235 50 42.5 200 235 35Ex. No. 5 P.O. 0.05 30 195 200 5 10 7553 195 210 15 0.1 195 200 5 17.5 59 185 215 30SPONTANEOUSLY HYPERTENSIVE RATS n = 2 Body weight(s): 300, 330 grams 0.05 60 175 175 0 7.5 81 185 200 15 0.1 175 190 15 20 53 185 210 25 0.05 90 170 170 0 5 88 180 190 10 0.1 170 175 5 10 76 175 190 15 0.05 120 165 165 0 1 98 175 185 10 0.1 165 177 12 11 74 175 185 10 0.05 180 165 165 0 1.5 96 175 178 3 0.1 165 170 5 9 79 170 183 13 0.05 240 160 170 10 12.5 69 160 175 15 0.1 165 180 15 12.5 71 175 185 10 0.05 300 155 165 10 6.5 84 170 173 3 0.1 155 175 20 20 53 155 175 20SPONTANEOUSLY HYPERTENSIVE RATS n = 2 Body weight(s): 340, 335 gramsCONTROL 0.05 0 180 218 38 39 185 225 40 0.1 175 225 50 49Ex. No. 3 I.V. 0.05 30 185 190 5 10 7453 185 200 15 0.1 180 190 10 9.5 81 183 192 9 0.05 60 175 175 0 0.5 99 184 185 1 0.1 200 200 0 2.5 95 200 205 5 0.05 90 170 185 15 12.5 68 180 190 10 0.1 180 198 18 16.5 66 183 198 15 0.05 120 175 190 15 22.5 42 180 210 30 0.1 180 205 25 17.5 64 190 200 10 0.05 180 185 190 5 9 77 185 198 13 0.1 195 210 15 17.5 64 180 200 20SPONTANEOUSLY HYPERTENSIVE RATS n = 2 Body weight(s): 330, 380 grams 0.05 240 175 200 25 25 36 185 210 25 0.1 175 210 35 27.5 44 190 210 20 0.05 300 178 198 20 49 175 195 20 0.1 175 205 30 30 39 175 205 30CONTROL 0.05 0 230 275 45 45 240 285 45 0.1 220 280 60 55 240 290 50Ex. No. 3 I.V. 0.05 30 235 235 0 1.5 9755 235 238 3 0.1 225 230 5 2.5 95 240 240 0 0.05 60 230 230 0 0 100 240 240 0 0.1 225 230 5 2.5 95 240 240 0 0.05 90 230 235 5 5 89 237 242 5 0.1 220 225 5 5 91 235 240 5SPONTANEOUSLY HYPERTENSIVE RATS n = 2 Body weight(s): 330, 345 grams 0.05 120 225 225 0 1.5 97 232 235 3 0.1 215 222 7 3.5 94 235 235 0 0.05 180 220 225 5 2.5 240 240 0 0.1 215 225 10 12.5 77 230 245 15 0.05 240 220 225 5 5 89 240 245 5 0.1 220 230 10 10 82 240 250 10 0.05 300 210 230 20 17.5 61 225 240 15 0.1 220 240 20 27.5 50 215 250 35CONTROL 0.05 0 230 260 30 35 200 240 40 0.1 220 260 40 45 200 250 50Ex. No. 3 P.O. 0.05 30 225 240 15 27.5 2155 195 235 40 0.1 220 250 30 37.5 17 195 240 45SPONTANEOUSLY HYPERTENSIVE RATS n = 2 Body weight(s): 310, 330 grams 0.05 60 210 240 30 32.5 7 215 250 35 0.1 215 255 40 40 11 205 245 40 0.05 90 205 230 25 30 14 210 245 35 0.1 215 245 30 37.5 17 205 250 45 0.05 120 205 220 15 27.5 21 205 245 40 0.1 205 230 25 27.5 39 210 240 30 0.05 180 205 240 35 30 14 205 230 25 0.1 210 240 30 32.5 28 205 240 35CONTROL 0.05 0 210 245 35 27.5 220 240 20 0.1 220 255 35 31 230 257 27Ex. No. 3 P.O. 0.05 30 215 238 23 19 3156 215 230 15 0.1 220 245 25 27.5 11 210 240 30SPONTANEOUSLY HYPERTENSIVE RATS n = 2 Body weight(s): 300, 310 grams 0.05 60 215 230 15 22.5 18 200 230 30 0.1 210 240 30 25 19 210 230 20 0.05 90 205 225 20 17.5 36 215 230 15 0.1 200 230 30 25 19 215 235 20 0.05 120 205 230 25 17.5 36 210 220 10 0.1 200 230 30 22.5 27 220 235 15 0.05 180 195 235 40 30 -9 220 240 20 0.1 200 230 30 30 3 215 245 30CONTROL 0.05 0 245 280 35 32.5 225 255 30 0.1 240 285 45 45 220 265 45Ex. No. 3 I.V. 0.05 30 245 245 0 0 10056 220 220 0 0.1 240 240 0 0 100 220 220 0CONTROL 0.05 60 240 240 0 0 100 190 190 0 0.1 230 235 5 5 89 185 190 5 0.05 90 230 230 0 0 100 190 190 0 0.1 235 240 5 5 89 180 185 5 0.05 120 225 240 15 7.5 77 195 195 0 0.1 235 245 10 10 78 195 205 10 0.05 180 225 235 10 7.5 77 195 200 5 0.1 230 242 12 11 76 195 205 10 0.05 240 235 245 10 9 72 185 193 8 0.1 235 260 25 20 56 195 210 15 0.05 300 230 240 10 11.5 65 195 208 13 0.1 240 245 5 15 67 190 215 25SPONTANEOUSLY HYPERTENSIVE RATS n = 2 Body weight(s): 320, 320 gramsCONTROL 0.05 0 220 265 45 35 220 245 25 0.1 215 270 55 40 225 250 25Ex. No. 3 I.V. 0.05 30 210 210 0 0 10057 220 220 0 0.1 210 211 1 0.5 99 215 215 0 0.05 60 230 230 0 0 100 215 215 0 0.1 220 230 10 5 88 215 215 0 0.05 90 230 235 5 2.5 93 215 215 0 0.1 205 225 20 10 75 215 215 0 0.05 120 208 215 7 3.5 90 210 210 0 0.1 205 220 15 7.5 81 220 220 0 0.05 180 195 220 25 13.5 61 210 212 2 0.1 210 230 20 10 75 215 215 0SPONTANEOUSLY HYPERTENSIVE RATS n = 2 Body weight(s): 310, 325 grams 0.05 240 230 240 10 8 77 214 220 6 0.1 220 240 20 17.5 56 210 225 15 0.05 300 210 225 15 10 71 215 220 5 0.1 210 235 25 25 38 210 235 25CONTROL 0.05 0 214 250 36 38 215 255 40 0.1 210 260 50 47.5 220 265 45Ex. No. 3 P.O. 0.05 30 210 235 25 25 3457 210 235 25 0.1 210 240 30 30 37 210 240 30 0.05 60 215 230 15 12.5 67 225 235 10 0.1 210 240 30 22.5 53 220 235 15 0.05 90 205 220 15 20 47 205 230 25 0.1 210 230 20 25 47 210 240 30SPONTANEOUSLY HYPERTENSIVE RATS n = 2 Body weight(s): 310, 325 grams 0.05 120 210 240 30 22.5 41 205 220 15 0.1 215 240 25 17.5 63 210 220 10 0.05 180 195 238 43 34 11 215 240 25 0.1 210 240 30 22.5 53 225 240 15__________________________________________________________________________
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The invention provides novel 2,3,6 substituted quinazolinones having the formula: ##STR1## wherein R 6 , R and X are as described in the specification, which have activity as angiotensin II (AII) antagonists.
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TECHNICAL FIELD
[0001] The present invention relates to a method for preparing a light olefin using an oxygen-containing compound, and a device for use thereof.
BACKGROUND
[0002] Light olefins, i.e. ethylene and propylene, are two important kinds of basic chemical raw materials, and the demand thereof is increasing. Generally, ethylene and propylene are produced via a petroleum scheme. However, the costs for producing ethylene and propylene from petroleum resources are increasing due to limited supply and relatively high price of petroleum resources. In recent years, techniques for preparing ethylene and propylene by converting substituent raw materials have been greatly developed. More and more attentions have been paid to the process of methanol-to-olefins (MTO), and the production scale of megatonnage has been achieved. As the world economy develops, the demand for light olefins, particularly propylene, is increasing day by day. It is reported as the analysis of CMAI Corporation that the demand for ethylene will increase at an average rate of 4.3% per year and the demand for propylene will increase at an average rate of 0.4% per year until 2016. Due to high-speed increase of the economy in China, all of the annual increase rates of the demand for ethylene and propylene in China exceed the average level of the world.
[0003] In early 1980s, UCC Corporation successfully developed SAPO series molecular sieves. Among others, SAPO-34 molecular sieve catalyst exhibits excellent catalytic performance when it is used in MTO reaction, and has very high selectivity for light olefins and very high activity. However, after the catalyst has been used for a period of time, the activity is lost due to carbon deposition. A remarkable induction period is present in the use of the SAPO-34 molecular sieve catalyst. In the induction period, the selectivity for olefins is relatively low and the selectivity for alkanes is relatively high. As the reaction time increases, the selectivity for light olefins gradually increases. After the induction period, the catalyst maintains high selectivity and high activity in a certain period of time. With further prolong of the time, however, the activity of the catalyst rapidly decreases.
[0004] U.S. Pat. No. 6,166,282 discloses a technique and a reactor for converting methanol to light olefins, which use a fast fluidized bed reactor, wherein after the completion of a reaction in a dense phase reaction zone having a relatively low gas speed, the gas phase rises to a fast separation zone having an inner diameter which rapidly becomes smaller, and most of the entrained catalyst is preliminarily separated using a special gas-solid separation apparatus. Since the product gas and the catalyst are rapidly separated after reaction, a secondary reaction is effectively prevented. Upon analog computation, the inner diameter of the fast fluidized bed reactor and the catalyst inventory required are both greatly reduced, compared to the conventional bubbling fluidized bed reactors. However, the carbon based yields of light olefins in this method are all typically about 77%, and there are problems concerning relatively low yields of light olefins.
[0005] CN101402538B discloses a method for increasing the yield of light olefins. This method provides a second reaction zone on the upper part of a first reaction zone for converting methanol to light olefins, and the diameter of the second reaction zone is greater than that of the first reaction zone to increase the residence time of the product gas from the outlet of the first reaction zone in the second reaction zone, such that the unreacted methanol, the generated dimethyl ether, and hydrocarbons having 4 or more carbons continue to react so as to achieve the object of increasing the yield of light olefins. This method may increase the yield of light olefins to some extent. However, since the catalyst come out from the first reaction zone has already carried a relatively great amount of deposited carbon and relatively high catalyst activity is required to crack hydrocarbons having 4 or more carbons, the conversion efficiencies of hydrocarbons having 4 or more carbons in the second reaction zone in this method are still relatively low, leading to a lower yield of light olefins.
[0006] CN102276406A discloses a method for increasing the production of propylene. This technique provides three reaction zones, wherein a first fast bed reaction zone is used for converting methanol to olefins, and a lift pipe reaction zone and a second fast bed reaction zone are connected in series to convert ethylene, hydrocarbons having 4 or more carbons, and unreacted methanol or dimethyl ether. In this patent application, the residence times of substances, such as hydrocarbons having 4 or more carbons, etc., in the lift pipe reaction zone and in the second fast bed reaction zone are relatively short and the conversion efficiencies are relatively low, such that the yield of propylene is relatively low.
[0007] CN102875289A discloses a fluidized bed reaction device with a lift pipe reactor arranged therein, which is used for increasing the yield of light olefins. A first raw material is passed into a fluidized bed reaction zone and is brought into contact with a catalyst to generate a product comprising light olefins, and at the meanwhile a spent catalyst is formed; a part of the spent catalyst is passed into a regenerator for regeneration to form a regenerated catalyst, and the other part of the spent catalyst is passed into a lift pipe with an outlet end located inside the reaction zone and is brought into contact with a second raw material so as to lift the spent catalyst into the reaction zone; and the regenerated catalyst is returned to the reaction zone of the fluidized bed reactor. Since the reaction device disclosed in this patent application does not comprise a stripping portion, the spent catalyst will be passed into the regenerator with carrying a part of the product gas, which is combusted with oxygen to reduce the yield of light olefins.
[0008] The technique for preparing olefins from methanol disclosed in CN102875296A provides three reaction zones, which are a fast bed, a downer, and a lift pipe. Since the catalyst is circulated among the regenerator, the fast bed, the lift pipe, and the downer, the flow direction is extremely complicated, the distribution and the control of the flow rate are extremely difficult, and the activity of catalyst greatly varies.
[0009] As well known in the art, the selectivity for light olefins is closely associated with the amount of carbon deposition on the catalyst. A certain amount of carbon deposition on SAPO-34 catalyst is needed to ensure a high selectivity for light olefins. Main reactors used in current MTO process are fluidized beds. The fluidized bed is close to a perfect mixing flow reactor, which has a wide distribution of carbon deposition on catalyst and is not advantageous for increasing the selectivity for light olefins. Since the catalyst-to-alcohol ratio is very small and the coke yield is relatively low in the MTO process, in order to achieve a lager and controllable catalyst circulation volume, it is required to control the amount of carbon deposition and the uniformity of carbon content on the catalyst to a certain level in the regeneration zone, thereby achieving the object of controlling the amount of carbon deposition and the uniformity of carbon content on the catalyst in the reaction zone. Therefore, it is a key technique in the MTO process to control the amount of carbon deposition and the uniformity of carbon content of the catalyst in the reaction zone to a certain level.
[0010] In order to solve the problems described above, some researchers propose the techniques, such as providing an upper and a lower reaction zones in a fluidized bed, two fluidized beds connected in series, and a fluidized bed, a lift pipe, and a downer connected in series, etc. These preliminarily disclose methods for controlling the amount of carbon deposition and the uniformity of carbon content of the catalyst, and certain advantageous effects have been obtained. However, the complexity and the difficulty for controlling the MTO process are increased at the meanwhile. The present invention proposes a solution in which a plurality of secondary reaction zones (regeneration zones) are formed by providing inner members in a dense phase fluidized bed, to solve the problem of controlling the amount of carbon deposition and the uniformity of carbon content of the catalyst so as to increase the selectivity for light olefins.
SUMMARY OF THE INVENTION
[0011] The technical problem to be solved by the present invention is the problem that the selectivity for light olefins is not high in the prior art, and the object is to provide a new method for increasing the selectivity for light olefins. This method is used in the production of light olefins, and has the advantages of good uniformity of carbon deposition on catalyst, relatively high yield of light olefins, and good economical efficiency of the production process of light olefins.
[0012] In order to achieve the above object, in one aspect, the present invention provides a method for preparing a light olefin using an oxygen-containing is compound, comprising the following steps:
[0013] step a) in which a raw material comprising the oxygen-containing compound is introduced in parallel from n feeding branch lines into 1 st to n th secondary reaction zones in a dense phase fluidized bed reactor, and is brought into contact with a catalyst to generate a light olefin product-containing stream and a spent catalyst, wherein said catalyst is sequentially passed through 1 st to n th secondary reaction zones, with the carbon content thereof increasing gradually, and wherein said dense phase fluidized bed reactor is divided by a material flow controller into n secondary reaction zones;
[0014] step b) in which the light olefin product-containing stream flowed out from the 1 st to n th secondary reaction zones is separated from the spent catalyst that it carries; said light olefin product-containing stream is passed into a product separation section, and after separation and purification, a light olefin product is obtained; the isolated spent catalyst is passed into the n th secondary reaction zone; and
[0015] step c) in which the spent catalyst flowed out from the n th secondary reaction zone, after being stripped and lifted, is passed into a dense phase fluidized bed regenerator for regeneration; said spent catalyst is sequentially passed through 1 st to m th secondary regeneration zones; a regeneration medium is introduced in parallel from in feeding branch lines of regeneration zone into the 1 st to m th secondary regeneration zones; the spent catalyst is brought into contact with the regeneration medium, with the carbon content thereof decreasing gradually; after the completion of the regeneration, the catalyst is returned back to the 1 st secondary reaction zone via stripping and lifting; wherein the dense phase fluidized bed regenerator is divided by a material flow controller into in secondary regeneration zones; wherein n≧2 and m≧2, more preferably 8≧n≧3 and 8≧m≧3.
[0016] In a preferred embodiment, in the dense phase fluidized bed reactor, the apparent linear velocity of gas in the material flow controller is less than or equals to the minimum fluidizing velocity of the catalyst.
[0017] In a preferred embodiment, in the dense phase fluidized bed regenerator, the apparent linear velocity of gas in the material flow controller is less than or equals to the minimum fluidizing velocity of the catalyst.
[0018] In a preferred embodiment, the catalyst comprises SAPO-34 molecular sieve.
[0019] In a preferred embodiment, the reaction conditions of the reaction zone in the dense phase fluidized bed are as follows: the apparent linear velocity of gas is 0.1-1.5 m/s, reaction temperature is 400-550° C., the bed density is 200-1200 kg/m 3 .
[0020] In a preferred embodiment, the average carbon deposition amount of the catalyst is increased sequentially in the 1 st to n th secondary reaction zones of the dense phase fluidized bed, wherein the average carbon deposition amount of the catalyst in the 1 st secondary reaction zone is 0.5-3 wt %, the average carbon deposition amount of the catalyst in the n th secondary reaction zone is 7-10 wt %.
[0021] In a preferred embodiment, the reaction conditions in the dense phase fluidized bed regeneration zone are as follows: the apparent linear velocity of gas is 0.1-1.5 m/s, the regeneration temperature is 500-700° C., and the bed density is 200-1200 kg/m 3 .
[0022] In a preferred embodiment, the average carbon deposition amount of the catalyst is decreased sequentially from the 1 st to m th secondary regeneration zones of the dense phase fluidized bed regeneration zone, wherein the average carbon deposition amount of the catalyst in the 1 st secondary regeneration zone is 3-10 wt %, and the average carbon deposition amount of the catalyst in the m th secondary regeneration zone is 0-3 wt %.
[0023] In a preferred embodiment, the oxygen-containing compound is methanol and/or dimethyl ether; the light olefin is any one of ethylene, propylene or butylenes, or a mixture thereof; and the regeneration medium is any one of air, oxygen-deficient air or water vapor, or a mixture thereof.
[0024] In another aspect, the present invention provides a dense phase fluidized is bed reactor for carrying out the above method, said dense phase fluidized bed reactor comprising a reaction zone, a gas-solid separation zone, and a stripping zone, characterized in that said reaction zone is divided by a material flow controller into n secondary reaction zones, wherein n≧2.
[0025] In another aspect, the present invention provides a dense phase fluidized bed regenerator for carrying out the above method, said dense phase fluidized bed regenerator comprising a regeneration zone, a gas-solid separation zone, and a stripping zone, characterized in that said regeneration zone is divided by a material flow controller into in secondary regeneration zones, wherein m≧2.
[0026] The advantageous effects of the present invention include, but are not limited to, the following aspects: (1) the dense phase fluidized bed has a relatively high bed density, a relatively low catalyst velocity, and a low abrasion; (2) the gas velocity in the material downward flow pipe of the material flow controller is less than or equals to the minimal fluidization velocity of the catalyst and the catalyst is in a dense phase packing state, such that a unidirectional dense phase conveying stream of the catalyst is formed, the backmixing of catalyst between adjacent secondary reaction zones (or adjacent secondary regeneration zones) is prevented, and the distribution of residence time is narrow; (3) the heat extraction member in the material flow controller has an effect of controlling the temperature of the reaction zone; (4) the reaction zone is divided into n secondary reaction zones by the material flow controller and the catalyst sequentially passes through the 1 st secondary reaction zone to the n th secondary reaction zone, such that the distribution of residence time is narrow and the uniformity of carbon content of the spent catalyst is greatly increased; (5) the regeneration zone is divided into in secondary regeneration zones by the material flow controller and the catalyst sequentially passes through the 1 st secondary regeneration zone to the m th secondary regeneration zone, such that the distribution of residence time is narrow and the uniformity of carbon content of the regenerated catalyst is greatly increased; (6) relatively precise control of carbon content of the is regenerated catalyst and the spent catalyst is achieved, the distribution of carbon content is relatively uniform, the selectivity for light olefins is increased, and the carbon content may be regulated as needed to optimize the ratio of propylene/ethylene; (7) since the distribution of carbon content of the catalyst is relatively uniform, the catalyst inventory required in the reaction zone decreases; (8) the configuration of a plurality of secondary reaction zones facilitates the achievement of large-scale reactors.
DESCRIPTION OF FIGURES
[0027] FIG. 1 is a schematic flow chart of the method in the present invention;
[0028] FIG. 2 is a structural schematic diagram of the dense phase fluidized bed comprising 4 secondary reaction zones in the present invention, wherein the arrows in the A-A sectional view show the flow direction of the catalyst between the secondary reaction zones;
[0029] FIG. 3 is a structural schematic diagram of the dense phase fluidized bed comprising 4 secondary regeneration zones in the present invention, wherein the arrows in B-B sectional view show the flow direction of the catalyst between the secondary regeneration zones;
[0030] FIG. 4 is a structural schematic diagram of the stripper in the present invention;
[0031] FIG. 5 is a structural schematic diagram of the material flow controller in the present invention.
[0032] The reference signs of the figures are illustrated as follows: 1 : reactor feed line; 1 - 1 : feeding branch line of 1 st secondary reaction zone; 1 - 2 : feeding branch line of 2 nd secondary reaction zone; 1 - 3 : feeding branch line of 3 rd secondary reaction zone; 1 - 4 : feeding branch line of 4 th secondary reaction zone; 2 : dense phase fluidized bed reactor; 2 - 1 : 1 st secondary reaction zone; 2 - 2 : 2 nd secondary reaction zone; 2 - 3 : 3 rd secondary reaction zone; 2 - 4 : 4 th secondary reaction zone; 3 : cyclone separator; 4 : product material line; 5 : stripper; 6 : water vapor line; 7 : lift pipe ; 8 : lifting gas line; 9 : regenerator feed line; 9 - 1 : feeding branch line of 1 st secondary regeneration zone; 9 - 2 : feeding branch line of 2 nd secondary regeneration zone; 9 - 3 : feeding branch line of 3 rd secondary regeneration zone; 9 - 4 : feeding branch line of 4 th secondary regeneration zone; 10 : dense phase fluidized bed regenerator; 10 - 1 : 1 st secondary regeneration zone; 10 - 2 : 2 nd secondary regeneration zone; 10 - 3 : 3 rd secondary regeneration zone; 10 - 4 : 4 th secondary regeneration zone; 11 : cyclone separator; 12 : exhaust gas line; 13 : stripper; 14 : water vapor line; 15 : lift pipe; 16 : lifting gas line; 17 : material flow controller; 18 : material overflow port; 19 : partition plate; 20 : orifice; 21 : material downward flow pipe; 22 : bottom baffle ; 23 : heat extraction member.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0033] In order to increase the selectivity for light olefins in the process of preparation of a light olefin using an oxygen-containing compound, the present invention provides a method for preparing a light olefin using an oxygen-containing compound, comprising the following steps:
a) a step in which a raw material comprising the oxygen-containing compound is introduced in parallel from n feeding branch lines into 1 st to n th secondary reaction zones in a dense phase fluidized bed reactor, and is brought into contact with a catalyst to generate a light olefin product-containing stream and a spent catalyst, wherein said catalyst is sequentially passed through 1 st to n th secondary reaction zones, with the carbon content thereof increasing gradually, and wherein said dense phase fluidized bed reactor is divided by a material flow controller into n secondary reaction zones; b) a step in which the light olefin product-containing stream flowed out from the 1 st to n th secondary reaction zones is separated from the spent catalyst that it carries; said light olefin product-containing stream is passed into a product separation section, and after separation and purification, a light olefin product is obtained; the isolated spent catalyst is passed into the n th secondary reaction zone; and c) a step in which the spent catalyst flowed out from the n th secondary reaction zone, after being stripped and lifted, is passed into a dense phase fluidized bed regenerator for regeneration; said spent catalyst is sequentially passed through 1 st to m th secondary regeneration zones; a regeneration medium is introduced in parallel from in feeding branch lines of regeneration zone into the 1 st to m th secondary regeneration zones; the spent catalyst is brought into contact with the regeneration medium, with the carbon content thereof decreasing gradually; after the completion of the regeneration, the catalyst is returned back to the 1 st secondary reaction zone via stripping and lifting; wherein the dense phase fluidized bed regenerator is divided by a material flow controller into in secondary regeneration zones.
[0037] Wherein n≧2, preferably 8≧n>3; m≧2, preferably 8≧m≧3.
[0038] Preferably, in the dense phase fluidized bed reactor, the apparent linear velocity of gas in the material flow controller is less than or equals to the minimum fluidizing velocity of the catalyst.
[0039] Preferably, in the dense phase fluidized bed regenerator, the apparent linear velocity of gas in the material flow controller is less than or equals to the minimum fluidizing velocity of the catalyst.
[0040] Preferably, the catalyst comprises SAPO-34 molecular sieve.
[0041] Preferably, the reaction conditions of the reaction zone in the dense phase fluidized bed are as follows: the apparent linear velocity of gas is 0.1-1.5 m/s, reaction temperature is 400-550° C., the bed density is 200-1200 kg/m 3 ; the average carbon deposition amount of the catalyst in the 1 st secondary reaction zone is 0.5-3 wt %, and the average carbon deposition amount of the catalyst in the n th secondary reaction zone is 7-10 wt %.
[0042] Preferably, the reaction conditions in the dense phase fluidized bed regeneration zone are as follows: the apparent linear velocity of gas is 0.1-1.5 m/s, the regeneration temperature is 500-700° C., and the bed density is 200-1200 kg/m 3 ; the average carbon deposition amount of the catalyst is decreased sequentially from the 1 st to m th secondary regeneration zones, the average carbon deposition amount of the catalyst in the 1 st secondary regeneration zone is 3-10 wt %, and the average carbon deposition amount of the catalyst in the m th secondary regeneration zone is 0-3 wt %.
[0043] Preferably, the oxygen-containing compound is methanol and/or dimethyl ether; the light olefin is any one of ethylene, propylene or butylene, or a mixture thereof; the regeneration medium is any one of air, oxygen-deficient air or water vapor, or a mixture thereof.
[0044] The technical solution provided in the present invention may further comprises:
[0045] (1) providing a dense phase fluidized bed reactor, comprising a reaction zone, a gas-solid separation zone, and a stripping zone, the reaction zone being divided by a material flow controller into n secondary reaction zones, wherein n≧2;
[0046] (2) providing a dense phase fluidized bed regenerator, comprising a regeneration zone, a gas-solid separation zone, and a stripping zone, the regeneration zone being divided by a material flow controller into in secondary regeneration zones, wherein m≧2.
[0047] Preferably, the raw material comprising an oxygen-containing compound is introduced into the dense phase fluidized bed reactor and is brought into contact with regenerated catalyst, resulting in a light olefin-containing product and a carbon-containing spent catalyst, meanwhile, the regenerated catalyst is sequentially passed through 1 st to n th secondary reaction zones, with the carbon content thereof increasing gradually.
[0048] Preferably, via stripping and lifting, the spent catalyst flowing out from the n th secondary reaction zone is passed into the dense phase fluidized bed regenerator for regeneration, the spent catalyst is sequentially passed through 1 st to m th secondary regeneration zone, and is brought into contact with the regeneration medium, with the carbon content thereof gradually decreasing, and then the catalyst is returned back to 1 st secondary reaction zone via stripping and lifting.
[0049] Preferably, the stream of the light olefin product is passed into separation section after separation with spent catalyst, and the isolated spent catalyst is passed into n th secondary reaction zone.
[0050] In a specific embodiment, the schematic flow chart for preparing a light olefin using a oxygen-containing compound in the present invention is as shown in FIG. 1 . The raw material comprising the oxygen-containing compound is introduced from reactor feed line ( 1 ) and breach lines ( 1 - 1 , . . . , 1 -n) thereof in parallel into secondary reaction zones ( 2 - 1 , . . . , 2 - n ) in the dense phase fluidized bed reactor ( 2 ), and is brought into contact with a catalyst comprising SAPO-34 molecular sieve, to generate a gas phase product stream and a spent catalyst. The gas phase product stream and the entrained spent catalyst are passed into a cyclone separator ( 3 ), wherein the gas phase product stream flows through the outlet of the cyclone separator and the product material line ( 4 ) and enters into the subsequent separation section, the entrained spent catalyst is passed into n th secondary reaction zone ( 2 - n ) via the dipleg of the cyclone separator; the regenerated catalyst from the dense phase fluidized bed regenerator ( 10 ) is passed into the dense phase fluidized bed reactor ( 2 ) via a stripper ( 13 ) and a lift pipe ( 15 ), wherein the bottom of the stripper ( 13 ) is connected to a water vapor line ( 14 ), and the bottom of the lift pipe ( 15 ) is connected to a lifting gas line ( 16 ); the regenerated catalyst is sequentially passed through 1 st to n th secondary reaction zones ( 2 - 1 , . . . , 2 - n ) in the dense phase fluidized bed reactor ( 2 ), and forms spent catalyst after carbon deposition; the regeneration medium is introduced from regenerator feed line ( 9 ) and branch lines ( 9 - 1 , . . . , 9 - m ) thereof into secondary regeneration zones ( 10 - 1 , . . . , 10 - m ) in the dense phase fluidized bed regenerator ( 10 ), and is brought into contact with the spent catalyst, to generate exhaust gas and regenerated catalyst after charking, and then the exhaust gas and the entrained regenerated catalyst are passed into a cyclone separator ( 11 ), from which, the exhaust gas is passed into a tail gas processing section through the outlet of the cyclone separator and exhaust gas line ( 12 ), and is emitted after processing, and the entrained regenerated catalyst is passed into m th secondary regeneration zone ( 10 - m ) via the dipleg of the cyclone separator. The spent catalyst from the dense phase fluidized bed reactor ( 2 ) is passed into the dense phase fluidized bed regenerator ( 10 ) via a stripper ( 5 ) and a lift pipe ( 7 ), wherein the bottom of the stripper ( 5 ) is connected to a water vapor line ( 6 ), and the bottom of the lift pipe ( 7 ) is connected to a lifting gas line ( 8 ). In the dense phase fluidized bed regenerator ( 10 ), the spent catalyst is sequentially passed through 1 st to m th secondary regeneration zones ( 10 - 1 , . . . , 10 - m ), and forms a regenerated catalyst after charking.
[0051] In a more specific embodiment, the structural schematic diagram of the dense phase fluidized bed reactor comprising 4 secondary reaction zones in the present invention is as shown in FIG. 2 . Three material flow controllers ( 17 ) and one baffle are vertically provided to separate the dense phase fluidized bed reaction zone into 4 secondary reaction zones. The catalyst is sequentially passed through the 1 st to the 4 th secondary reaction zones and is then passed into the stripper.
[0052] In a more specific embodiment, the structural schematic diagram of the dense phase fluidized bed regenerator comprising 4 secondary regeneration zones in the present invention is as shown in FIG. 3 . Three material flow controllers ( 17 ) and one baffle are vertically provided to separate the regeneration zone into 4 secondary regeneration zones. The catalyst is sequentially passed through the 1 st to the 4 th secondary regeneration zones and is then passed into the stripper.
[0053] In a more specific embodiment, the structural schematic diagram of the stripper in the present invention is as shown in FIG. 4 . The opening on the tube wall on the upper part of the stripper is a material overflow port ( 18 ) between n th secondary reaction zone (or m th secondary regeneration zone) and the stripper.
[0054] In a more specific embodiment, the structural schematic diagram of the material flow controller in the present invention is as shown in FIG. 5 . The material flow controller ( 17 ) is composed of a partition plate ( 19 ), an orifice ( 20 ), a material downward flow pipe ( 21 ), a bottom baffle ( 22 ) and a heat extraction member ( 23 ). The catalyst is passed into the material downward flow pipe from the top of the downward flow pipe, wherein the apparent linear velocity of gas is less than or equals to the minimal fluidizing velocity, the catalyst in the material downward flow pipe is in a dense phase packing state, and a material flow driving force is formed to drive the catalyst to flow into a next secondary reaction zone (or regeneration zone) via the orifice. A coil structure may be used as the heat extraction member, which is fixed onto the partition plate.
[0055] Preferably, in the above technical solutions, the apparent linear velocity of gas in the dense phase fluidized bed reaction zone is 0.1-1.5 m/s; the apparent linear velocity of gas in the dense phase fluidized bed regeneration zone is 0.1-1.5 m/s; the apparent linear velocity of gas in the material flow controller is less than or equals to the minimum fluidizing velocity of the catalyst; the catalyst includes SAPO-34 molecular sieve; a feed inlet is provided at the bottom of the reaction zone, and the feed includes methanol, dimethyl ether etc.; the stripping medium in the stripper includes water vapor; an inlet for regeneration medium is provided at the bottom of the regeneration zone, and the regeneration medium includes air, oxygen-deficient air, water vapor etc.; the reaction temperature in the reaction zone is 400-550° C., the bed density is 200-1200 kg/m 3 , the average amount of carbon deposition on the catalyst increases sequentially from 1 st to n th secondary reaction zones, the average amount of carbon deposition in the 1 st secondary reaction zone is 0.5-3 wt %, the average amount of carbon deposition in the n th secondary reaction zone is 7-10 wt %; the reaction temperature in the regeneration zone is 500-700° C., the bed density is 200-1200 kg/m 3 , the average amount of carbon is deposition on the catalyst decreases sequentially from 1 st to m th secondary regeneration zones, the average amount of carbon deposition in the 1 st secondary regeneration zone is 3-10 wt %, and the average amount of carbon deposition in the m th secondary regeneration zone is 0-3 wt %. Using the method of the present invention, the object of controlling the amount of carbon deposition on catalyst, improving the uniformity of the carbon content and increasing the selectivity for light olefins can be achieved. Therefore, it has significant technical advantages, and is useful in the industrial production of light olefins.
[0056] For better illustrating the present invention, and facilitating the understanding of the technical solution of the present invention, the exemplary but non-limiting examples of the present invention are provided as follows.
EXAMPLE 1
[0057] 4 secondary reaction zones were provided in the dense phase fluidized bed reactor, and 4 secondary regeneration zones were provided in the dense phase fluidized bed regenerator. The raw material comprising an oxygen-containing compound was passed into the dense phase fluidized bed reactor and was brought into contact with a catalyst comprising SAPO-34 molecular sieve, to generate a gas phase product stream and a spent catalyst. The gas phase material and the entrained spent catalyst were passed into a cyclone separator. The gas phase product stream was passed into a subsequent separation section via an outlet of the cyclone separator, and the entrained spent catalyst was passed into 4 th secondary reaction zone via the dipleg of the cyclone separator. The regenerated catalyst was passed into the dense phase fluidized bed reactor through a stripper and a lift pipe, and sequentially passed through 1 st to 4 th secondary reaction zones, forming a spent catalyst after carbon deposition. The spent catalyst was further passed into the dense phase fluidized bed regenerator through a stripper and lift pipe, and sequentially passed through 1 st to 4 th secondary regeneration zones, forming a regenerated is catalyst after charking. The reaction conditions in the dense phase fluidized bed reactor were as follows: the reaction temperature was 400° C., the linear velocity of gas was 0.3 m/s, the bed density was 1000 kg/m 3 , the average amount of carbon deposition in the 1 st secondary reaction zone was 2 wt %, the average amount of carbon deposition in 2 nd secondary reaction zone was 6 wt %, the average amount of carbon deposition in 3 rd secondary reaction zone was 8 wt %, and the average amount of carbon deposition in 4 th secondary reaction zone was 10 wt %; the reaction conditions in the dense phase fluidized bed regenerator were as follows: the reaction temperature was 500° C., the linear velocity of gas was 0.3 m/s, the bed density was 1000 kg/m 3 , the average amount of carbon deposition in 1 st secondary regeneration zone was 7 wt %, the average amount of carbon deposition in 2 nd secondary regeneration zone was 4 wt %, the average amount of carbon deposition in 3 rd secondary regeneration zone was 2 wt %, and the average amount of carbon deposition in 4 th secondary regeneration zone was 1 wt %. The reaction product was analyzed by on-line gas phase chromatography, and the carbon based yield of light olefins was 91.1 wt %.
EXAMPLE 2
[0058] 3 secondary reaction zones were provided in the dense phase fluidized bed reactor, and 2 secondary regeneration zones were provided in the dense phase fluidized bed regenerator. The raw material comprising an oxygen-containing compound was passed into the dense phase fluidized bed reactor and was brought into contact with a catalyst comprising SAPO-34 molecular sieve, to generate a gas phase product stream and a spent catalyst. The gas phase material and the entrained spent catalyst were passed into a cyclone separator, the gas phase product stream was passed into a subsequent separation section via an outlet of the cyclone separator, and the entrained spent catalyst was passed into 3 rd secondary reaction zone through the dipleg of the cyclone separator. The regenerated catalyst was passed into the dense is phase fluidized bed reactor through a stripper and a lift pipe, and sequentially passed through 1 st to 3 rd secondary reaction zones, forming a spent catalyst after carbon deposition. The spent catalyst was passed into the dense phase fluidized bed regenerator through a stripper and lift pipe, and sequentially passed through 1 st to 2 nd secondary regeneration zone, forming a regenerated catalyst after charking. The reaction conditions in the dense phase fluidized bed reactor were as follows: the reaction temperature was 450° C., the linear velocity of gas was 0.5 m/s, the bed density was 900 kg/m 3 , the average amount of carbon deposition in 1 st secondary reaction zone was 3 wt %, the average amount of carbon deposition in 2 nd secondary reaction zone was 7 wt %, and the average amount of carbon deposition in 3 rd secondary reaction zone was 9 wt %; the reaction conditions in the dense phase fluidized bed regenerator were as follows: the reaction temperature was 600° C., the linear velocity of gas was 0.7 m/s, the bed density was 700 kg/m 3 , the average amount of carbon deposition in 1 st secondary regeneration zone was 4 wt %, and the average amount of carbon deposition in 2 nd secondary regeneration zone was 2 wt %. The reaction product was analyzed by on-line gas phase chromatography, and the carbon based yield of light olefins was 90.5 wt %.
EXAMPLE 3
[0059] 6 secondary reaction zones were provided in the dense phase fluidized bed reactor, and 5 secondary regeneration zones were provided in the dense phase fluidized bed regenerator. The raw material comprising an oxygen-containing compound was passed into the dense phase fluidized bed reactor, and was brought into contact with a catalyst comprising SAPO-34 molecular sieve, to generate a gas phase product stream and a spent catalyst. The gas phase material and the entrained spent catalyst were passed into a cyclone separator, the gas phase product stream was passed into a subsequent separation section via an outlet of the cyclone separator, and the entrained spent catalyst was passed into 6 th secondary reaction zone via the dipleg of the is cyclone separator. The regenerated catalyst was passed into the dense phase fluidized bed reactor through a stripper and a lift pipe, and sequentially passed through 1 st to 6 th secondary reaction zones, forming a spent catalyst after carbon deposition. The spent catalyst was further passed into the dense phase fluidized bed regenerator through a stripper and a lift pipe, and sequentially passed through 1 st to 5 th secondary regeneration zones, forming a regenerated catalyst after charking. The reaction conditions in the dense phase fluidized bed reactor were as follows: the reaction temperature was 480° C., the linear velocity of gas was 0.7 m/s, the bed density was 700 kg/m 3 , the average amount of carbon deposition in 1 st secondary reaction zone was 1 wt %, the average amount of carbon deposition in 2 nd secondary reaction zone was 3 wt %, the average amount of carbon deposition in 3 rd secondary reaction zone was 4 wt %, the average amount of carbon deposition in 4 th secondary reaction zone was 5 wt %, the average amount of carbon deposition in 5 th secondary reaction zone was 6 wt %, and the average amount of carbon deposition in 6 th secondary reaction zone was 7 wt %; the reaction conditions in the dense phase fluidized bed regenerator were as follows: the reaction temperature was 650° C., the linear velocity of gas was 1.0 m/s, the bed density was 500 kg/m 3 , the average amount of carbon deposition in 1 st secondary regeneration zone was 5 wt %, the average amount of carbon deposition in 2 nd secondary regeneration zone was 3 wt %, the average amount of carbon deposition in 3 rd secondary regeneration zone was 2 wt %, the average amount of carbon deposition in 4 th secondary regeneration zone was 1 wt %, and the average amount of carbon deposition in 5 th secondary regeneration zone was 0.01 wt %. The reaction product was analyzed by on-line gas phase chromatography, and the carbon based yield of light olefins was 91.4 wt %.
[0060] The present invention has been described in detail above, but the invention is not limited to the specific embodiments described herein. It will be appreciated by those skilled in the art that other modifications and is variations can be made without departing from the scope of the invention. The scope of the invention is defined by the appended claims.
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A method for preparing a light olefin using an oxygen-containing compound, and a device for use thereof, more specifically, taking methanol and/or dimethyl ether as main starting materials, using a multi-stage (n≧2) dense phase fluidized bed reactor and a multi-stage (m≧2) catalyst regenerator, which the invention solves the problem in the prior art of the uniformity of catalyst carbon deposition and the carbon content being difficult to control and the light olefin selectivity being low.
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FIELD OF THE INVENTION
The present invention relates to an improved machine making it possible to carry out continuously the twisting or cabling of yarns followed by additional thermal treatment.
BACKGROUND OF THE INVENTION
Machines, used particularly for the production of yarns for carpets, have been provided for a very long time, as emerges particularly from FR-A-1,455,499 and from U.S. Pat. No. 3,525,205. It has also been proposed to use such machines for treating partially drawn synthetic yarns, drawing being carried out at the double-twist spindle, as emerges from FR-A-2,414,568.
As emerges from these documents, such installations consist of a central stand which supports a plurality of identical workstations comprising, as seen in the direction of passage of the yarn:
a single-twist or double-twist spindle supporting a yarn package,
means for the take-up of the yarn,
a thermal treatment oven arranged either vertically (FR-1,455,499) or horizontally (U.S. Pat. No. 3,525,205), followed by a cooling zone, and
means for winding up the treated yarn.
In such installations, the yarn is maintained in the relaxed state during the thermal treatment and during the cooling phase prior to reeling.
Although the machines which are the subject of the abovementioned patents relate to the twisting of a single yarn, it has been proposed for a very long time to use similar machines for carrying out direct cabling operations, as emerges from U.S. Pat. No. 3,820,316. For this purpose, in such a case, the yarn coming from the package mounted on the spindle is combined with a second yarn which comes from a second reel mounted in a stationary manner on the stand of the machine and which is fed through the shank of the said spindle as far as a cabling head arranged in the extension of the latter.
SUMMARY OF THE INVENTION
Now an improvement upon such a type of machine has been found, this being the subject of the present invention, making it possible to improve the quality of the yarns produced, particularly as regards the feel and appearance of the article, for example a carpet, produced from such yarns.
In general terms, the machine according to the invention is of the type comprising, in a similar way to the teachings of U.S. Pat. No. 3,525,205, a central stand supporting a plurality of identical workstations, each comprising:
a double-twist or cabling spindle supporting a package of yarn intended to be twisted or cabled together with a second yarn;
means for the take-up of the yarn, making it possible to eliminate the tension which occurs as a result of the twisting or cabling operation;
yarn-heating means followed by a cooling zone; and
means for winding up the treated yarn.
In a similar way to the teachings of U.S. Pat. No. 3,820,316, in the machine according to the invention, which makes it possible to carry out both a twisting operation and a direct cabling operation, is characterized in that:
the heating means consist of a rectilinear oven arranged vertically or approximately vertically
the yarn executes a to-and-fro movement inside the said oven, a return system for said yarn being provided to an extremity of said oven in order to realize this to-and-fro.
This machine is characterized in that:
the yarn is introduced into and extracted from the oven by way of its lower end;
the return system is arranged at the top of the oven and is constituted by a take-up system;
the capability of perfectly controlling the tensions imparted to the yarn during the phases of thermal treatment and of cooling. Such a possibility is achieved due to the presence of the take-up system which is provided in the upper part of the oven and which makes it possible to impart an exact constant tension during the period of the rise in temperature, which takes place between the entry delivery means and the said return and take-up member, and then to maintain the yarn in the completely relaxed state during the second passage through the oven and through the cooling zone.
In a first embodiment according to the invention, after thermal treatment and before winding, the yarn is received on a moving relaxation belt, where it forms a reserve, the receiving speed of the winding assembly being regulated so that the quantity of yarn put in reserve is maintained between two predetermined minimum and maximum values.
In another embodiment, the cooled path of the yarn is provided by means of rotary guide elements interposed between the exit of the oven and a tensioner positioned upstream and in the plane of symmetry of the winding system.
In both embodiments, the double-twist spindle and the winding system are advantageously positioned one above the other and are offset laterally in relation to the setting oven.
However, the invention and the advantages which it affords will be understood better from the exemplary embodiments which are given below and which are illustrated by the accompanying diagrams in which:
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 and 2 are a side view and a front view, respectively, of a workstation of a machine according to the invention;
FIGS. 3 and 4 are views, similar to those of FIGS. 1 and 2, of a variant relating to how the cooling of the yarn is carried out on a machine according to the invention;
FIG. 5 is a diagrammatic detail view of the means used for relaxing the yarn during its cooling phase in the embodiment illustrated in FIGS. 1 and 2;
FIGS. 6 and 7 are partial views showing, in a side view (FIG. 6) and in a front view (FIG. 7), the structure of the take-up device arranged at the entrance of the oven;
FIGS. 8 and 9 are enlarged partial views showing a side view and a front view of the structure of an embodiment of the take-up device provided at the top of the oven; and
FIGS. 10 and 11 are likewise partial side and front views of a second type of take-up device which can be used at the top of the oven.
DETAILED DESCRIPTION OF THE INVENTION
Referring to these figures, each workstation of a machine according to the invention comprises a conventional double-twist or cabling spindle (1) making it possible to carry out either twisting in the conventional way or a direct cabling operation. Preferably, the spindle is driven by an individual motor and therefore supports a reel (2) of the yarn (3) to be treated. The double-twist spindle (1) makes it possible to impart to the yarn (3) two twisting turns for each revolution of the said spindle. When the said spindle is used for carrying out a direct cabling operation, it has a hollow shank, and a second yarn is fed through the latter in order to be combined with the yarn (3), carried by the spindle, at a cabling head (4) which is arranged in the extension of the axis of the said spindle (1).
The actual treatment zone is arranged downstream of the double-twist or direct cabling assembly (1).
This treatment zone comprises, in the direction of the path of the yarn, a delivery means (5) of the positive type.
This delivery means is advantageously of the type illustrated in FIGS. 6 and 7 and is composed essentially of an assembly of the type with a capstan (6) and with a pressing cylinder (7), the said assembly making it possible, in association with a grooved cylinder (20) (see FIG. 7), to achieve a reeving of the yarn (3) (or of the cabled yarn) and therefore very high accuracy in the speed of take-up of the said yarn as well as to eliminate the tension which occurs as a result of the twisting or cabling operation.
It should be noted that, for the sake of clarity, the yarn (3) has not been illustrated in FIG. 2 between the exit of the spindle (2) and the delivery means (5). Moreover, the pressing cylinder (7) is shown in the inoperative position in FIG. 6 by thin lines.
The delivery means (5) is arranged at the entrance of the actual thermal treatment oven (8), the said oven being arranged vertically or approximately vertically, as illustrated in the accompanying figures, where it forms an angle of approximately five degrees with the vertical.
This oven is a conventional oven of the type used on false-twist texturing equipment.
According to the invention, a take-up and return system, designated by the general reference (10), is arranged at the top of the oven, the said system making it possible to cause the yarn to execute a second passage through the oven (8), during which it is maintained in the completely relaxed state.
According to the embodiment illustrated in FIGS. 8 and 9, this take-up and return system (10) consists of an assembly of the "yarn detensioner" or "overspeed delivery means" type, comprising two dishes (20, 21) between which the yarn passes and which are rotated positively, preferably by means of an individual motor (22), as illustrated in FIGS. 8 and 9. Such a delivery means can drive the yarn by sliding and takes up the latter at a speed higher than the normal run-off speed. It makes it possible, as a function of the variations in the speed of take-up of the yarn, to obtain automatic self-regulation of the consists of an assembly of the "yarn detensioner" or "overspeed delivery means" type, comprising two dishes (20, 21) between which the yarn passes and which are rotated positively, preferably by means of an individual motor (22), as illustrated in FIGS. 8 and 9. Such a delivery means can drive the yarn by sliding and takes up the latter at a speed higher than the normal run-off speed. It makes it possible, as a function of the variations in the speed of take-up of the yarn, to obtain automatic self-regulation of the tension at the exit of the delivery means, this tension being maintained at a very low value.
According to another embodiment, as illustrated in FIGS. 10 and 11, the take-up and return system (10) can consist of a positive delivery means of the press-roller type. In such a case, the yarn (3) passes over the surface of a cylindrical guide (23) likewise rotated by means of a motor (22), and the roller (24), subjected to the action of a restoring element (25) (spring), exerts pressure on the yarn.
At the exit of the take-up and return system (10), as stated above, the yarn (3) passes through the oven (8) a second time, being maintained under a minimal tension. The vertical or approximately vertical position of the oven (8) makes it possible to take advantage of gravity so that the yarn remains perfectly straight.
At the exit of the oven (8), the yarn is transferred, preferably by means of a guide chute (26), to means for cooling the yarn in the relaxed state. The guide chute (26) has a V-shaped cross-section.
In the first embodiment illustrated in FIGS. 1, 2 and 5, the means for cooling the yarn in the relaxed state consist of a relaxation belt (11) arranged horizontally below the oven (8). This belt may be either individual for each workstation or common to all the stations and, in that case, extends over the entire width of the machine.
After relaxation, the yarn (3) passes over a recovery system (12), in order subsequently to be fed to the conventional winding means (13).
The receiving speed of the winding assembly (13) is adjusted by means of a reserve detector (20) which makes it possible to bring about an acceleration for a given duration, so that the yarn (3) put in reserve in the form of turns is maintained between two predetermined minimum l and maximum L values, for example between 150 mm and 350 mm in length.
In the second embodiment illustrated in FIGS. 3 and 4, the cooling of the yarn is carried out by causing it to pass around return elements consisting of freely rotating rollers (14, 15), the yarn being fed to the winding system (13) by means of a hysteresis brake (16) which is adjusted so that the said yarn (3) is maintained, upstream, under minimal tension.
Such a machine design has numerous advantages over the solutions of the prior art, particularly as regards its flexibility of use, thus allowing the production of a wide variety of different yarns, this being achieved simply by adjusting the tensions which are imparted to the yarns in the various treatment zones, as demonstrated by the concrete examples given below as a non-limiting indication.
EXAMPLE 1
Production of a yarn of the cabled type consisting of two polyamide yarns each having a linear density of 1250 dtex and being twisted at 160 turns/metre
Such a yarn is produced on the machine according to the invention, as illustrated in FIGS. 1 and 2, the yarn (3), which comes from the reel carried by the spindle, being combined at the cabling point (4) with a second yarn (not shown) which comes from an additional support mounted on the stand of the machine and fed through the hollow shank of the spindle.
The machine settings for producing such a cabled yarn are as follows:
______________________________________speed of the spindle (1) 1500 revs/minallowing direct cabling:twist imparted by the spindle 160 turns/m(1):speed of the take-up (5): 40.6 m/min.length of the oven (8): 2.25 mspeed of the take-up and 47 m/min.return element (10):tension of the yarn during 3 gramsthe first passage between thedelivery means (5) and thetake-up (10):tension of the yarn during 0 gramsthe second passage and in thecooling zone:winding tension downstream of 140 gramsthe tensioner (12):receiving speed of the 40 m/min.winding means (13): (an average)storage length on the between 15 andconveyor belt (11) during the 30 cmcooling phase:temperature of the oven (8): 220° C.______________________________________
Such a procedure makes it possible to obtain a yarn which can be used for the production of carpets and which has an improved appearance and feel in comparison with articles produced from conventional yarns.
EXAMPLE 2
Production of a carpet yarn from a polyamide 6.6 yarn having a linear density of 2100 dtex and a twist of 70 turns/metre
This yarn is produced on a machine according to the invention, as illustrated in FIGS. 3 and 4, and under the following conditions:
______________________________________speed of the double-twist 2625 revs/minspindle (1):twist imparted by the spindle 70 turns/m(1):speed of the take-up (5): 75 m/min.length of the oven (8): 2.25 mspeed of the take-up and 85 m/min.return element (10):tension of the yarn during 5 gramsthe first passage between thedelivery means (5) and thetake-up (10):tension of the yarn during 3 gramsthe second passage and in thecooling zone:winding tension downstream of 140 gramsthe tensioner (12):receiving speed of the 74 m/min.winding means (13): (on average)distance between the two 200 cmguides (14, 15) defining thecooling length:temperature of the oven (8): 220° C.______________________________________
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An improved machine for continuously twisting or cabling, as well as thermally treating of yarns includes a central stand capable of supporting a plurality of stations. Each station includes a direct cabling or double twist spindle for supporting and twisting or cabling a first yarn package together with a second yarn. The treatment zone is located downstream from the spindle wherein the yarn is delivered using a take-up which eliminates tension resulting from the cabling or twisting operation. The treatment zone includes a vertically disposed oven and adjacent cooling area. A take-up and return system adjacent the oven allows multiple passes to be taken through the oven, as needed, to treat the yarn under minimal tension to the cooling area and to a winding system.
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BACKGROUND OF THE INVENTION
The present invention relates to security of data communications in a wireless system, and in particular to such a system wherein an encryption key used by a transmitter and a receiving device may be varied and reprogrammed by a user in order to enhance the system security, wherein the encryption key is not conveyed or easily read or decrypted by human means.
Security systems utilizing short range radio frequency communications consist of a control, an RF receiver, and a variety of transmitter products that detect and transmit to the control via the RF Receiver the state of various transducers such as smoke, motion, shock & vibration detectors, door and window switches, etc. In addition to these devices, wireless keypads having numeric or alphanumeric input keys are used to remotely arm and disarm the system via the use of personal security codes entered into the keypad and transmitted to the receiver and control. Finally, wireless keys with unique serial numbers, previously learned by the system, can also be employed by the user to arm or disarm the system or to open and close a garage door, turn lights on or off, etc.
Wireless keypads and keys presently in use are designed with RF ranges of several hundred feet beyond the periphery of a protected premises. This introduces a new security problem since unwanted intruders, skilled in the art of RF receiver and transmission technology in conjunction with computer technology, can remotely and surreptitiously capture, analyze, and playback the transmissions from these devices in order to gain entry into the premises without detection by the associated security system. For example, an intruder may be in an unobserved location one hundred feet away from the protected premises and employ suitable RF equipment which could record and playback transmitted messages from an authorized user's wireless key or keypad used to disarm the security system prior to or upon entering the protected premises. The nature of the messages need not be analyzed by the intruder so long as the playback is a repeat of the same messages and in the same sequence which disarmed the security system. This is all that is necessary to counteract the protection afforded by a wireless key even with a very large serial number previously learned by the security system. In the case of the wireless keypad, the user's personal security code can be determined from unencrypted transmitted messages used to arm or disarm the system, or by simply opening a garage door or turning on a light, etc. Once the user's personal security code is thus obtained, the intruder can enter the premises any time thereafter and disarm the security system by using that security code at the system's wired security keypad.
There are many encryption and corresponding decryption algorithms used in various communication systems requiring secrecy of data and other critical information transmitted over a network from being intercepted and deciphered by unwanted sources sharing that same (wired or wireless) network. In one such system, marketed by MICROCHIP TECHNOLOGY INC. as an HCS300 Code Hopping Encoder, a unique transmitter serial number is programmed by the manufacturer at the time of production. An encryption key is generated during production by using a key generating algorithm, which uses as its inputs the transmitter serial number and a 64-bit manufacturer's code. Thus, an encryption key is generated which is unique to each transmitting device, but which cannot be changed by the user at any time and is readily breakable if the manufacturer's code and the transmitter serial number are determined. Thus, the manufacturer's code must be carefully controlled since it is a pivotal part of the overall system security. The transmitter serial number, encryption key, and sync counter number are stored in EEPROM in the transmitter. After installation of the system, when a transmitting device is activated by a user, the encoder uses the pre-stored encryption key and sync count from EEPROM to generate an encrypted sync count, which it then loads into a data word along with an unencrypted serial number and the information desired to be transferred. The decoder at the receiver then uses the received serial number to fetch from its memory the last sync count and the encryption key for that transmitter. The decryption algorithm uses the key to decrypt the received encrypted sync count and compares it against the stored sync count. If these numbers are within a predetermined range (i.e. 16), then the algorithm passes and the message is considered valid. This methodology is termed "code hopping" since the sync count is incremented or changed with a predetermined algorithm known to the transmitter and receiver with every activation of the transmitter, and the receiver and transmitter each track the sequence independently.
This type of system utilizes a preset manufacturer's code to generate the encryption key, which is not changeable for a given device with a given serial number. This is problematic and disadvantageous since the manufacturer's code is of record with the manufacturer and possibly others in privity with the system, and the code could be compromised and used to determine the encryption key for a given transmitter since the transmitter serial number is transmitted to the receiver in unencrypted format. Thus, the key could readily be reverse engineered by an intruder who determines these fixed, unchanging data. Once an intruder has ascertained the encryption key, he may intercept a transmission, decrypt the sequence number, and be able to break into the system by changing or incrementing his own number generator and encrypting a message with this data.
It is therefore desired for the system to utilize encryption keys which are randomly generated and therefore unknown to anyone, thus eliminating the possibility that the key may be compromised. In addition, it is desired to enable the encryption key to be easily changed by a user, thus enhancing the security of the system, rather than having only one, fixed encryption key for each transmitting device.
The present invention relates to the use of novel security encryption and decryption methodologies and algorithms, plus unique procedures to provide an existing wireless security system with a high degree of immunity from being defeated by intruders of high technical ability using RF receiving, transmitting, recording, playback, and computational equipment. The nature of the encryption, decryption, message formats, and procedures are uniquely designed to provide the associated security systems the ability to communicate with existing unencrypted wireless devices as well as the new encrypted ones without changes being required of existing associated security controls.
In particular, with the advent of new encrypted data transmission technologies, devices such as wireless keypads and keys with encrypted data transmissions are being added to existing systems which are still required to communicate with devices having unencrypted data transmissions. It is therefore desirable for the receivers in such systems to be able to communicate seamlessly with devices transmitting data messages in either an encrypted or unencrypted data format.
Further, the advent of new devices with encrypted data formats has led to the need for such devices to be registered, or learned, by the receiver for subsequent data transmissions. In particular, the receiver needs to register an encryption key associated with a transmitting device, and needs to be able to synchronize an internal sequence number with a sequence number generator on the device so that the communications are synchronized properly. The receiver also needs to be able to update the encryption key information in its store in order to provide a high degree of security. Finally, the system needs to be able to de-register, or unlearn a device when it becomes stolen or lost, so that an intruder having the device cannot gain unauthorized access to the secured premises. It is advantageous to implement these functions using a minimum of additional computational resources in the receiver. This allows the function to be added to existing products without significantly redesigning the product.
It is therefore an object of the present invention to provide a communications system and methods whereby the problems of the prior art described above are overcome.
SUMMARY OF THE INVENTION
The present invention relates to improvements in encryption methodologies used in a wireless data communications system suitable for use in a wireless security system. The wireless communications system is comprised of a receiving station having a receiver and a control unit, and a plurality of transmitting devices which communicate with the control via the receiver. The transmitter devices each locally provide their own encryption key which is stored in the transmitter and initially registered with the receiver, which is then utilized by the transmitter (along with a sequence number) to encrypt subsequent data messages, and which is also then used by the receiver to decrypt those messages. A sequence number generator (which may increment or change in a predetermined algorithm) is used to synchronously track the message sequence at both the transmitter and receiver. The key is preferably generated at the transmitter device in a random fashion. The user may change the encryption key for any transmitting device at any time and re-register the new random key with the receiver accordingly. The encrypted device registration (learning) methods are user-friendly and immune from detection by technically skilled intruders with special RF equipment. Selected transmitting devices may be deleted or de-registered from the receiver, or the entire store of keys and sequence numbers may be de-registered at one time. Importantly, no record of the encryption key, whether written, stored in ROM, or otherwise, exists except for the local storage at the transmitter and the receiver. In another aspect of the invention, the receiver processes encrypted and non-encrypted messages, interchangeably, within the same wireless security system.
Thus, a first major aspect of the invention is a method of configuring the receiver with an encryption key useful for decrypting encrypted data message transmissions. The method comprises the steps of randomly generating at the transmitting device a new encryption key and storing it in memory, transmitting to the receiver a data message comprised of the new encryption key and a device identification code unique to the transmitting device, receiving the data message at the receiver, and storing in a memory table the device identification code and the new encryption key. The receiving station and the transmitting device may first be placed into a programming mode in order to configure the receiver with the encryption key. A sequence number generator in the transmitting device is initialized to an initial state, and the initial state is included in the data message along with the new encryption key and the device identification code unique to the transmitting device. This message may itself be encrypted using encryption algorithms known to both the receiver and transmitter.
After received by the receiver, the data message may be stored in the memory table at the receiver by first determining if a previous data record exists in the memory table which comprises the device identification code, then overwriting the previous data record with the new data message if such a previous data record exists, or adding the new data message as a new record in the memory table if such a previous data record does not exist.
The configuration or registration process may be verified by transmitting to the receiver a second data message comprised of the device identification code and an encrypted version of the sequence number generator initial state, receiving the second data message at the receiver and fetching from the memory table the previously stored encryption key and sequence number generator initial state matched with the identification code from the received second data message, using the fetched encryption key to decrypt the encrypted sequence number generator initial state received from the second data message, comparing the decrypted sequence number generator initial state with the fetched sequence number generator initial state, and providing an indication that the receiver has successfully registered the transmitting device when the comparison step has passed.
The second major aspect of the invention is a method of configuring the receiver to de-register all of the transmitting devices and temporarily disable subsequent encrypted data communications therewith pending re-registration of a transmitting device. The method comprises the steps of configuring the receiving station and the transmitting device into a programming mode, transmitting to the receiver from one of the previously registered transmitting devices a first data message comprised of a command to delete all registration data from an internal memory table, deleting all registration data from the receiver internal memory table, temporarily disabling the receiver from responding to further encrypted data messages, and transmitting to the receiver from the transmitting device a second data message in unencrypted format, the second data message comprising a command to cause an indication (such as an audible beep) that the de-registration process was successful.
In the alternative to de-registering all the devices, a selected one of the devices may be de-registered (if the identification code is known) by configuring the receiving station and a different one of the previously registered transmitting devices into a programming mode, transmitting to the receiver from the transmitting device a first data message comprised of a command to delete the registration data associated with the selected device from an internal memory table, deleting the registration data from the receiver internal memory table, and temporarily disabling the receiver from responding to further encrypted data messages from the selected transmitting device.
The third major aspect of the invention is a method for automatically discriminating between unencrypted and encrypted messages, which comprises the steps of receiving at the receiving station a message from a transmitting device, storing the message in a buffer, analyzing a portion of the stored message to determine if was validly received, and further processing the message portion as a validly received unencrypted message when the message portion has been so determined to have been validly received. When the message portion has, however, been so determined to have not been validly received, then the entire stored message is analyzed to determine if it was validly received. The entire stored message is then further processed as an encrypted message when it has been so determined to have been validly received, and it is ignored when it has been so determined to have not been validly received.
This methodology is successful because an encrypted data message is longer than an unencrypted message, and thus by allowing the receiver to store an entire data message and first analyzing a portion of the entire message, it can be determined if that portion is a valid (unencrypted) message. If the portion cannot be validated, then the entire message is examined to ensure that it is a valid (encrypted message). Preferably, the message portion comprises a cyclic redundancy character, and the message portion is analyzed by performing a cyclic redundancy check routine on the message portion and comparing the results to the message portion cyclic redundancy character. Thus, if the cyclic redundancy check routine passes, the message portion must be valid and the message is unencrypted. If the message portion is not an unencrypted message, then the message will also preferably comprise a message cyclic redundancy character, and the message is analyzed by performing a cyclic redundancy check routine on the message and comparing the results thereof to the message cyclic redundancy character. Notably, the message portion cyclic redundancy character and the message cyclic redundancy character are located in different positions of the message.
The present invention is embodied by a secure data communications system suitable for transmission of data messages, comprising a plurality of remote transmitting devices for transmitting the data messages, and a receiving station comprising a data receiver for receiving the data messages from the transmitting devices. Each of the devices of the present invention comprises a random key generator for randomly generating data encryption keys suitable for use in encrypting data messages prior to transmission, a sequence number generator for keeping track of the transmission sequence number, the sequence number generator being changed for each data transmission, a memory for storing the randomly generated encryption key and a device identification code unique to the transmitting device, means for encrypting data prior to transmission, the encrypting means utilizing the encryption key and sequence number stored in non-volatile memory, and transmitter means for transmitting a data message comprised of an encrypted data field, an unencrypted device identification field, and an encrypted sequence number field. The receiver accordingly comprises a memory table comprising a plurality of data records, each of the data records comprising a device identification code, an encryption key, and a transmission sequence number associated with one of the transmitting devices, means for fetching from the memory table the data record associated with a data message received from a transmitting device by utilizing a device identification code from the received data message, means for decrypting the sequence number and data field from the received data message by using the encryption key from memory, means for comparing the decrypted received sequence number with the transmission sequence number fetched from memory, and means for allowing the decrypted received data message to be transmitted to a control unit associated with the receiver when the decrypted received sequence number and the transmission sequence number fetched from memory are within a predetermined range.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is an overall block diagram of a wireless security system suitable for use with the present invention;
FIG. 2 is a block diagram of the transmitter encoder section of the present invention;
FIG. 3 is a block diagram of the decoder section of the receiver of FIG. 1;
FIG. 4 is a diagram of the message formats used in the present invention;
FIG. 5 is a flowchart of the method for changing encryption keys in the present invention;
FIG. 6 is a flowchart of the de-registration process of the present invention; and
FIG. 7 is a flowchart of the automatic message format discrimination of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 1 is an overall block diagram of a wireless security system used with the secure data communications system of the present invention. Illustrated are a plurality of transmitting devices 2, in particular a wireless keypad 2a, a wireless key 2b, and a sensor 2c such as a smoke sensor well known in the art. Although transmitting devices are used in the preferred embodiment, it is understood that transceiving devices, having receiving functions as well as transmitting functions, may be used as well. The transmitting devices are in wireless, i.e. radio frequency (RF) communication with a receiving station 4, which is comprised of an RF receiver 6, a control unit 8, and a keypad 10. The keypad 2a typically has numeric or alphanumeric keys 3 for inputting a personal identification number (PIN) in order to gain access to the security system, e.g. to disarm the system prior to entering the guarded premises. The wireless key 2b typically has a few non-numeric keys 5 with dedicated programmable functions, e.g. opening a garage door, or turning on a light within the guarded premises. An authorized user activates the transmitting device 2a or 2b, and an encrypted command is generated by an encoder section 7 and sent by an RF transmitter 9 to the receiver 6. The receiver 6 receives and processes the message with an RF receiver 11 and then decrypts the message with a decoder section 13, as explained further below, and passes on the command information in unencrypted format to the control unit 8 to which it is wired. The keypad 10 allows a user to execute certain commands locally, such as arming or disarming the system, entering a programming mode (to be described herein), and the like. The smoke sensor 2c transmits messages to the receiver 6 in standard, unencrypted format as well known in the art. The control unit 8 and keypad 10 are also well known in the art of security systems and need not be explained in detail here. The receiver 6 provides both unencrypted and encrypted data communications with the appropriate transmitting device 2 through the auto-discrimination process of the present invention, as will be explained in detail herein. Importantly, in accordance with the present invention, the encryption methodologies are transparent to the control unit 8, and thus a receiver 6 in accordance with the invention may be made compatible with various control units 8 already on the market. In addition, due to the auto-discrimination aspect of the invention, the receiver 6 is able to determine automatically if a certain transmission is unencrypted or encrypted, and it can process it accordingly and pass it on to the control 8 in a similarly transparent fashion. Thus, prior art unencrypted transmitting devices such as sensor 2c may be used without modification with the receiver 6 of the present invention.
The encoder 7 is shown in the block diagram of FIG. 2, and comprises a random key generator 21, encryption logic 22, a sequence number generator 24, and a non-volatile memory 26 such as an EEPROM for storing an identification number (Device ID) unique to each transmitting device, the current randomly generated encryption key, and the current sequence number for the transmitting device 2. The Device ID is programmed at the factory by the manufacturer, identifies the device uniquely, and in general is unchangeable. The encryption key and sequence number are variable, however, as explained below.
In normal, data communications operation, the data message to be formed by the encoder 7 and transmitted to the receiver 6 comprises a data field 28, a Device ID field 30, a sequence number field 32, and a CRC field 34. The data field 28 comprises the data desired to be sent to the control; e.g. a request by the user to disarm the system, along with the user's entered PIN. The data field 28 is sent in normal operation in encrypted format, and is derived by the encryption logic 22 in conjunction with the key previously generated by the random key generator 21 and stored in both the transmitter EEPROM 26 and the receiver 6 via a registration (learning) process along with the current sequence number stored in the EEPROM 26. (This data flow is shown by dotted lines 23 and 25, and is not part of the present invention but is provided herein for purposes of illustration and completeness). The combination of the randomly generated key and the sequence number for encryption purposes may be termed a "superkey" since it is more secure than the encryption key alone The Device ID is loaded into the message in field 30 in standard, unencrypted format, and will be used by the receiver 6 to fetch the encryption key stored locally at the receiver. The sequence number field 32 (along with key or keypad data in field 28) is sent in encrypted format and is derived by the sequence number stored in EEPROM 26 and changed or incremented for every transmission by the sequence number generator 24, and is used by the receiver 6 to ensure that the communication is received from an authorized transmitter. The sequence number generator increments or changes in a predetermined fashion, which is known by both the receiver and the transmitter. The algorithm may be a simple increment by one, two, four, etc. or may be a pseudo-randomly changing sequence. The CRC (cyclic redundancy character) field 34 is filled with a CRC character generated in accordance with techniques well known in the art, and is used by the receiver 6 to ensure the integrity of the data being transmitted.
Although it is preferred to generate the encryption key in a random fashion in order to provide maximum security, it is contemplated that other ways of providing encryption keys may be implemented, such as a sequential count provided by a counter or shift register, a sequence of predetermined non-random numbers stored in memory, etc.
The receiver 6 comprises a decoder section 13, shown in FIG. 3, which comprises a memory table 42 such as an EEPROM which contains data records having sequence number and encryption key data stored therein along with the associated Device ID. That is, for each transmitter registered with the receiver, a record exists in memory 42 which comprises the unique transmitter identification number Device ID, the most recent sequence number for that transmitter, and the encryption key for that transmitter. When a normal data encrypted message is received, the decoder 13 searches its memory table 42 looking for a match of the received (unencrypted) transmitter identification number Device ID, and when it finds the proper record, it fetches the encryption key and the stored sequence number for that transmitter. The decoder 13 uses the fetched key and sequence number as a superkey to decrypt with decryption logic 44 the encrypted sequence number 32 from the received message. The decoder then compares, with comparison logic 46, the decrypted new sequence number with the stored sequence number, and, if they are within a predetermined range of each other, it decrypts the message data field and flags the data as valid with a GO signal and passes it on to the control for further processing. This is shown by the dotted lines in FIG. 3. The sequence number is kept in synchronization with the current transmitter sequence number by overwriting the sequence number in memory 42 with the decrypted new sequence number.
Importantly, the present invention allows the user to easily and readily register any transmitting device's randomly generated encryption key with the receiver, to change the existing encryption key of any such device in such a fashion that there is no human readable record of the key (and therefore no one knows the updated key), thus ensuring the security of the system.
FIG. 4 illustrates in detail the message format of the present invention for both unencrypted messages (Standard Format A) and encrypted messages (Encrypted Format B). With reference to Encrypted Format (B), each encrypted wireless key 2b or keypad 2a is identified by the receiver using a unique, factory-configured, 16-bit number in N9-N12 (field 30) referred to here as the Device ID (distinguished from a wireless key serial number ID or a user security code in D1-D6 that is passed on to and recognized only by the control). This unique Device ID must be registered or "learned" by the receiver before the transmitting device can communicate its normal D1-D6 data to the control via encrypted messages to the receiver. Since the receiver processes multiple, encrypted keys and keypads as well as unencrypted wireless devices, the receiver must be able to add or delete encrypted Device IDs and their unique encryption keys to its internal non-volatile memory 42.
In order to avoid possible manipulation by technically skilled intruders, the user first places the security control into a programming mode of operation, which is called a TEST mode in the preferred embodiment, using his or her multi-digit security (PIN) code. For example, this may be done by depressing a specific key sequence on the wireless device 2 and/or a specific key sequence on the keypad 10 at the receiving station 4. It is only following reception of this command from the control and throughout duration of this TEST mode, that the receiver will permit the addition (learning) or deletion (unlearning) of encrypted wireless devices. The learning process is summarized here as follows with reference to the flowchart in FIG. 5.
To learn a new encrypted wireless key 2b or keypad 2a, the control is first placed in its TEST mode as shown at step S1. The keypad is then placed in an encryption learning mode by activating special keys (not used during normal operation) appropriate to the device. For example, the user may need to depress three keys at once in order to trigger the programming or TEST mode. In this encryption learning mode, the wireless key or keypad clears its sequence number generator 24 to an initial state (STATE 0 ) at step S2 and generates a random encryption key KEY at step S3 which it stores internally in memory 26 and which it will use, along with the sequence number, as a superkey in the encryption process. In step S4, it then repeatedly transmits two 5-message sequences, or pentads, in which each of the messages in a given pentad are identical and of the 96-bit message format as shown in FIG. 4. The pentad message format is described fully in co-pending application Ser. No. 08/650,292, filed on May 20, 1996, and assigned to the assignee of this application. Each message of the first 5-message pentad is unencrypted wherein the encryption key is contained in pre-determined positions within N1-N8 (field 28); the unique Device ID is in N9-N12 (field 30); the initial sequence number STATE 0 is in N13-N16 (field 32); and a cyclic redundancy character CRC is in N17-N20 (field 34). The receiver will associate the new random encryption key with the Device ID provided the control is in the TEST mode; the correct system code exists in the status byte; and at least two messages of the pentad exactly match. The random encryption key, together with the corresponding Device ID and the initial sequence number STATE 0 are then inserted into the memory table 42. None of this data is sent to the control since it is intended only for registration with the receiver.
At step S5, the memory table 42 at the decoder 13 is searched to determine if the Device ID and corresponding key and sequence data has already been stored from an earlier registration. If found at step S6, the decoder 13 will simply overwrite the old encryption key and sequence number associated with that Device ID as shown at step S7. If no Device ID match is found, then the device is being registered for the very first time, and the data is written into a new location in memory 42 as shown by step S8.
The second of the dual pentads is encrypted in positions N1-N8 (field 28) and N13-N16 (field 32) using only the encryption key with the encryption logic 22 as shown at step S9 and transmitted with the unencrypted Device ID as shown at step S10. Note that in normal operation, the random key and current sequence number are used as a superkey to encrypt (and decrypt) the data, but in this learning process only the random key is used. N1-N8 (field 28) contains a special command which may be used to cause the control to issue a distinctive audible annunciation (i.e., 3 short beeps). N13-N16 (field 32) contains the sequence number encrypted with the random key. Thus, the second (encrypted) pentad serves to provide audible acknowledgment of the learning process provided by the first (unencrypted) pentad, as shown at step S14. This process continues until terminated by the user using a special keying sequence. More than one encrypted wireless device can thus be learned (by more than one receiver if required) with each device having its own random encryption key associated with its Device ID.
At step S11, the encryption key and stored sequence number are fetched from the memory table 42 as a function of the Device ID received in the encrypted message. The fetched encryption key is used by the decryption logic 44 to decrypt the received sequence number (step S12), and step S13 compares the decrypted sequence number with the stored sequence number. If these are within a predetermined range of each other (i.e. within 100), then the test has passed and a GO signal is issued to provide the indication of successful registration such as a beep at step S14. If the comparison fails, then an indication is made (optionally) at step S15 that the device has not been successfully registered.
It is noted that although the use of a second (encrypted) message to verify that the registration was successful is used in the preferred embodiment, this verification step is optional, and the system may proceed upon the receipt of just the first message containing the new encryption key.
Although the superkey actually changes with each transmission since the sequence number changes, it is a good practice for the user to periodically change the random key portion of the superkey in order to further immunize the security system from being defeated by technically skilled intruders. This is easily done with the present invention by placing the security system into the programming or TEST mode and repeating the registration procedure described above. A new encryption key will automatically be generated by the device as a consequence of making it enter the encryption learning mode. When the system is in TEST mode and a new randomly generated encryption key is received by the receiver, it searches the memory table 42 to see if the Device ID has already been stored from an earlier registration. If found, the receiver will simply overwrite the old encryption key and sequence number associated with that Device ID. This process may be repeated for each of the encrypted devices in the system without increasing the size of the receiver's database since no new devices were added. New encryption keys, known only by the receiver and each respective device, can thus be generated by the user whenever the user desires to do so, further confounding the would-be intruder.
To delete, or unlearn, encrypted devices which were lost or stolen, it is most secure to first delete all of the devices previously learned and then to re-learn the devices remaining in the system. This follows from the fact that, in order to keep the learning process user-friendly, it should not be required of the user to keep human readable records or assign human readable identification to each encrypted device to be learned by the receiver. It should only be required of the receiver to keep an internal record of each Device ID and associated random key learned, both of which need not be known by the user. Also, since a device that is lost or stolen is not available for use in a deletion process, it is most secure for the user to simply delete the entire database in memory 42 and re-learn the devices known to be in trusted hands. This same re-learning process is recommended to the user to periodically change the encryption key of any one or all devices as described later.
Therefore, with reference to the flowchart of FIG. 6, to delete all of the devices previously learned from the receiver's memory 42, the user first places the control in the programming or TEST mode at step S20 and then activates a special keying sequence using a wireless keypad. This causes the wireless keypad to transmit dual pentad message sequences as with the learning process but with the following differences: the first pentad at step S22 will conform to message format (B) in FIG. 4 with FFFF hex in the sequence number position N13-N16, in place of the normal encrypted sequence number, which indicates that the entire memory 42 is to be deleted. The encrypted data in N1-N8 will be a special code, such as A00000 hex, to instruct the receiver to delete all of the Device IDs from its encryption database. Only after receiving at least two of these first 5 messages which exactly match the same data just described, will the receiver delete at step S23 its entire encryption database in the non-volatile memory 42 and respond thereafter to only unencrypted messages of format (A) in FIG. 4. The second message pentad at step S24 will be of the unencrypted format (A) with a simple unencrypted message that may be used to cause the control to emit an audible annunciation at step S25 to acknowledge the deletion. The user can immediately, or later on, enter the learning mode and re-learn one or more of the desired devices.
In an alternative embodiment, the entire memory table 42 need not be deleted if a user is able to keep a log of which devices are registered with the system and in what order they are registered. When it is desired to de-register a particular device, a code may be entered via any of the wireless keys still registered with the receiver or with a specially designated wireless key, and an instruction may be issued to the receiver to delete only the encryption key record for the selected device. This method of de-registration is advantageous since it allows selective de-registration and does not require the user to re-register the remaining devices, but it is less secure in that it does require the user to keep a log of which devices are registered with the receiver. This procedure is exemplified by steps S26, S27 and S28.
In another major aspect of the invention, the receiver is able to auto-discriminate and automatically differentiate unencrypted messages from encrypted messages and pass the data on to the control in a seamless and transparent fashion. Differentiating encrypted from unencrypted RF transmission messages within the same wireless security system is demonstrated by the two wireless message formats presented in FIG. 4. In this figure, twenty 4-bit nibbles, N1-N20 plus a 16-bit preamble amounts to a maximum (encrypted) message length of 96 bits. A standard (unencrypted) message length is 64 bits long consisting of a 16-bit preamble plus the twelve 4-bit nibbles, N1-N12. The decrypted or standard unencrypted data, D1-D6, represents the data originally keyed on a wireless keypad by the user, (packetized in groups of up to 6 digits), or a unique 24-bit wireless key serial number. The single 8-bit status byte includes special device information used by the control to differentiate wireless keypad data from non-wireless keypad data, such as may originate from wireless keys and standard transmitters previously programmed in the security system. In the case of wireless keypad, the status byte also contains a system code. N1-N6 contains keypad data rather than a serial number. The system code is manually programmed into each keypad and control. It insures that transmissions from keypads are accepted only by controls which have been programmed with the same system code.
This system code is initially transmitted to the receiver by the control to insure that only system devices are processed by the receiver, whether they are of the encrypted or unencrypted versions. It is distinct from the Device ID contained in N9 thought N12. The latter is unique to each keypad and is programmed into the keypad at the time of manufacture. Its use is completely transparent to the user. Once the transmitter is registered with the receiver, the system code is no longer an essential requirement.
A Cyclic Redundancy Check (CRC) code is appended to each transmission (N17 through N20) in order to verify that the transmission is received without error. It is also used in differentiating between encrypted and unencrypted transmissions as described below.
Before analyzing the received message, the receiver allows for storage at step S30 of the entire 80 information bits, N1-N20 since in the preferred embodiment it is simpler for the receiver not to anticipate the length of the message. An unencrypted message format (A) is assumed if correct CRC occurs following examination of the 48 bits, N1-N12, at steps S32 and S33. In this case the remaining 32 bits, N13-N20, are ignored and the standard data contents contained in N1-N8 are sent to the control by the receiver via a standard wired interface, as shown at step S34. If the N1-N12 portion of the received message fails the CRC check, an encrypted message format (B) is assumed if correct CRC then occurs from N1 to N20, as shown at steps S35 and S36. In this case the encrypted portions of this message, N1-N8, and N13-N16, are decrypted by the receiver with the same encryption key used by the wireless key or keypad which transmitted the encrypted message, as shown at step S37. The wireless key or keypad ID contained in N9-N12, as well as the CRC in N17-N20, is transmitted unencrypted in order for the receiver to locate the encryption key associated with that specific wireless device stored in its database, as has been previously described. If both CRC's fail, then the message is ignored at step S38. Note that the order of CRC calculation can be changed; the order described above was chosen in order to lessen the computational requirements of the receiver since it is more likely, in this scenario, that the message will be in unencrypted format than in encrypted format. If, however, the converse is true, then the encrypted format CRC would be checked first.
It can be seen, from the above discussion, how the receiver differentiates an encrypted message from one that is a standard, unencrypted one. Namely, it allows for reception and storage of the maximum of 80 information bits, in anticipation of an encrypted message, even if the received message turns out to be of the standard unencrypted message only 48 bits long. Then it examines N9-N12 for correct CRC. If the CRC is correct, the standard unencrypted message is assumed followed by the process described above for format (A). If CRC fails in those bit positions, it checks for correct CRC in N17-N20. If the CRC is correct there, the encrypted message is assumed followed by the process described for format (B). If both CRC checks fail, an error in reception has occurred and the received data is discarded. It is with this method that the receiver can process encrypted and unencrypted messages interchangeably.
The circuitry and logic used to implement the encoding functions and decoding functions described herein may be in the form of microprocessors and associated memory devices such as ROM, RAM, EEPROM, etc. as well known in the art of circuit design. The various functions and algorithms described herein, as exemplified by the provided flowchart diagrams, are readily implemented by programming techniques and encryption and decryption methodologies known the art. In addition to standard microprocessor-based circuitry, the above-described functions may be integrated within a dedicated application-specific integrated circuit (ASIC), dedicated logic chips, or any combination thereof.
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Disclosed are three major aspects relating to wireless transmission of encrypted data messages in a security system wherein the receiver stores locally an encryption key utilized by the transmitting device to encrypt the data message and the receiver uses the encryption key to decrypt an encrypted data message, and wherein a sequence number generator is used to synchronously track the message sequence at both the transmitter and receiver. A first major aspect involves encrypted device registration (learning) methods that are user-friendly and immune from detection by technically skilled intruders with special RF equipment, and periodic user-friendly changing of the encryption key per encrypted transmitting device in the system. A second major aspect involves encrypted device de-registration (unlearning, or deletion) that is likewise user friendly. A third major aspect of the invention allows the receiver to process encrypted and non-encrypted messages, interchangeably, within the same wireless security system.
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BACKGROUND OF THE INVENTION
The present invention relates to a dual tubing release apparatus and actuating apparatus therefor for use in well operations. More specifically, the present invention relates to an improved simultaneous concentric dual tubing release apparatus such as those described in U.S. patent application Ser. No. 773,773, filed on Sept. 5, 1985 now U.S. Pat. No. 4,655,298.
The well completion apparatus described in the above-identified application includes an apparatus for the simultaneous decoupling of concentric tubing strings through the use of a shifting tool run on a wireline or slickline in the well.
One of the decoupling apparatus includes a movable sleeve positioned between the first and second tubing strings adjacent the couplings for releasing the lower sections thereof. As the movable sleeve is slid by the shifting tool run on a wireline or slickline within a chamber formed between the tubing strings, collet fingers on the detachable couplings are released allowing the lower tubing sections to fall to the bottom of the well with the perforating gun.
In another embodiment, the movable sleeve includes a plurality of lugs which extend through the second tubing string towards the center of the tubing. These lugs can be engaged by a positioning tool lowered on a wireline or slickline into the well. The wireline or slickline can then be raised or lowered causing the sleeve to shift and detach the tubing.
SUMMARY OF THE INVENTION
The present invention is directed to an apparatus and method of operation for the release of concentric tubing strings used in well operations.
The apparatus includes a tubing release assembly and an air chamber assembly as an actuating tool.
The tubing release assembly comprises a housing, release sleeve, adjustment nut, pull tube mandrel, pull tube adapter, pull tube latch and retainer ring.
The air chamber assembly as an actuating tool comprises a lower end plug, a housing, a housing retainer, seal element assembly, upper and lower shear pin retainers, upper element cone, release ring, setting mandrel, upper end plug, retrieving mandrel, and match drill assembly.
In an alternative embodiment, the tubing release assembly comprises a housing, release sleeve, adjustment nut, pull tube mandrel, pull tube adapter having a ball seat therein and pull tube latch. The alternative embodiment of the tubing release assembly is actuated by a ball being pressured against the ball seat of the pull tube adapter.
Additional features and advantages of the invention will become more fully apparent from the following detailed description and claims taken in conjunction with the attached drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1A and 1B are cross-sectional views of the tubing release assembly of the present invention.
FIGS. 2A and 2B are cross-sectional views of the actuating tool.
FIGS. 3A and 3B are cross-sectional views of the tubing release assembly and air chamber assembly received therein.
FIGS. 4A and 4B are cross-sectional views of an alternative embodiment of the tubing release assembly of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
Referring to FIGS. 1A and 1B, the tubing release assembly 10 of the present invention is shown in its preferred embodiment.
Referring, more specifically, to FIG. 1A, a portion of the pull tube mandrel 12, upper housing 14, release sleeve 16, and lower housing 90 are shown.
As shown in FIG. 1A, the portion of the pull tube mandrel 12 comprises an elongated annular cylindrical member having, on the exterior thereof, first cylindrical surface 20, second cylindrical surface 22 having, in turn, first annular recess 24 therein and second annular recess 26 therein and, on the interior thereof, first threaded bore 28, first cylindrical bore 30, and second cylindrical bore 32 having, in turn, annular recess 34 therein, and third cylindrical bore 36. The portion of the pull tube mandrel 12 further includes a plurality of apertures 38 which allow fluid communication between the exterior of the mandrel 12 to the interior thereof.
The portion of the upper housing 14 comprises an elongated annular cylindrical member having, on the exterior thereof, cylindrical surface 42 and, on the interior thereof, threaded bore 44, first cylindrical bore 46 having, in turn, annular recess 48 therein containing annular elastomeric seal 50 which sealingly engages second cylindrical surface 22 of pull tube mandrel 12, second cylindrical bore 52, third cylindrical bore 54, fourth cylindrical bore 56, fifth cylindrical bore 58, sixth cylindrical bore 60 having a diameter smaller than bore 58 and seventh cylindrical bore 62 having a diameter greater than bore 60. The portion of the upper housing 14 shown further includes a plurality of first threaded apertures 64 threadedly receiving a plurality of threaded fasteners 66 therein, a plurality of second threaded apertures 68 receiving a plurality of threaded set screws 70 therein and a plurality of apertures 72 which allow fluid communication from the exterior of the upper housing 14 to the interior thereof.
The portion of the release sleeve 16 comprises an elongated annular cylindrical member having on the exterior thereof first cylindrical surface 74 having, in turn, annular recesses 76 containing annular elastomeric seals 78 therein and annular recess 80 and second cylindrical surface 82 and, on the interior thereof, cylindrical bore 84 having, in turn, first annular recesses 86 therein containing annular elastomeric seals 88 therein.
The portion of the lower housing 90 comprises a plurality of collet fingers 92 having enlarged heads 94 thereon having, in turn, exterior surfaces 96 which engage fifth cylindrical bore 58 of upper housing 14 and interior surfaces 98 which slidingly engage second cylindrical surface 82 of release sleeve 16.
Referring to FIG. 1B, the remaining portion of the tubing release assembly 10 is shown.
The remaining portion of the tubing release assembly 10 comprises a portion of pull tube mandrel 12, a portion of upper housing 14, a portion of release sleeve 16, a portion of lower housing 90, adjustment nut 100, pull tube adapter 102, pull tube latch 104, and retainer ring 106.
The portion of pull tube mandrel 12 comprises an elongated annular cylindrical member having, on the exterior thereof, a continuation of second cylindrical surface 22, and, on the interior thereof, a continuation of third cylindrical bore 36 and second threaded bore 40.
The portion of the upper housing 14 comprises an elongated annular cylindrical member having, on the exterior thereof, a continuation of cylindrical surface 42 and, on the interior thereof, a continuation of seventh cylindrical bore 62. The upper housing 14 further includes annular end surface 108.
The portion of the release sleeve 16 comprises an elongated annular member having, on the exterior thereof, a continuation of second cylindrical surface 82 and, on the interior thereof, a continuation of cylindrical bore 84 having a second annular recess 110 therein.
The portion of the lower housing 90 comprises an elongated annular cylindrical member having, connected to one end thereof, a plurality of collet fingers 92, on the exterior thereof, first cylindrical surface 114 which slidingly engages seventh cylindrical bore 62 of upper housing 14, second cylindrical surface 116, and third cylindrical surface 118, and, on the interior thereof, first cylindrical bore which slidingly mates with second cylindrical surface 82 of release sleeve 16 and second cylindrical bore 124.
The adjustment nut 100 comprises an elongated annular cylindrical member having, on the exterior thereof, first cylindrical surface 126, second cylindrical surface 128 and threaded surface 130 and, on the interior thereof, threaded bore 132 which releasably, threadedly engages threaded surface 120 of lower housing 90 and cylindrical bore 134. The adjustment nut 100 further includes a plurality of threaded apertures 131 which releasably, threadedly engage a plurality of set screws 133 installed therein which in turn, have one end thereof engaging third cylindrical surface 118 of lower housing 90.
The pull tube adapter 102 comprises an elongated annular cylindrical member having, on the exterior thereof, threaded surface 136 which releasably, threadedly engages second threaded bore 40 of pull tube mandrel 12, first cylindrical surface 138, annular shoulder 140, second cylindrical surface 142, and third cylindrical surface 144 having, in turn, annular recess 146 therein and, on the interior thereof, cylindrical bore 148.
The pull tube latch 104 comprises an elongated annular cylindrical member having, on one end thereof, a plurality of collet fingers 150 having, in turn, enlarged heads 152 thereon which releasably engage annular recess 146 in third cylindrical surface 144 of pull tube adapter 102 and enlarged interior projections 154 which abut the end 156 of pull tube adapter 102, the collet fingers 150 being separated from each other by a plurality of longitudinal slots 158 and, on the exterior thereof, cylindrical surface 160 and threaded surface 162, and, on the interior thereof, cylindrical bore 164.
As shown in FIG. 1B, when the tubing release assembly 10 is assembled, a resilient annular retainer ring 106 is installed resiliently engaging second annular recess 110 of cylindrical bore 84 of release sleeve 16 and abutting annular surface 140 of pull tube adapter 102 being retained thereon by the end 166 of pull tube mandrel 12.
Referring to FIGS. 2A and 2B, the upper portion of the air chamber assembly 500 is shown in its preferred embodiment.
As shown in FIG. 2A, the upper portion of the air chamber assembly 500 includes retrieving mandrel 502, upper end plug 504, a portion of the setting mandrel 506, upper element cone 508, upper shear pin retainer 510, a portion of bonded seal element assembly 512, and release ring 514.
The retrieving mandrel 502 comprises an elongated cylindrical member having, on one end thereof, threaded surface 516 and on the exterior thereof, first cylindrical surface 518, second cylindrical surface 520 having, in turn, annular recess 522 therein, third cylindrical surface 524 having, in turn, annular recess 526 therein containing annular elastomeric seals 528.
The upper end of plug 504 comprises an elongated annular cylindrical member having, on the exterior thereof, frusto-conical surface 530, cylindrical surface 532, and threaded surface 534 and, on the interior thereof, first cylindrical bore 536 which slidingly engages first cylindrical surface 518 of retrieving mandrel 502 and second cylindrical bore 538.
The portion of the setting mandrel 506 shown comprises an elongated annular cylindrical member having, on the exterior thereof, first cylindrical surface and second cylindrical surface 542 having, in turn, an annular recess 544 therein and, on the interior thereof, threaded bore 546 which releasably, threadedly engages thread surface 534 of upper end plug 504, first cylindrical bore 548, frusto-conical bore 550, second cylindrical bore 552 having, in turn, annular recess 554 therein, third cylindrical bore 556 which slidingly, sealingly engages annular elastomeric seals 528 on retrieving mandrel 502 and fourth cylindrical bore 558. Also shown, included in setting mandrel 506 are a first plurality of apertures 560 which allow fluid communication between the first cylindrical surface 540 of the exterior of the mandrel 506 and third cylindrical bore 556 of the interior of mandrel 506 and a second plurality of apertures 562 which allow fluid communication between the second cylindrical surface 542 of the mandrel 506 and the fourth cylindrical bore 558 of the mandrel 506.
The upper element cone 508 comprises an annular cylindrical member having, on the exterior thereof, cylindrical surface 564 having, in turn, annular recess 566 therein and, on the interior thereof, 568 having, in turn, annular recess 570 therein containing annular elastomeric seals 572 which slidingly, sealingly engage second cylindrical surface 542 of setting mandrel 506. The upper element cone 508 further includes a plurality of apertures 574 having a plurality of shear pins 576 contained therein which, in turn, have a portion of each pin 576 retained within annular recess 544 of setting mandrel 506.
The upper shear pin retainer 510 comprises an annular cylindrical member having exterior surface 578, interior surface 580 and a plurality of apertures 582 therein having, in turn, a plurality of threaded pins 584 therein, each pin 584 having a portion thereof engaging annular recess 566 of upper element cone 508.
The portion of the bonded seal element assembly 512 comprises an elongated, annular cylindrical member having, on one end thereof, annular elastomeric member 586, on the exterior thereof, cylindrical surface 588, on the interior thereof, cylindrical bore 590 and a plurality of apertures 592 therethrough.
As further shown in FIG. 2A, the release ring 514 comprises an annular resilient member which is retained on retrieving mandrel 502 in annular recess 522 therein and resiliently engages annular recess 554 in setting mandrel 506.
Referring to FIG. 2B, the remaining portion of the air chamber assembly 500 comprises a portion of bonded seal element assembly 512, a portion of setting mandrel 506, lower shear pin retainer 594, match drill assembly 596, housing 598, lower end plug 600 and housing retainer 602.
The portion of the bonded seal element assembly 512 comprises an elongated, annular cylindrical member having cylindrical surface 588, cylindrical bore 590 and annular elastomeric member 604 bonded to the other end thereof.
The portion of setting mandrel 506 comprises an elongated annular cylindrical member having, on the exterior thereof, a continuation of second cylindrical surface 542 having, in turn, second annular recess 606 therein, third annular recess 608 therein and fourth annular recess 610 therein containing annular elastomeric seal 612 and, on the interior thereof, a continuation of fourth cylindrical bore 558.
The lower shear pin retainer 594 comprises an annular cylindrical member having exterior cylindrical surface 614 and interior cylindrical bore 616.
The match drill assembly 596 comprises an elongated annular cylindrical member having, on the exterior thereof, first cylindrical surface 618 and second cylindrical surface 620 and, on the interior thereof, first cylindrical bore 622 having, in turn, annular recess 624 therein containing annular elastomeric seal 626 which slidingly, sealingly engages second cylindrical surface 542 of setting mandrel 506, second cylindrical bore 628, and threaded bore 630. The match drill assembly further includes a first plurality of apertures 632 having, in turn, a plurality of shear pins 634 therein, each pin 634 having a portion thereof engaging third annular recess 606 in setting mandrel 506 and a second plurality of apertures 636 which allow fluid communication from the exterior of the match drill assembly 596 to the interior thereof.
The housing 598 comprises an elongated annular cylindrical member having, on the exterior thereof, threaded surface 638 which threadedly engages threaded bore 630 of match drill assembly 596, first cylindrical surface 640, first annular frusto-conical surface 642, second cylindrical surface 644, second annular frusto-conical surface 646, and third cylindrical bore 650 and threaded bore 652.
The lower end plug 600 comprises an elongated cylindrical member having first cylindrical surface 654 having, in turn, annular recesses 656 therein containing annular elastomeric seals 658 which sealingly engage cylindrical bore 650 of housing 598, threaded surface 660 which releasably, threadedly engages threaded bore 652 of housing 598, second cylindrical surface 662, and frusto-conical annular surface 664
Also shown in FIG. 2B is housing retainer 602 which comprises an annular resilient member retained on setting mandrel 508 in annular recess 608 therein.
Referring to FIGS. 4A and 4B, an alternative emobidment assembly 1000 of the present invention is shown.
Referring, more specifically, to FIG. 4A, a portion of the pull tube mandrel 1012, upper housing 1014, release sleeve 1016, and lower housing 1090 are shown.
As shown in FIG. 4A, the portion of the pull tube mandrel 1012 comprises an elongated annular cylindrical member having, on the exterior thereof, first cylindrical surface 1020, second cylindrical surface 1022 having, in turn, first annular recess 1024 therein and, on the in interior thereof, first threaded bore 1028, first cylindrical bore 1030, and second cylindrical bore 1032 having, in turn, annular recess 1034 therein, and third cylindrical bore 1036. The portion of the pull tube mandrel 1012 further includes a plurality of apertures 1038 which allow fluid communication between the exterior of the mandrel 12 to the interior thereof.
The portion of the upper housing 1014 comprises an elongated annular cylindrical member having, on the exterior thereof, cylindrical surface 1042 and, on the interior thereof, threaded bore 1044, first cylindrical bore 1046 having, in turn, annular recess 1048 therein containing annular elastomeric seal 1050 which sealingly engages second cylindrical surface 1022 of pull tube mandrel 1012, second cylindrical bore 1052, third cylindrical bore 1054, fourth cylindrical bore 1056, fifth cylindrical bore 1058, sixth cylindrical bore 1060 having a diameter smaller than bore 1058 and seventh cylindrical bore 1062 having a diameter greater than bore 1060. The portion of the upper housing 1014 shown further includes a plurality of first threaded apertures 1064 threadedly receiving a plurality of threaded fasteners 1066 therein, a plurality of second threaded apertures 1068 receiving a plurality of threaded set screws 1070 therein and a plurality of apertures 1072 which allow fluid communication from the exterior of the upper housing 1014 to the interior thereof.
The portion of the release sleeve 1016 comprises an elongated annular cylindrical member having on the exterior thereof first cylindrical surface 1074 having, in turn, annular recesses 1076 containing annular elastomeric seals 1078 therein and annular recess 1080 and second cylindrical surface 1082 and, on the interior thereof, cylindrical bore 1084 having, in turn, first annular recesses 1086 therein containing annular elastomeric seals 1088 therein. The release sleeve 1016 further includes a plurality of apertures 1110 therethrough to allow fluid communication from the interior to the exterior thereof.
The portion of the lower housing 1090 comprises a plurality of collet fingers 1092 having enlarged heads 1094 thereon having, in turn, exterior surfaces 1096 which engage fifth cylindrical bore 1058 of upper housing 1014 and interior surfaces 1098 which slidingly engage second cylindrical surface 1082 of release sleeve 1016.
Referring to FIG. 4B, the remaining portion of the tubing release assembly 1000 is shown.
The remaining portion of the tubing release assembly 1000 comprises a portion of pull tube mandrel 1012, a portion of upper housing 1014, a portion of release sleeve 1016, a portion of lower housing 1090, adjustment nut 1100, pull tube adapter 1102, and pull tube latch 1104.
The portion of pull tube mandrel 1012 comprises an elongated annular cylindrical member having, on the exterior thereof, a continuation of second cylindrical surface 1022, and, on the interior thereof, a continuation of third cylindrical bore 1036 and second threaded bore 1040.
The portion of the upper housing 1014 comprises an elongated annular cylindrical member having, on the exterior thereof, a continuation of cylindrical surface 1042 and, on the interior thereof, a continuation of seventh cylindrical bore 1062. The upper housing 1014 further includes annular end surface 1108.
The portion of the release sleeve 1016 comprises an elongated annular member having, on the exterior thereof, a continuation of second cylindrical surface 1082 and, on the interior thereof, a continuation of cylindrical bore 1084.
The portion of the lower housing 1090 comprises an elongated annular cylindrical member having, connected to one end thereof, a plurality of collet fingers 1092, on the exterior thereof, first cylindrical surface 1114 which slidingly, sealingly engages seventh cylindrical bore 1062 of upper housing 1014 and has annular recess 1015 containing annular elastomeric seal 1011 therein, second cylindrical surface 1116, and third cylindrical surface 1118, and, on the interior thereof, first cylindrical bore 1120 which slidingly, sealingly mates with second cylindrical surface 1082 of release sleeve 1016 and has annular recess 1121 containing annular elastomeric seal 1122 therein, and second cylindrical bore 1124.
The adjustment nut 1100 comprises an elongated annular cylindrical member having, on the exterior thereof, first cylindrical surface 1126, second cylindrical surface 1128 and threaded surface 1130 and, on the interior thereof, threaded bore 1132 which releasably, threadedly engages threaded surface 1118 of lower housing 1090 and cylindrical bore 1134. The adjustment nut 1100 further includes a plurality of threaded apertures 1131 which releasably, threadedly engage a plurality of set screws 1133 installed therein which in turn, have one end thereof engaging third cylindrical surface 1118 of lower housing 1090.
The pull tube adapter 1102 comprises an elongated annular cylindrical member having, on the exterior thereof, threaded surface 1136 which releasably, threadedly engages second threaded bore 1040 of pull tube mandrel 1012, cylindrical surface 1138, having, in turn, annular recess 1140 therein and, on the interior thereof, cylindrical bore 1142.
The pull tube adapter 1102 further includes annular cylindrical ball seat 1144 having, on the exterior thereof, cylindrical surface 1145 having, in turn, annular recess 1146 containing annular elastomeric seal 1147 therein sealingly engaging bore 1142 of the adapter 1102 and annular recess 1148 and, on the interior thereof, annular frusto-conical ball seal 1141 and bore 1149 therethrough. The annular cylindrical ball seal 1144 is releasably retained within the bore 1142 of pull tube adapter 1102 by a plurality of shear pins 1103 which, in turn, are releasably retained within threaded apertures 1139 of adapter 1102 and have a portion thereof engaging annular recess 1148 of seal 1144.
The pull tube latch 1104 comprises an elongated annular cylindrical member having, on one end thereof, a plurality of collet fingers 1150 having, in turn, enlarged heads 1152 thereon which releasably engage annular recess 1140 in the cylindrical surface 1138 of pull tube adapter 1102 and enlarged interior projections 1154 which abut the end 1156 of pull tube adapter 1102, the collet fingers 1150 being separated from each other by a plurality of longitudinal slots 1158 and, on the exterior thereof, cylindrical surface 1160 and threaded surface 1162, and, on the interior thereof, cylindrical bore 1164.
OPERATION OF THE TUBING RELEASE ASSEMBLY
Referring to FIGS. 3A and 3B, the operation of the tubing release assembly 10 of the present invention by the air chamber assembly 500 will be described.
When in use, the tubing release assembly 10 has tubing filled with fluid connected to first threaded bore 28 of pull tube mandrel 12 and threaded bore 44 of upper housing 14 and threaded fasteners 66 are disengaged from annular recess 24 of pull tube mandrel 12.
The air chamber assembly 500 is lowered into the tubing release assembly 10 by the air chamber assembly 500 having a slickline, or the like, attached to threaded surface 516 of retrieving mandrel 502.
The air chamber assembly 500 is lowered into the tubing release assembly 10 until second annular frusto-conical surface 646 of housing 598 of air chamber assembly 500 abuts annular frusto-conical bore 163 of pull tube latch 104 of the tubing release assembly 10 (see FIG. 3B).
When this occurs, apertures 592 in bonded seal assembly 512 of air chamber assembly 500 are aligned with apertures 38 of pull tube mandrel 12 of tubing release assembly 512 and annular elastomeric members 586 and 604 are positioned on either side of apertures 592.
Internal chamber 700 of the air chamber assembly 500 is at atmospheric pressure when the air chamber assembly 500 is landed into tubing release assembly 10. Before the actuation of air chamber assembly 500, apertures 562 in setting mandrel 506 are sealingly covered by upper element cone 508 to prevent fluid flow through apertures 562 with the shear pins 576 retaining the upper element cone 508 stationary on setting mandrel 506.
As hydrostatic fluid pressure of the fluid in the tubing connected to the tubing release assembly 10 is trying to shear shear pins 634 in shear pin retainer 594, the shearpins 634 must always have sufficient strength to prevent the hydrostatic fluid pressure of the fluid in the tubing from causing the pins to shear.
To actuate the air chamber assembly 500 after it is received in tubing release assembly 10, the application of a downhole force on the retrieving mandrel 502 of air chamber assembly 500 is made. When this force is applied, shear pins 576 and 634 are sheared thereby allowing setting mandrel 506 to move downwardly with respect to upper element cone 508, bonded seal assembly 512, shear pin retainer 594 and housing 598 until annular shoulder 541 of setting mandrel 506 abuts the upper end of upper element cone 508 and shear pin retainer 510 thereby aligning the apertures 562 in the setting mandrel 506 with the apertures 592 in bonded seal assembly 512 of chamber assembly 500 and apertures 38 of pull tube mandrel 12 of tubing release assembly 10.
With the downward movement of the setting mandrel 506 abuttingly engaging upper end of upper element cone 508 and shear pin retainer 510 the annular elastomeric members 586 and 604 firmly, sealingly engage second cylindrical bore 32 of pull tube mandrel 12 with the alignment of apertures 562, 592 and 38 respectively, the annular chamber 15 of tubing release assembly 10 is vented to, or placed in communication with, chamber 700 of air chamber assembly 500.
With the venting of annular chamber 15 of the tubing release assembly 10 with, or in fluid communication with, the chamber 700 of the air chamber assembly 500 since the chamber 700 is initially at atmospheric pressure and the fluid in annular chamber 15 is at the hydrostatic fluid pressure in the tubing which has been trapped in annular chamber 15 when the air chamber assembly 500 is lowered into tubing release assembly 10 by pull tube mandrel 12 of assembly 10 sealingly engaging bonded seal assembly 512 of air chamber assembly 500, the fluid in the tubing flows through apertures 38 in pull tube mandrel 12, from annular chamber 15 and flows into chamber 700 thereby causing a pressure differential across release sleeve 16 since release sleeve 16 has hydrostatic fluid pressure acting on one side thereof through apertures 72 in upper housing 14. When this pressure differential across release sleeve 16 is sufficient to cause shearing of shear pins 70, the release sleeve 16 moves upwardly through annular chamber 15 into the upper enlarged portion thereof with the end surface 75 of release sleeve 16 possibly abutting annular surface 53 of upper housing 14 and essentially atmospheric pressure acting on the outer side thereof by the venting of trapped hydrostatic fluid pressure in annular chamber 15 to chamber 700 of air chamber assembly 500. When the release sleeve 16 moves upwardly, the retainer ring 106 is resiliently compressed inwardly until the release sleeve 16 has moved thereby when it springs outwardly past end surface 85 of the sleeve 16 to prevent any downward movement of the sleeve 16 in the tubing release assembly 10.
When the release sleeve 16 no longer has a portion thereof abutting enlarged heads 152 of collet fingers 150 of pull tube latch 104, the collet fingers 150 are cammed outwardly to disengage annular recess 146 of the pull tube adapter 102 by the weight of the tubing string attached to pull tube latch 104 thereby releasing the latch 104 from adapter 102.
Similarly, since the end 85 of release sleeve 16 moves upwardly past enlarged heads 94 of collet fingers 92 of lower housing 90, due to the weight of the tubing string attached to adjustment nut 100, the enlarged heads 94 disengage annular frusto-conical surface 59 and move past sixth cylindrical bore 60 of upper housing 14 thereby releasing the upper housing 14 from lower housing 90.
Also, when release sleeve 16 moves upwardly through annular chamber 15 and abuts end surface 53 of upper housing 14, since the annular elastomeric seals 78 of sleeve 16 no longer sealingly engage fourth cylindrical bore 56 of upper housing 14, fluid is free to bypass through apertures 72 in upper housing 14 and around the release sleeve 16 thereby relieving the pressure differential around sleeve 16 thereby acting as an auto-release of the air chamber assembly 500.
Alternately, the air chamber assembly 500 may be removed from the tubing release assembly 10 an upward jarring force is applied through the slickline, or the like, connected to retrieving mandrel 502 of the air chamber assembly 500. The jarring force causes release ring 514 to resiliently compress out of engagement with annular recess 554 of setting mandrel 506 thereby allowing retrieving mandrel 502 to move upwardly in setting mandrel 506 until release ring 514 springs outwardly from second cylindrical bore 552, while still engaging annular recess 552 of retrieving mandrel 502, into first cylindrical bore 548 and abuts end surface 539 of upper end plug 504. At this time, annular elastomeric seals 528 no longer sealingly engage third cylindrical bore 556 thereby allowing fluid communication through apertures 560 in setting mandrel 506, through third cylindrical bore 556 and into chamber 700. This upward movement of retrieving mandrel 502 also causes upward movement of setting mandrel 506 until housing retainer 602 springs outwardly into annular cavity 666 abutting the upper wall thereof thereby allowing fluid flow past the end of setting mandrel 506, past annular elastomeric seal 612 and through apertures 636 in match drill assembly 596 thereby allowing fluid flow to bypass annular elastomeric members 586 and 604 of bond seal element assembly 512.
Referring to FIGS. 4A and 4B, the operation of the tubing release assembly 1000 of the present invention by the ball 2000 and increased fluid pressure actuating thereon will be described.
When in use, the tubing release assembly 1000 has tubing filled with fluid connected to first threaded bore 1028 of pull tube mandrel 1012 and threaded bore 1044 of upper housing 1014 and threaded fasteners 1066 are disengaged from annular recess 1024 of pull tube mandrel 1012.
The ball 2000 is inserted and falls into the tubing release assembly 1000 until it seats on ball seat 1144.
After the ball 2000 lands on frusto-conical annular seat 1141 of ball seat 1144, the fluid pressure in the tubing is increased and act through apertures 1038 in pull tube mandrel 1012 and apertures 1110 of release sleeve 1016 thereby causing a pressure differential across release sleeve 1016 since release sleeve 1016 has hydrostatic fluid pressure acting on one side thereof through apertures 1072 in upper housing 1014. When this pressure differential across release sleeve 1016 is sufficient to cause shearing of shear pins 1070, the release sleeve 1016 moves upwardly through annular chamber 1015 into the upper enlarged portion thereof with the end surface 1075 of release sleeve 1016 possibly abutting annular surface 1053 of upper housing 1014.
When the release sleeve 1016 no longer has a portion thereof abutting enlarged heads 1152 of collet fingers 1150 of pull tube latch 1104, the collet fingers 1150 are cammed outwardly to disengage annular recess 1140 of the pull tube adapter 1102 by the weight of the tubing string attached to pull tube latch 1104 thereby releasing the latch 1104 from adapter 1102.
Similarly, since the end 1085 of release sleeve 1016 moves upwardly past enlarged heads 1094 of collet fingers 1092 of lower housing 1090, due to the weight of the tubing string attached to adjustment nut 1100, the enlarged heads 1094 disengage annular frusto-conical surface 1059 and move past sixth cylindrical bore 1060 of upper housing 1014 thereby releasing the upper housing 1014 from lower housing 1090.
Also, when release sleeve 1016 moves upwardly through annular chamber 1015 and abuts end surface 1053 of upper housing 1014, since the annular elastomeric seals 1078 of sleeve 1016 no longer sealingly engage fourth cylindrical bore 1056 of upper housing 1014, fluid is free to bypass through apertures 1072 in upper housing 1014 and around the release sleeve 1016 thereby relieving the pressure differential around sleeve 1016.
While the invention has been illustrated with respect to the present preferred embodiments, it will be appreciated that numerous modifications and changes could be made without departing from the spirit or essential characteristics of the invention. For example, the chamber 700 of the air chamber assembly 500 may be at any desired fluid pressure level.
Other modifications and changes to the invention will be apparent to those skilled in the art. Accordingly, all changes or modifications which come within the meaning and range of equivalency of the claims are to be embraced within their scope.
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An apparatus and method of operation for the release of concentric tubing strings used in well operations. In the preferred embodiment, the apparatus includes a tubing release assembly and an air chamber assembly as an actuating tool. The tubing release assembly comprises a housing, release sleeve, adjustment nut, pull tube mandrel, pull tube adapter, pull tube latch and retainer ring. The air chamber assembly as an actuating tool comprises a lower end plug, a housing, a housing retainer, seal element assembly, upper and lower shear pin retainers, upper element cone, release ring, setting mandrel, upper end plug, retrieving mandrel, and match drill assembly. Alternately, the tubing release assembly may be actuated by a ball and increased fluid pressure level within the interior of the tubing release assembly.
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The present invention relates to a method for causing the focus of laser light to jump from one of a plurality of laminated recording layers of a multilayer disk to a different one and for playing back data recorded in the different layer. The invention also relates to a playback apparatus used for the method.
The manner in which a playback apparatus for reading data from an optical multilayer disk directs a light beam at the disk is schematically shown in FIG. 1.
In this figure, a multilayer disk 1 has three recording layers, for example. This disk has a first recording layer 3, a second recording layer 4, and a third recording layer 5. Protective layers 2 and 6 are formed on the front side of the first recording layer 3 and on the rear side of the third recording layer 5, respectively.
In the illustrated example, laser light is focused by an objective lens 7 incorporated in an optical pickup device (not shown). The laser light is transmitted through the transparent protective layer 2 and focused onto the second recording layer 4. Under this condition, data can be read from the second recording layer 4.
In this case, the laser light focused by the objective lens is reflected by the second recording layer 4. The reflected light travels toward the objective lens and is returned to the pickup device, where the reflected light is received. In this way, data recorded on the recording layer 4 is read out. One example of construction of such playback apparatus is shown in FIG. 2.
In FIG. 2, laser light reflected by the multilayer disk 1 is received by a detector 11, which is divided into four parts, or 11A, 11B, 11C, and 11D. The light is received by the detector parts 11A and 11C, which are disposed diagonally. The light is converted into electrical signals which are then summed up by an adder 12. The resulting sum signal (A+C) is amplified by a preamplifier 13 and applied to a subtracter 16 and also to adders 20, 25. The light is also received by the detector parts 11B and 11D which are arranged diagonally, and converted into electrical signals. These electrical signals are summed up by another adder 14. The resulting sum signal (B+D) is amplified by another preamplifier 15 and applied to the subtracter 16 and also to the adders 20, 25.
The subtracter 16 produces an output signal c, or a focus error signal {(A+C)-(B+D)}, which is then equalized by a phase-compensating circuit 17 and applied to one terminal of a switch 18. A focus search drive voltage signal having a given characteristic is supplied from a focus search driver circuit 19 to the other terminal of the switch 18. Either signal selected by the switch 18 is supplied via a driver amplifier 28 to a focus driver coil 29 to drive it. In this way, an objective lens mounted inside the optical pickup device is moved relative to the optical disk 1.
In this case, if the result of a detection is that the optical disk 1 is in focus, then the switch 18 produces the focus error signal {(A+C)-(B+D)}. If the result of the detection is that the optical disk 1 is not in focus, then the focus search drive voltage signal is produced.
In the initial state created by turning on the power supply or the like, the focus search drive voltage signal is produced from the switch 18.
The adder 20 creates an output signal a, or playback RF signal (A+B+C+D), which is applied to one terminal of a comparator 21. This signal is compared with a reference voltage V1 applied to the other terminal of the comparator 21. That is, in the comparator 21, the playback RF signal (A+B+C+D) is compared with the reference voltage V1. When the level of the RF signal is in excess of the reference voltage V1, the disk is regarded as being in focus, and the comparator 21 delivers a focus OK signal (signal b) of H level. This focus OK signal turns on a switch 23.
When the level of the playback RF signal (A+B+C+D) is less than the reference voltage V1, the disk is regarded as being out of focus, and the comparator 21 produces a signal of L level. This signal turns off the switch 23.
The focus error signal {(A+C)-(B+D)} delivered from the subtracter 16 is compared with a reference voltage V2 of zero potential by a comparator 22. The comparator 22 produces a zero-crossing detection signal which is produced when the focus error signal {(A+C)-(B+D)} crosses the zero point. When the focus OK signal is being produced, the zero-crossing detection signal passes through the switch 23 and is applied as a signal d to a central processing unit (CPU) 24. The CPU 24 senses that the disk is just in focus by detecting the trailing edge of the zero-crossing detection signal.
The adder 25 creates the playback RF signal (A+B+C+D) which is supplied to a data decoder 27 via an RF preamplifier 26. Data read from the optical disk 1 is decoded by the data decoder 27 and supplied to the CPU 24.
The CPU 24 senses how many recording layers in the optical disk 1 by referring to the subcode R included in subcodes in the supplied data. The CPU 24 also senses which recording layer is the presently read recording layer by referring to layer data recorded in the subcode S included in the subcodes.
At this time, the CPU 24 detects the trailing edge of the zero-crossing detection signal applied via the switch 23. The CPU produces a focus ON signal e indicating that the disk is in focus at that timing. This focus ON signal e controls the switch 18 in the manner described above.
That is, the CPU 24 is designed so that it receives the subcodes and the focus error signal {(A+C)-(B+D)} from the data decoder 27 and can sense whether the desired recording layer is in focus or not.
FIG. 3 is a waveform diagram illustrating the operation of the playback apparatus shown in FIG. 2. The operation of the playback apparatus is now described by referring to FIG. 3. Signal waveforms a-e shown in this figure correspond to signals a-e, respectively, shown in FIG. 2.
We now describe a case in which the light is to be focused onto the second recording layer of the optical disk 1 consisting of the three recording layers. The playback apparatus first detects the number of recording layers of the optical disk 1. Then, data for making a jump to the second recording layer is set.
It is assumed that a search is started at timing H. The focus driver coil 29 is driven with the focus search drive voltage signal. The objective lens 7 mounted in the optical pickup device is moved. If the optical disk 1 is gradually brought to a focus, the playback RF signal a produced from the adder 20 exceeds the reference voltage V1. The comparator 21 produces the focus OK signal b of H level, as shown. This turns on the switch 23, permitting the output from the comparator 22 to be fed to the CPU 24. The focus error signal c is compared with the reference voltage V2 which is at zero potential, by the comparator 22. The comparator 22 produces the zero-crossing detection signal d, and this signal is applied to the CPU 24.
The focus error voltage characteristic shown as the signal c is depicted in FIG. 4. The distance traveled by the focus from the optical focal point is plotted on the horizontal axis. The error voltage is plotted on the vertical axis. As shown, the focus error voltage characteristic changes like the letter S. A focus servo operation which is a feedback control is carried out by making use of the straight range in the center of the characteristic. When the error voltage decreases down to zero, an optical focused condition is accomplished. To detect this focused condition, the CPU 24 detects the trailing edge of the zero-crossing detection signal d. That is, if the trailing edge of the zero-crossing detection signal d is detected, the CPU 24 judges that a focused condition has been attained. Then, the CPU 24 produces the focus ON signal e. The switch 18 passes the output from the phase-compensating circuit 17 under the control of the focus ON signal e.
As a result, focus servo is started to be applied at timing I, for example. The apparatus is so controlled that the presently focused recording layer is maintained in focus.
By this focus servo control, the first recording layer is focused. Subcodes recorded in the first recording layer are read out, decoded by the data decoder 27, and supplied to the CPU 24. Data used to make a jump to the second recording layer is fetched from the subcodes and read into the CPU 24 which refers to data about the number of layers in the optical disk 1. Data is to be read from this second recording layer. The focus ON signal is made to go low (L) at timing J. At this time, a search of the second recording layer for data is started.
That is, the focus search drive voltage signal from the focus search driver circuit 19 is supplied to the focus driver coil 29 to move the objective lens 7 in the optical pickup. Thus, a search is made.
As this objective lens 7 moves, the focus error signal c changes as shown in FIG. 3 according to the error voltage characteristic shown in FIG. 4. At moment K, the second trailing edge of the zero-crossing detection signal of the focus error signal is detected. At this time, the result of detection is that the optical pickup device is focused onto the second recording layer.
In particular, the focus ON signal e from the CPU 24 is fed to the switch 18. The focus error signal c from the phase-compensating circuit 17 drives the focus driver coil 29 via the driver amplifier 28. This causes the focus servo to apply to the second recording layer. Hence, data recorded on the second recording layer is read out.
In the above-described focus servo technique, the focus servo is applied generally at a point where the amplitude of the playback RF signal assumes a maximum value or the jitter of the playback RF signal is set to a minimum value.
However, when the focus servo is set in this way, the focus servo is not applied in such a way that the focus balanced point agrees with the optical focus balanced point as shown in FIG. 4. Rather, the focus servo is generally applied in such a manner that the point agrees either with a focus balanced point R1 (as shown in FIG. 5) or R2 deviating from the optical focus balanced point.
The main cause of the above-described deviation of the focus balanced point is optical aberration. Offset of the focus servo is a minor cause. This optical aberration differs among different optical disks or different recording layers. As a consequence, the focus balanced point at which optimal reading is done differs among optical disks or recording layers.
In this case, the peak height value measured from the focus balanced point at which the S-shaped error voltage characteristic is read optimally to a positive peak P1 is different from the peak height value measured from the focus balanced point at which optimum reading is done to a negative peak P2.
When the focus servo is applied in such a manner that the point is the focus balanced point R1 or R2 deviating from the optical focus balanced point in this way, reading from the optical disk 1 is done well. However, we have found that if a focus jump from one recording layer to another for switching the recording layer being read is attempted, the focus servo to the next recording layer gets easily out of order.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide a method and apparatus for playing back data from an optical multilayer disk, the method and apparatus being characterized in that a focus jump from one recording layer to another is permitted but focus servo to the next recording layer can be stably applied after the focus jump.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a view showing the relation between an optical disk and an optical pickup device for use in a method according to the invention;
FIG. 2 is a block diagram showing one example of the construction of the prior art multilayer disk playback apparatus;
FIG. 3 is a waveform diagram illustrating the operation of the prior art multilayer disk playback apparatus shown in FIG. 2;
FIG. 4 is a diagram showing a focus error voltage characteristic having an optical focus balanced point;
FIG. 5 is a diagram of a focus error voltage characteristic, illustrating a focus balancing voltage in the prior art multilayer disk playback apparatus;
FIG. 6 is a block diagram showing one embodiment of an apparatus for playing back a multilayer disk, the apparatus embodying a method of playing back the multilayer disk in accordance with the present invention;
FIG. 7 is a diagram showing examples of focus error voltage characteristics, illustrating focus jump of a multilayer disk playback apparatus according to the invention; and
FIGS. 8A and 8B are waveform diagrams showing variations of a focus error voltage signal when a focus jump is made by a multilayer disk playback apparatus according to the invention.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 6 is a block diagram showing the configuration of one embodiment of an apparatus according to the invention in which the apparatus is designed to play back an optical multilayer disk. The apparatus embodies a method of playing back the optical multilayer disk in accordance with the invention.
In this figure, a detector 11 receives laser light reflected by an optical disk 1 having a plurality of recording layers and converts it into an electrical signal. The detector 11 is divided into four parts 11A-11D. To facilitate understanding, it is assumed in the present embodiment that the optical disk to be played back has two recording layers. The output signals from the detector parts 11A and 11C produced in response to received light are summed up by an adder 12 and amplified by a preamplifier 13. The signal is then fed to one input terminal of a focus balance-setting circuit 16-2. The output signals from the detector parts 11B and 11D in response to received light are summed up by another adder 14 and amplified by another preamplifier 15. Then, the signal is inverted in sign by an inverter 16-1 and applied to the other input terminal of the focus balance-setting circuit 16-2. In this way, the focus balance-setting circuit 16-2 creates a focus error voltage {(A+C)-(B+D)} which is the difference between the output signal (A+C) from the preamplifier 13 and the output signal (B+D) from the preamplifier 15.
The focus balance-setting circuit 16-2 is a circuit for adjusting the focus error voltage so that optimum reading from the optical disk 1 can be done. This circuit comprises means for setting focus balancing voltages corresponding to the recording layers of the optical disk 1 and producing the set voltages, together with a means for producing a reference focus balancing voltage whose error voltage characteristics are in a neutral state. In the configuration shown in FIG. 6, the means for producing a focus balancing voltage to the first recording layer of the optical disk 1 is a variable resistor Ra, for example. The means for producing a focus balancing voltage to the second recording layer is a variable resistor Rc. The means for producing the reference focus balancing voltage whose error voltage characteristics are in a neutral state is a variable resistor Rb.
Plural focus error voltages produced by the focus balance-setting circuit 16-2 are applied to a selector 16-3. Any one of the focus error signals {(1-K) (A+C)-(1+K) (B+D)} (signal c) is selected and delivered. This coefficient K is set by the focus balance-setting circuit 16-2. An optimum coefficient K is preset for the recording layer. Alternatively, the coefficient K is automatically set so that the amplitude of the RF playback signal is increased to its maximum value or that the jitter is reduced to a minimum. The output from the selector 16-3 is equalized by a phase-compensating circuit 17 and applied to one terminal of a switch 18. The switch 18 passes a focus drive voltage produced either from the phase-compensating circuit 17 or from the focus search driver circuit 19. The output voltage from the switch is power-amplified by the driver amplifier 28 and supplied to the focus driver coil 29, thus driving it. As a result, the objective lens (not shown) is moved in the direction of the optical axis so that the light is focused onto the desired layer on the optical disk 1.
In the adder 20, the output from the preamplifier 13 and the output from the preamplifier 15 are summed up to create a playback RF signal (A+B+C+D) (signal a). This signal a is compared with a reference voltage V1 in a comparator 21. When the level of the signal a exceeds the reference voltage V1, the output signal b goes high (H). A focus OK signal turns on the switch 23 which receives a zero-crossing detection signal from a comparator 22 that compares a focus error voltage {(1-K) (A+C)-(1+K) (B+D)} with a reference voltage V2 of zero potential, the focus error voltage being delivered from the selector 16-3. When the focus OK signal is fed to the switch 23, the zero-crossing detection signal d from the comparator 22 is fed to the CPU 24. The CPU 24 detects the trailing edge of the zero-crossing detection signal d.
The adder 25 produces the sum of the output from the preamplifier 13 and the output from the preamplifier 15 to create the playback RF signal (A+B+C+D). This playback RF signal is amplified by an RF preamplifier 26 and then decoded by a decoder 27. The decoded signal contains subcodes P-W which can contain information other than main information in the optical disk 1. Decoded subcodes are supplied to the CPU 24. The CPU 24 reads data about the number of recording layers on the optical disk 1, for example, from the subcode R of the subcodes read from the optical disk 1. At the same time, the CPU 24 reads data indicating the number given to the recording layer which is presently being read, for example, from the subcode S of the subcodes.
When the CPU 24 senses from the applied zero-crossing detection signal d that the optical disk 1 is in focus, a focus ON signal e is fed to the switch 18. The switch 18 passes the output signal from the phase-compensating circuit 17.
Then, the operation of the multilayer disk playback apparatus shown in FIG. 6 is described by referring to the above-described waveform diagram of FIG. 3. It is assumed that in the initial state established by turning on the power supply or the like, the switch 18 is connected to the focus search driver circuit 19 and the output from the variable resistor Ra for the first recording layer is selected by the selector 16-3.
Then, the focus driver coil 29 is driven according to the focus search drive signal produced from the driver amplifier 28, and the objective lens in the optical pickup is moved relative to the optical disk 1.
As this movement is made, the focus error voltage signal c is created, as shown in FIG. 3, from light reflected by the optical disk 1, the light being received by the detector 11. The error voltage signal is delivered from the selector 16-3. Zero-crossing of the focus error voltage signal c produced from the selector 16-3 is detected by the comparator 22.
The adder 20 creates the playback RF signal a from light reflected by the optical disk 1, the light being received by the detector 11. The playback RF signal a produced by the adder is compared with the reference voltage V1 by the comparator. When the level of the playback RF signal a exceeds V1, a high-level signal is produced as shown in FIG. 3. The high-level signal from the comparator 21 is the focus OK signal b, which turns on the switch 23.
Therefore, the zero-crossing detection signal d produced by the comparator 22 is fed to the CPU 24 via the switch 23. When the trailing edge of the zero-crossing detection signal d is detected, the CPU 24 judges that the optical disk 1 is brought to a focus, and produces the focus ON signal e. The switch 18 is thereby connected to the phase-compensating circuit 17, thus forming a feedback loop. As a result, focus the servo acts.
This makes it possible to read data from the first recording layer of the optical disk 1. If the laser light jumps from the first recording layer to another recording layer due to a scratch or the like during the reading of the data, the layer jump can be easily detected by reading data about the subcode S, for example, in the subcodes.
The operation performed when the focus is made to jump from the first recording layer to the second recording layer, for example, is next described. Characteristic operations of this case are briefly described by referring to FIG. 7.
FIG. 7 shows three focus error voltage characteristics. The focus error voltage characteristic indicated by the broken line is the focus error voltage characteristic concerning one layer of the optical disk 1 and corresponds to the first recording layer in this example. The focus error voltage characteristic indicated by the dot-and-dash line is the focus error voltage characteristic concerning another layer of the optical disk 1 and corresponds to the second recording layer in this example. The focus error voltage characteristic indicated by the solid line is the focus error voltage characteristic concerning a neutral state having an optical focus balanced point.
Optimum reading from the first recording layer can be done at focus balanced point R1. Optimum reading from the second recording layer can be done at focus balanced point R2. Therefore, the focus balance-setting circuit 16-2 adjusts the variable resistance Ra to vary the coefficient K. When an optically focused condition is accomplished, the circuit produces the focus error voltage which is a focus balancing voltage (E1). The circuit varies the variable resistance Rc to change the coefficient K. When an optically focused condition is accomplished, the circuit produces the focus error voltage which is a focus balancing voltage (E2).
Since the optimum focus balancing voltage differs among different recording layers in this way, the focus servo easily gets out of order after a jump of the focus as described above.
Accordingly, in the present invention, where the focus is made to jump from the first recording layer to the second recording layer, immediately before the execution of the jump, the focus error voltage characteristic is made to shift to the focus error voltage characteristic which is in a neutral state and has the optical focus balanced point indicated by the solid line in FIG. 7. Specifically, the selector 16-3 is so controlled that the neutral reference focus balancing voltage is produced, using the variable resistor Rb instead of the focus balancing voltage produced, using the variable resistor Ra best suited for the first recording layer. Then, the focus is made to jump to the second recording layer. Thereafter, the selector 16-3 is so controlled that the focus balancing voltage is produced, using the variable resistor Rc adapted for the second recording layer instead of the reference focus balancing voltage produced, using the variable resistor Rb.
In this way, the focus servo acts on the second recording layer stably after the focus jump. This assures that data can be read from the second recording layer. The above description is provided in further detail by referring to the waveform diagram illustrating changes in the focus error voltage signals shown in FIGS. 6, 8A, and 8B. It is assumed that at timing A shown in FIG. 8A, the focus is made to jump from the first recording layer to the second recording layer at the timing A. A control signal is fed from a system controller incorporated in a playback apparatus (not shown) to the selector 16-3, thus producing the neutral reference focus balancing voltage, using the variable resistor Rb. Then, the CPU 24 causes the focus ON signal e to drop, so that the switch 18 permits the focus search driver circuit 19 to produce the focus search drive signal. In this manner, the objective lens in the pickup moves. The selector 16-3 produces a focus error voltage as shown in FIG. 8A. The focus passes over the first layer, and the second layer is gradually focused. When the amplitude of the RF playback signal created by the detector 11 in response to the received light exceeds the reference voltage V1, the comparator 21 produces the focus OK signal b, thus turning on the switch 23. When the trailing edge of the zero-crossing detection signal supplied from the comparator 22 to the CPU 24 is detected, the CPU 24 supplies the focus ON signal e so as to turn it on. The switch 18 passes the focus error signal c produced from the phase-compensating circuit 17. This timing is taken as timing B.
As a result, the focus servo acts. The selector 16-3 is controlled by a control signal so as to select the output, using the variable resistor Rc. Consequently, the selector 16-3 produces the focus balancing voltage best suited for the second recording layer at timing C at which the focus servo system stabilizes.
Accordingly, the focus servo stably acts on the second recording layer. This assures that data can be read from the second recording layer.
FIG. 8B shows variations of the focus error voltage signal where the focus is made to jump from the second recording layer to the first recording layer. In this case, at timing D, i.e., immediately before the jump of the focus, the focus balancing voltage in a neutral state is produced, using the variable resistor Rb. Then, the CPU 24 causes the focus ON signal e to drop, thus permitting the switch 18 to pass the focus search drive signal delivered from the focus search driver circuit 19. As a consequence, the objective lens in the pickup moves. The focus error voltage which is directed toward the first recording layer as shown in FIG. 8B is delivered from the selector 16-3. In this case, the level of the focus error voltage changes in the positive direction and then varies in the negative direction while approaching the first layer, unlike the above-described case.
The focus passes over the second layer, and the first layer is gradually focused. When the amplitude of the RF playback signal created by the detector 11 in response to the incoming light exceeds the reference voltage V1, the comparator 21 produces the focus OK signal b, thus turning on the switch 23. When the trailing edge of the zero-crossing detection signal supplied from the comparator 22 to the CPU 24 is detected, the CPU 24 supplies the focus ON signal e to the switch 18 so as to control it. The switch 18 passes the focus error signal c produced from the phase-compensating circuit 17. This timing is taken as timing E.
This permits application of the focus servo. The selector 16-3 is controlled by a control signal so as to select the output produced, using the variable resistor Ra. Consequently, the selector 16-3 produces the focus balancing voltage best suited for the first recording layer at timing F at which the focus servo system is settled.
Accordingly, the focus servo stably acts on the first recording layer. This assures that data can be read from the first recording layer.
With respect to the focus balancing voltage which is in a neutral state, the positive peak and the negative peak of the focus error voltage characteristic are ideally equal to each other. If the amount of error produced is about ±1 to 2 μm when converted into a distance traveled by the focus, then no problem arises.
In the description provided thus far, the focus balance-setting circuit 16-2 is built, using the variable resistors for the recording layers and the variable resistor producing a focus balancing voltage which is in a neutral state. The present invention is not limited to this structure. Each variable resistor may be constructed from an electronic volume. Furthermore, the focus balance-setting circuit 16-2 may be composed of one electronic volume, and the focus balancing voltage produced as described above may be varied at given timing. In this case, the selector 16-3 can be omitted.
Since the present invention is constructed as described thus far, even if the focus is made to jump from one recording layer of a multilayer disk to another, the focus servo can be applied stably after the jump of the focus. This assures that data can be read from the recording layer after the jump of the focus. In addition, the structure used for this purpose can be simplified.
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There is disclosed a method of playing back information from an optical multilayer disk having a plurality of recording disks stacked on top of each other, by the use of an optical pickup device. In order to switch the focused recording layer from a first one to a second one so that data is read from the second recording layer, the focus balanced condition of the pickup device is switched from a setting providing a focus error characteristic adapted for the first recording layer to a reference setting providing a neutral focus error characteristic. Then, the focal point of the pickup device is moved from the first recording layer. Subsequently, the pickup device is focused onto the second recording layer, and data is read from the second recording layer. Thereafter, the focus balanced condition of the pickup device is switched to a setting adapted to the second recording layer.
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BACKGROUND OF THE INVENTION
This invention relates to pressure regulating apparatus for use with vehicle tires and particularly to a pressure regulator which can be set to regulate the pressure in the vehicle tire by adjusting the biasing force of a spring which urges a valve member to close an inlet port from a pressure source.
It is known to provide a valve mechanism wherein a spring, which normally biases a closure member towards a valve seating, is adjustable to regulate the pressure passing into the valve through an air inlet port. Such adjustment may be made by means of a screw threaded into part of the valve housing and acting on one end of the spring. Rotation of the screw in one direction or another thus increases or decreases the biasing force of the spring.
Such pressure regulators are disclosed in British patent specifications numbers 1567402, 138694, 336624, 384760, 1580240 and U.S. Pat. Nos. 2,690,757, 2,987,071, 4,869,306 and 4,883,107.
It is also known from British patent specification 8172/1910 to provide a spring biased pressure relief valve wherein the spring is located between a bridging member and the valve head, and where the biasing force of the spring is adjustable by moving the bridge member upwardly or downwardly with respect to the spring. The bridging member locates in slots in the valve housing and is secured in its desired position by means of nuts.
British patent specification 2215438-A shows a spring biased relief valve wherein a pin extends transversely form a plunger which is in engagement with the spring and the pin is engaged by a rotary camming face formed in part of the valve housing. Rotation of the plunger causes a camming action on the plunger to adjust the biasing force of the spring.
In all the above patent specifications the adjustment of the tire pressure is a slow operation.
There is, however, a need particularly in the case of military vehicles, e.g. personnel carriers operating in desert conditions or other soft or boggy terrain to be able to adjust the tire pressure downwardly with a great degree of urgency and accuracy.
In some circumstances a vehicle may suddenly arrive at an area of such difficult terrain and it is important to be able to either advance or withdraw without undue delay. Thus, in order to combat the effect of the ground conditions, there is a need to quickly lower the tire pressure in order to provide a "footprint" of larger area to increase the traction of the vehicle.
SUMMARY OF THE INVENTION
Accordingly, a general object of the invention is to provide improvement is in one or more of these respects, or generally.
In an embodiment of the invention there is provided tire pressure control apparatus for use in co-operation with a vehicle tire inflation valve wherein a movable pressure regulator member is adapted to cooperate with a valve-regulating spring member to provide at least two spaced positions of said pressure regulator member corresponding to respective differing pressures in the tire, between which positions said pressure regulator member can be shifted in one step.
The pressure regulator member may comprise adjustable pin and slot means which enables variation of compression of the valve-regulating spring member. The use of pin and slot means enables adjustment of the tire pressure between two pre-determined values to be effected both quickly and accurately.
In an embodiment the pin means are rotatable about an axis parallel to the longitudinal axis of the vehicle tire inflation valve. In this embodiment the pin means may be located on the pressure regulator member and the slot means may be located on co-operating sleeve means.
In a further embodiment of the invention there is provided tire pressure regulating apparatus including a housing comprising an outer sleeve having a first end portion and a second end portion,
an inner sleeve member located within a pair of axial bores formed in the outer sleeve,
the inner sleeve member extending axially between a first end and a second end and having a pressure chamber in communication with a pressure inlet port,
pressure inlet valve means having passageways capable of connecting the pressure inlet port with atmosphere,
a spring member adapted to urge the pressure inlet valve means into sealing relationship with a seating formed on the pressure inlet port,
the spring member locating at one end with the pressure inlet valve means and at the other end with a pressure regulator member, the valve means, the spring member and the pressure regulator member being axially movable within an axial bore formed in the inner sleeve member,
the inner sleeve member being further provided with longitudinally extending slots,
the outer sleeve being formed with helical slots at its periphery and a plurality of recesses connecting with those slots,
the pressure regulator member having a radially extending pin passing through the longitudinally extending slots in the inner sleeve member and into the helical slots and recesses in the outer sleeve,
a screw plug affixed within a bore at the second end of the inner sleeve member and adapted to be screwed on to a stem of a conventional vehicle tire valve; a stationary plug having passageways formed thereon or therethrough and affixed within the bore in the second end of the inner member, the stationary plug having a tire valve stem depressing nipple depending axially therefrom,
whereby the biasing force of the spring may be adjusted by locating the radially extending pin in the pressure regulator member in a desired recess formed in the outer sleeve member.
BRIEF DESCRIPTION OF THE DRAWINGS
The above object and features of the invention will become clear from the following description which is given by way of example only with reference to the accompanying drawings in which:
FIG. 1 is a side elevation with part shown in section of a tire pressure regulating apparatus according to an embodiment the invention,
FIG. 2 is a longitudinal section view through the tire pressure regulating apparatus of FIG. 1, and
FIG. 3 is an exploded perspective view of the component parts of the apparatus.
FIG. 4 is a somewhat enlarged fragmentary sectional view of the apparatus shown in FIG. 2.
FIG. 5 is similar to FIG. 4 but shows another embodiment of the invention.
DESCRIPTION OF PREFERRED EMBODIMENTS
Referring to the drawings a control apparatus V as oriented in the drawings comprises a cylindrical housing 2 having a upper portion a lower portion of reduced diameter 6. A knurled head 8 is provided at one end of the housing. The portion 4 is formed with a bore 10 and the portion 6 is formed with a bore 12. An inner sleeve 14, formed with longitudinal slots 16 is freely rotatable within the housing 2.
The housing 2 is provided at its periphery with a pair of diametrically opposed helical slots 18, and a number of short recesses 20A, 20B, 20C and 20D extend from the helical slots in the direction parallel to the axis of the housing.
Slidably located within a bore 22 formed in the inner sleeve 14 are spring seats 24 and 26, and a pressure regulator member a compression spring 28 is fitted therebetween around spigots 30, 32.
The inlet valve 24 is formed at its lower end with a further short spigot 34 which is grooved to retain an O-ring 36, and passageways 37 are provided on its periphery.
The regulator member 26 has a cylindrical extension 38 which terminates as a head 40, and a pin 42 extends radially from the regulator member 26 to pass freely through each of the slots 16 and into the helical grooves 18 or one of the sets of dramatically opposing adjustment recesses 20A, 20B, 20C or 20D.
A rubber boot 44 envelopes part of the housing 2 in order to preclude ingress of foreign material e.g. road grime, sand or water.
The lower end portion of the inner sleeve 14 is formed with a bore 46 or pressure inlet port and a valve seat 48 against which the O-ring 36 locates during sealing operation of the valve.
A plug 50 having passageways 52 formed therein is shrink fitted into the bore 46 and has an axially projecting nipple 54 which extends into a screw threaded hole 56 in a further plug 58 which is also a tight fit in the lower portion of the bore 46.
In use, a vehicle tire is first inflated to its maximum pressure after which the control apparatus V is secured thereto by screwing the plug 58 on to the valve stem 60 of the road wheels so that the nipple 54 depresses the conventional tire pressure relief valve rod 62 to allow the air within the tire to escape through the valve stem 60. The air passes under pressure through the passages 52 in the plug 50 and acts on the lower face of the inlet valve 24 to urge that valve to seat against the biasing effect of the spring 28. Clearly, when the biasing force of the spring is equivalent to the pressure within the tire the inlet valve will remain in its operative position with the O-ring firmly compressed against the seat 48. When the pressure in the tire exceeds the biasing force of the spring then the inlet valve and its O-ring is lifted off of the valve seat 48 so that air under pressure escapes through passageways 37 and thence through the bore 22, slots 16 in the inner sleeve and helical slots 18 and recesses 20 to finally pass between the boot 44 and its contact points with the body 2 of the control apparatus.
In order to maintain the tire at its normal maximum recommended pressure the spring 28 is selected to provide a biasing force at least equal to the effect of that pressure. Initially the head 40 is manually depressed in order to move the pin 42 out of its engaging recess 20 and into the helical slot 18. Further downward pressure applied to the head 40 causes the pin 42 to cooperate with the slots 18 until it reaches the limit of the extent of the slot when manual pressure on the head is relaxed to enable the pin to be located in the lowermost recess 20D. The biasing force of the spring is then at its greatest and the vehicle is used in the normal manner whilst it operates under normal road surface conditions. When the surface conditions change such that a rapid increases in the size of the "footprint" of the tire is needed to allow the vehicle to have sufficient traction and low enough ground pressure to continue proceeding, the vehicle is preferably, but not necessarily stopped and then each of the units V is adjusted rapidly to allow air to escape from the respective tires.
Thus, the head 40 of each unit in turn is depressed to move the ends of the pin 42 from its engaging recess 20D into the helical slot 18 after which further downward pressure on the head 40 causes the housing 2 to rotate about the inner sleeve 14 until the pin aligns with the recess 20C, 20B, 20A as required to reduce the air pressure in the tires to the equivalent of the biasing force of the spring, so adjusted.
It is found that such adjustment can be rapidly and accurately effected by the use of the valve of the invention.
The vehicle may remain stationary to allow the tire pressure to stabilise, or may be driven whilst the pressure reduces towards the stabilised level selected.
In order that loss of tire pressure does not occur due to the effect of an unduly bumpy road surface or terrain, the unit V may be unscrewed and removed from the Schraeder valves on the road wheels. Thus, sudden jolts which would otherwise have temporarily increased the tire pressures above that preset by the spring are made ineffective. The units would of course be replaced when their use again becomes expedient.
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Apparatus for use in co-operation with a conventional tire inflation valve which enables the pressure in a tire to be reduced to a pre-determined value in a one step process. A movable pressure regulator member, comprising a pin and slot arrangement, co-operates with a valve regulating spring to close a valve member, once the pressure in the tire has reached the required valve.
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This is a continuation of application Ser. No. 08/723,506 filed Sep. 30, 1996, which is a continuation of application Ser. No. 08/546,063 filed Oct. 20, 1995, which is a continuation of application Ser. No. 08/322,373 filed Oct. 13, 1994, which is a continuation of application Ser. No. 08/226,374 filed Apr. 12, 1994, which is a continuation of application Ser. No. 07/883,572 filed May 15, 1992, all now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a position detecting device, and more particularly a technology, useful in a device for generating predetermined signal codes at different positions by sliding motion of sliding pieces or brushes on conductive patterns, for preventing generation of erroneous signals by defective contacts or chattering between the brushes and the conductive patterns.
2. Related Background Art
For example, in a zoom lens for a camera, it is already known to correct the diaphragm aperture and the amount of light emission from an electronic flash unit according to the regulation of the focal length. For such correction it is necessary to detect the set position of the focal length of the zoom lens.
For this purpose there is employed a signal generating device as shown in FIG. 4, comprising an arc-shaped conductive pattern member 5 bearing thereon conductive patterns 5a1, 5a2, 5a3, 5a4 constituting plural tracks, and a brush member 6 provided with plural brushes 6a, 6b, 6c, 6d sliding respectively on said conductive patterns 5a1, 5a2, 5a3, 5a4. The brushes 6a, 6b, 6c, 6d are mutually short circuited and respectively slide on the conductive patterns 5a1, 5a2, 5a3, 5a4 together with the movement of the zoom lens barrel. The conductive pattern 5a4 is taken, for example, as a ground pattern, with which the pattern 5a1, 5a2 or 5a3 is short circuited according to the position of the brush member 6. Therefore, code signals can be obtained from the conductive patterns depending on the position of the brush member 6.
Such a such signal generating device has been associated with a drawback of erroneous signal generation by so-called chattering, resulting from bouncing of the brushes at their sliding motion on the conductive patterns and on the insulating portions. Also, such errors in the signals may arise from defective contacts between the brushes and the conductive patterns, due, for example, to smears on the conductive patterns or on the brushes.
With such conductive patterns 5a1-5a4, an end pattern such as 5a1 is considered as an important position, and a code signal for reversing the drive is released when the brush member 6 reaches this position.
In such case, as will be apparent from FIG. 9, if defective contact arises between the conductive pattern 5a1 and the corresponding brush when the brush member arrives at a position B, the generated code signal becomes the same as that of the important position 26a, thereby leading to a serious error in function such as inversion of the driving direction. Also, if defective contact arises between the conductive pattern 5a1 and the corresponding brush when the brush member arrives at a position A, the generated code signal becomes the same as that of another important position 26b, resulting in another serious error in function.
SUMMARY OF THE INVENTION
In consideration of the foregoing, an object of the present invention is to provide a position detecting device capable of preventing generation of erroneous signals by defective contact or chattering between the conductive pattern and the brush and enabling precise detection of position.
Another object of the present invention is to prevent generation of a signal code the same as that of an important position, even in the presence of chattering or defective contact between the conductive pattern and the corresponding brush, thereby effectively preventing serious error in the function of a device.
The above-mentioned objects can be attained, according to the present invention, by a position detecting device provided with a pattern member having conductive patterns which are arranged on plural tracks and are adapted to provide plural signal lines with predetermined signal codes depending on different positions, a slidable member having plural sliding pieces capable of sliding on the tracks of said conductive patterns, and signal process means for reading said code signals by the contact between said pattern member and said slidable member and detecting the position based on said code signals, said position detecting device comprising signal discrimination means for reading said signal code plural times and recognizing said read signal code as a proper signal code when a same signal code is read at least for a predetermined number of times.
Also, the position detecting device of the present invention, may have a pattern member, slidable member and signal process means as mentioned above, and may further include signal discrimination means adapted to read said signal code plural times and recognize said signal code as a proper signal code when a same signal code is read over at least a predetermined time.
In the first-mentioned position detecting device, said signal discrimination means reads the signal code corresponding to the relative position of said pattern member and brush member, but said signal code is recognized as a proper signal code only when the same signal code is read a predetermined plural number of times. Consequently the probability of generation of erroneous signals, such as by chattering, becomes extremely small and precise detection of position is rendered possible.
Also, in the second-mentioned position detecting device, said signal discrimination means reads the signal code corresponding to the relative position of said pattern member and brush member, but said signal code is recognized as a proper signal code only when the same signal code is read over a predetermined time. Consequently the probability of generation of erroneous signals, such as by chattering, becomes extremely small and precise detection of position is rendered possible.
The above-mentioned objects can also be attained, according to the present invention, by a position detecting device provided with a pattern member having conductive patterns which are arranged on plural tracks and are adapted to provide plural signal lines with predetermined signal codes depending on different positions, a slidable member having plural sliding pieces capable of sliding on the tracks of said conductive patterns, and signal process means for reading said code signals by the contact between said pattern member and said slidable member and detecting the position based on said code signals, said position detecting device comprising memory means which stores in advance a train of proper code signals to be generated by said conductive patterns at the different positions, and comparator means for discriminating the adequateness of the code signal read from said signal lines by comparison of said code signal with the train of code signals stored in said memory means.
Said comparator means is advantageously so constructed as to discriminate the read code signal as a proper code signal when the read code signal is same as the previously read one, or, if not the same, the read code signal varies according to the sequence of code signal train stored in said memory means.
In the above-mentioned position detecting device, the memory means in advance stores a train of proper code signals to be generated when said slidable member moves to different positions with respect to said conductive patterns. Said comparator means discriminates the code signal read from the signal lines as a proper code signal when said read code signal is the same as the previously read one, or, if not the same, said read code signal varies from the previously read one according to the sequence of code signal train stored in said memory means. If the read code signal varies according to the sequence of said code signal train, the slidable member is considered to have moved to a next position between the previous code signal reading and the present code signal reading, so that the code signal is identified to be properly generated.
The foregoing objects can further be attained, according to the present invention, by a signal setting device provided with a pattern member having conductive patterns which are arranged on plural tracks and are adapted to provide plural signal lines with predetermined signal codes depending on different positions, and a brush member having plural brushes mutually connected electrically and capable of sliding on the tracks of said conductive patterns, wherein said conductive patterns are so constructed that erroneous signals codes generated by defective contact between said conductive patterns and the corresponding brushes, are different from the signal code corresponding to an important position.
For example, the signal code corresponding to the important position may be so constructed that two or more signal lines which do not become conductive at the same time in normal positions are conductive, or that all the signal lines are conductive.
In the above-explained structure, even when conduction failure occurs by chattering or defective contact in one or more sets of conductive pattern and corresponding brush in one of the normal positions, the signal code generated in such situation is different from the signal code at the important position. For this reason such signal code is not mistaken for an important signal code. Also, in case a signal code including conductive state in two or more lines which do not assume the conductive state at the same time in normal positions is taken as the signal code for an important position, an erroneous signal code generated, such as by chattering, in the course of signal reading at normal positions is not mistaken for an important signal code. The applies to a case in which a signal code, with all the signal lines in the conductive state, is taken as the signal code for such important position.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic block diagram of a camera employing a position detecting device of the present invention;
FIG. 2 is a flow chart of the control sequence of the position detecting device constituting a first embodiment of the present invention;
FIG. 3 is a flow chart of the control sequence of the position detecting device constituting another embodiment of the present invention;
FIG. 4 is a perspective view showing details of an encoder for code signal generation;
FIG. 5 is a flow chart of the control sequence of the position detecting device constituting still another embodiment of the present invention;
FIG. 6 is a schematic block diagram of a camera employing a signal setting device of the present invention;
FIG. 7 is a view showing the arrangement of conductive patterns in a signal setting device embodying the present invention;
FIG. 8 is a view showing the arrangement of conductive patterns in a signal setting device constituting another embodiment of the present invention; and
FIG. 9 is a view showing the arrangement of conductive patterns in a conventional signal setting device.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the following there will be explained an embodiment of the present invention, with reference to the attached drawings. FIG. 1 illustrates the structure of a camera employing a position detecting device embodying the present invention. The illustrated camera consists of an interchangeable lens 1 with an automatic focusing mechanism and a camera body 2. Said automatic focusing mechanism can be of known structure, and therefore will not be explained further.
The interchangeable lens 1 is provided with a focusing optical system L, an encoder 3, and a CPU 4 composed, for example, of a one-chip microcomputer. The encoder 3 has the aforementioned structure shown in FIG. 4, in which the brush member moves on the conductive patterns along with the movement of the focusing optical system L.
Signal lines a1, a2, a3 respectively connected to the conductive patterns 5a1, 5a2, 5a3 of the encoder 3 and a ground line a4 are connected to ports of the CPU 4, which thus reads the code signals from said encoder 3. More specifically, a voltage of +5 V, for example, is applied through a resistor (not shown) to the signal lines a1, a2, a3, which are selectively short circuited with the ground line a4 by the brush member, depending on the shape of the conductive patterns, whereby the CPU 4 can detect the conduction or non-conduction state between the signal lines a1, a2, a3 and the ground line a4 as low and high-level signals. In this manner the CPU 4 receives a code signal corresponding to the position of the brush member.
In FIG. 1, the CPU 4 principally identifies the adequateness of the code signal entered from the encoder 3, as will be explained later. A CPU 7, composed of a one-chip microcomputer and provided in the camera body 2, effects control necessary for phototaking operations, such as auto focusing and exposure control.
In the following there will be explained the prevention of erroneous signals by the CPU 4. The encoder 3 shown in FIG. 1 has the structure shown in FIG. 4 with conductive patterns 5a1-5a4, among which the pattern 5a4 is at the ground level. Insulating portions of the patterns are indicated by 5b. The brush member 6 is equipped with four brushes 6a, 6b, 6c, 6d and is at the ground level in normal state. When the brush member 6 is in a position range A of the pattern member 5, there is generated a code signal Sa with outputs to the CPU 4 shown in Table 1.
TABLE 1______________________________________ code Sa!Input line to CPU 5a1 5a2 5a3______________________________________Status High High Low______________________________________
Similarly, when the brush member 6 is in a position range B of the pattern member 5, there is generated a code signal Sb with outputs to the CPU 4 shown in Table 2.
TABLE 2______________________________________ code Sb!Input line to CPU 5a1 5a2 5a3______________________________________Status Low High Low______________________________________
Although said code signal Sb shown in Table 2 is to be generated when the brush member 6 is within the range B of the pattern member 5, a code signal Sa is instead generated if the brush 6a is lifted by bouncing as the conductive pattern 5a1 assumes the high level state.
The CPU 4 prevents the generation of an erroneous output signal by a sequence shown in FIGS. 2 or 3. FIG. 2 shows the control sequence of the CPU 4 in the position detecting device constituting one embodiment of the present invention. When a code signal is provided from the encoder 3, a counter in the CPU 4 is reset to a count n=0, and a memory M for storing the entered code signal S is cleared (step S21). Then the code signal S is read for the first time (step S22) and is compared with the information in the memory M (step S23). If the code signal is different, the counter is reset to n=0 (step S24), and the read code signal S is stored in the memory (step S25). Then a second reading is conducted (step S22) and comparison with the information of the memory M is conducted in a similar manner as in the first time (step S23). If the code signals entered for the first and second readings are the same, the second reading becomes equal to the content of the memory M whereby the count n of the counter is increased by one (step S26). Then the content n of the counter is compared with a predetermined number α n (step S27), and, if said content n is smaller, a third code reading is conducted (step S22) and is similarly processed. When the count n reaches α n in the repetition of the above-explained sequence, the output of the current encoder position is identified as S (step S28). A proper signal code is thus detected and entered into the CPU 7 of the camera body 2. Subsequently reading of the next code signal is initiated in a similar manner.
FIG. 3 shows the control sequence of the CPU 4 in the position detecting device constituting another embodiment of the present invention. In this embodiment, a proper code signal is identified if a same code signal is entered for a predetermined period α t , instead of the number α n of times of entries of same code signal as in the foregoing embodiment. Referring to FIG. 3, when a code signal is provided from the encoder 3, a timer in the CPU 4 is reset to t=0, and a memory M for storing the code signal S is cleared (step S31). Then the code signal S is read for the first time (step S32) and is compared with the content of the memory M (step S33). If both are different, the timer is reset to t=0 (step S34), and the read code signal is stored in the memory M (step S35).
Subsequently the code signal is read for the second time (step S32) and is compared with the content of the memory M as in the first time (step S33). If the code signals read for the first and second times are the same, the code signal read at the second reading becomes equal to the content of the memory M, and there is discriminated whether the timer is set at t=0 (step S36). If the timer is identified to be at t=0, starting of the timer is instructed (step S37). Then a third reading is conducted (step S32). If the read code signal is same as the content of the memory M, the timer is not at t=0 (step S36) as it has already been started. In this case the time t of the timer is compared with a predetermined time α t (step S38), and, if t is shorter, a fourth reading is conducted in a similar manner (step S32). When the time t reaches α t in the repetition of the above-explained sequence, the output of the current encoder position is identified as S (step S39). Subsequently reading of the next code signal is initiated in a similar manner.
In the present invention, as explained in the foregoing, the code signal is read plural times, and the read code signal is identified as a proper code signal when the same code signal is read for a predetermined number of times or for a predetermined period. Therefore, erroneous detection of position can be prevented even when an erroneous signal is temporarily generated, such as by chattering, and errors in the camera functions can thus be avoided.
FIG. 5 shows the control sequence of the CPU 4 for preventing the generation of error signals in a position detecting device constituting still another embodiment of the present invention. When a code signal is provided from the encoder 3, a memory M in the CPU 4 is cleared (step S51). Said memory M provides a work area for temporarily storing the entered code signal as a reference code.
Then, the code signal S is read for the first time (step S52), and comparison is conducted in order to discriminate whether said read code signal S is equal to a reference code stored in said memory M or codes adjacent to said reference code (step S53). If said read code signal S is not equal to the reference code nor the adjacent codes, the read code signal S is stored in the memory M (step S54), and a second code reading is conducted (step S52). At the first code reading, said comparison indicates the absence of coincidence because the memory M is cleared in advance.
Then the code signal S read in the second reading is compared, as in the first time, with the reference code stored in the memroy M or with the code adjacent to said reference code (step S53). The CPU 4 stores, in an internal memory, a train of proper signal codes to be generated corresponding to the different positions of the encoder 3, and said comparison with the adjacent code is conducted by the comparison of the read code signal with said train of signal codes. If the code signal S read in the second reading coincides with the code signal read in the first reading, namely the reference code stored in the memory M, said code signal read in the second reading is stored as the reference code in the memory M (step S55), and is identified as the proper current output of the encoder (step S56). Also, when the code signal read in the second reading coincides with a code signal adjacent to the reference code signal which is read in the first reading and stored in the memory M, the code signal S read in the second reading is stored as a new reference code in the memory M (step S55) and identified as the proper current output of the encoder (step S56).
In the following there will be explained a specific example. If the brush member 6 is within the range B of the encoder pattern 5 at the first code signal reading, there is read the code Sb shown in Tab. 2. Said code signal Sb is compared with the content of the memory M. Since the memory M has been cleared in advance, the code Sb is identified as the reference code and stored in the memory M.
Then the second code reading is conducted, and, if the read code S is again Sb, it coincides with the reference code stored in the memory M. Said code Sb is therefore stored as the reference code in the memory M, and the output corresponding to the current encoder position is identified as Sb.
If an erroneous code Sx induced by a brush chattering at the second code reading is entered and is different from the reference code Sb or the adjacent codes Sa, Sc, said code Sx is set as the reference code in the memory M. Then, if the proper code Sb is entered at the third code reading, comparison is conducted in a similar manner as explained above and the code Sb is again stored as the reference code in the memory M. Then, if the code Sb is again entered at the fourth reading, the entered code coincides with the reference code. Therefore, said code Sb is stored as the reference code in the memory M and is identified as the proper output corresponding to the current encoder position. Said identification is executed, for example, by storing said code Sb, as the output corresponding to the current encoder position, in a predetermined work area of the memory, and said code Sb stored in said work area is subsequently sent to the CPU 7 of the camera body 2.
In the above-explained sequence, the read code S is considered to match the reference code if said read code S coincides with the reference code or with one of the adjacent codes. This is based on a concept that the error in detection of position can be tolerated to the adjacent codes and is in consideration of the possibility that the code reading takes place at the boundary of different positions of the encoder in the course of movement of the brush. However, the present invention is not limited to the coincidence of the read code with one of the reference code and the adjacent codes, but may also be expanded to the coincidence of the read code with one of the reference code, adjacent codes thereof and codes adjacent to said adjacent codes.
According to the present invention, as explained in the foregoing, a proper code signal is identified in consideration of the case that the read code signal has varied according to the code train corresponding to the different positions of the encoder. Therefore, even if an erroneous code is temporarily generated, such as by chattering, an erroneous detection of position based on such code can be prevented a proper and the code signal can be identified reliably, in consideration of the status of actual use such as the movement of the brush member.
In the following there will be explained still another embodiment of the present invention. FIG. 6 illustrates the structure of a camera employing a signal setting device embodying the present invention. The illustrated camera consists of an interchangeable lens 1 with an automatic focusing mechanism, and a camera body 2. Said automatic focusing mechanism can be of known structure, and therefore will not be explained further.
The interchangeable lens 1 is provided with a focusing optical system L, an encoder 3, and a CPU 4 composed, for example, of a one-chip microcomputer. The encoder 3 has the aforementioned structure shown in FIG. 4, in which the brush member moves on the conductive patterns along with the movement of the focusing optical system L.
Signal lines a, b, c, d respectively connected to the conductive patterns of the encoder 3 and a ground line G are connected to ports of the CPU 4, which thus reads the code signals from said encoder 3. More specifically, a voltage of, for example, +5 V is applied through a resistor (not shown) to the signal lines a, b, c, d which are selectively short circuited with the ground line G by the brush member, depending on the shape of the conductive patterns, whereby the CPU 4 can detect the conduction or non-conduction state between the signal lines a, b, c, d and the ground line G as low- and high-level signals. In this manner the CPU 4 receives a code signal corresponding to the position of the brush member.
FIG. 7 shows an example of the conductive pattern member employed in the encoder 3 shown in FIG. 6. Said conductive pattern member is provided, for example, on a flexible printed circuit board (FPC), with conductive patterns being shown by hatched areas. End portions 5a, 5b of the conductive patterns serve for generating code signals for reversing the driving direction of the focusing optical system L and constitute important positions in the system. Positions between said important positions 5a, 5b are normal positions for detecting the position of the focusing optical system L.
The ground pattern G is formed continuously so that it is in contact with the corresponding brush regardless of the position. Each of said signal lines can be short circuited with the ground pattern through the brush member depending on the presence or absence of the conductive pattern, whereby a code signal corresponding to the brush position is applied to the CPU 4. Stated differently, the position of the brush member can be identified by the combination of conductive and non-conductive states between the signal lines a, b, c, d and the ground line G. In the present embodiment, when the brush member moves to the right from a certain position and reaches the important position 5b, the driving direction is reversed to the left by a code signal generated at said important position.
In the conductive patterns shown in FIG. 7, two or more signal lines which assume the conductive state in the important positions 5a, 5b do not assume the conductive state simultaneously in the normal positions. Therefore, even if a signal line which should be in the conductive state becomes non-conductive because of chattering, for example there is not generated a code signal the same as that of the important position. Stated differently, the patterns containing additional conductive lines, in addition to the conductive patterns at the important positions, should not be present at the normal positions.
The above-mentioned condition can be met if a plurality or all the signal lines are made conductive with the ground line G at the important positions. In case of the patterns shown in FIG. 7, the signal lines a, b and d are shortcircuited with the ground line G at the important position 5a, but these three lines do not become conductive at the same time in other positions, for example C and E. Also the signal lines a and c are conductive with the ground line at the important position 5b, but these two lines do not assume the conductive state simultaneously at other positions. Consequently an error signal generated such as by chattering cannot be mistaken for the signals of the important positions.
The configuration of FIG. 7, not requiring a conductive pattern nor a signal line exclusive for the detection of important positions, allows reduction of the width of the conductive pattern member and the number of ports of the CPU 4.
FIG. 8 illustrates a flexible printed circuit board constituting the conductive pattern member in another embodiment of the signal setting device of the present invention. In the present embodiment, exclusive conductive patterns 7a, 7b are provided in the important positions 6a, 6b at both ends. Between said conductive patterns 7a, 7b there are provided normal positions for detecting the position of the focusing optical system L.
In the conductive patterns shown in FIG. 8, there are provided signal lines connected to the conductive patterns 7a, 7b at the important positions 6a, 6b, and, when the brush member reaches one of these important positions 6a, 6b, the exclusive conductive pattern 7a or 7b is short circuited with the ground pattern G so that the presence of the brush member in one of these important positions can be easily recognized. In the normal positions, even if a non-conductive state occurs by chattering in any of the signal lines, for example, the resulting code signal is different from that of the important position since the exclusive conductive patterns 7a, 7b are not short circuited with the ground pattern G. The present configuration provides an advantage of increased freedom for pattern designing in the normal positions, because exclusive conductive patterns are employed for identifying the important positions.
Although the important positions are defined at the end portions of conductive patterns in the foregoing description, the important positions may be provided among the normal positions, or may be increased in number. Also, said important positions are defined in the foregoing description for providing code signals for reversing the driving direction of a lens device, but the present invention is applicable generally to mechanical devices provided with position dependent electronic control.
As explained in the foregoing, the present invention is capable of securely preventing erroneous functions fatal to the system, since the signals read in the normal positions are not mistaken, even in the presence of chattering or the like, for the signals of the important positions. Also, in case the conductive patterns and signal lines exclusive for the important positions are not employed, the width of the board constituting the conductive pattern member can be reduced, whereby the entire device can be made more compact. Also, in such case the number of ports of the CPU can be reduced, so that the CPU can be utilized in a more efficient manner.
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A position detecting device comprises a pattern member having conductive patterns arranged in plural tracks; a slidable member having plural sliding pieces capable of sliding on the conductive patterns, wherein each of the sliding pieces assumes either a conductive state in contact with one of the conductive patterns or a non-conductive state not in contact with the conductive pattern; a signal processing device for detecting sets of the conductive patterns and the sliding pieces in conductive state, by transmitting electrical signals through the conductive patterns and the sliding pieces; and a discriminating device for identifying the relative position between the conductive patterns and the sliding pieces when the the conductive patterns and the sliding pieces in conductive state are detected at least a predetermined number of times or over at least a predetermined period of time.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates generally to an improved audio preamplifier of the type used for receiving input of stringed instruments and, more particularly, but not by way of limitation, it relates to an audio switching and amplifying apparatus wherein solid state logic circuitry control signal amplification through multiple vacuum tube stages.
2. Description of the Prior Art
The use of vacuum tubes in musical instrument amplifiers and pre-amplifiers is quite old and well-known. Indeed, all amplifiers prior to the advent of solid state amplifiers in the late 1950's were constructed utilizing hard, vacuum tube technology. By the same token, solid state logic circuitry and programmable logic technology in general is quite commonplace today in digital electronics and particularly in digital computer design. However, Applicant does not know and has been unable to discover any teachings that would combine the two approaches, i.e., the use of programmable solid state logic circuitry in con-junction with vacuum tube amplifier design for music audio reproduction.
SUMMARY OF THE INVENTION
The present invention relates to improvements in vacuum tube amplifier control and fidelity by using programmable solid state logic circuitry in combination therewith. A programmable logic device provides sequenced output command pulses to logic switching circuitry which controls signal routing, gain control and signal combining through three vacuum tube gain stages. Output from the three gain stages is then applied through a multi-channel volume and tone control array whereupon the signal is input to a final output amplifier stage with cathode follower output to the next stages.
Therefore, it is an object of the present invention to provide a pre-amplifier for selectively providing multi-channel output of distinctly different instrument sounds.
It is also an object of the present invention to provide a pre-amplifier for guitar output signals that provides more efficient switching between channels and sounds.
It is still another object of the invention to enable a speaker contour filter for simulating the frequency response of a typical guitar speaker cabinet.
Finally, it is an object of the present invention to provide a logic controlled multi-channel pre-amplifier offering distinct sound selection and having provision for multiple effects loops.
Other objects and advantages of the invention will be evident from the following detailed description when read in conjunction with the accompanying drawings which illustrate the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic diagram of the programmable logic circuitry of the present invention;
FIG. 2 is a schematic diagram of first stage amplifier of the invention;
FIG. 3 is a schematic diagram of the second and third stage amplifiers of the present invention; and
FIG. 4 is a schematic diagram of the power output stage of the programmable pre-amplifier.
DETAILED DESCRIPTION OF THE INVENTION
Referring to FIG. 1, the logic control circuitry includes a programmable array logic device 10 that functions to control the front panel and foot switch decode logic for the pre-amplifier. Programmable logic device 10 is controlled by a clock generator, an op-amp oscillator 12 (type LN324AN) providing a clock pulse output on lead 14, e.g., 50 to 60 Hertz, for input to pin 1 of logic device 10. Other inputs applied to logic device 10 are CH3BOOST at pin 2, BUTTON at pin 3, FS1 at pin 4, and FS2 at pin 5 (footswitch inputs). A reset is input at pin 6 while CH2BOOST is input at pin 7. Pin 8 receives input of a delay signal from an op-amp comparator 22 (type LN324AN) via lead 24 and this signal effects a mute time-out.
Program control outputs from logic device 10 include a mute output on pin 19 and lead 26 for input to the delay comparator 22. Pin 18 provides a CHANNEL 1 output on lead 28 which is applied through a type 2N3904 transistor 30 to produce an ASW2 output (analog switch 2). Lead 28 is also applied to the base of yet another type 2N3904 transistor 32 to produce a CHISNK output (CHANNEL 1 turn-on) on collector output lead 34. Pin 17 provides output on lead 36 to a type 2N3904 transistor 38 which generates ASW1 output on lead 40. Pin 16 of logic device 10 provides output on a lead 42 to the base of another similar type transistor 44 to produce CHIIISNK output on lead 46, and output lead 42 is also applied to energize an op-amp 48 to generate SLOSTART signal as output on lead 50. Finally, output pin 15 of logic device 10 connects to a lead 52 that is dually connected to the base of a type 2N3904 transistor 54 to generate ASW3 output at lead 56 and it is connected to the base of a similar transistor 58 to generate CHIISNK output on lead 60. An output 62 is diode connected to respective output leads 34 and 60 to conduct a BRTLED signal that is used to energize LED indicators throughout the circuitry.
The program for the programmable array logic device 10 is as follows:
______________________________________/** Inputs **/Pin 1 = CLK ; /*System clock - approx 5 ms. */Pin 2 = CHA3DRIVE ; /*Front Panel DRIVE PULL switch */Pin 3 = !BUTTON ;/*Front Panel select button */Pin 4 = SWA ; /*Footswitch bit0 */Pin 5 = SWB ; /*Footswitch bitl */Pin 6 = !RESET ; /*Not reset */Pin 7 = CHA2DRIVE ; /*Front panel DRIVE PULL switch */Pin 8 = DELAY ; /*Mute timeout input *//** Outputs **/Pin 12 = Q0 ; /*Machine */Pin 13 = Q1 ; /*State */Pin 14 = Q2 ; /*State */Pin 15 = CHANN2 ; /*OP1,3 */Pin 16 = CHANN3 ; /*OP2,6,ASW1 */Pin 17 = DRIVE ; /*Selects DRIVE Circuit */Pin 18 = CHANN1 ;Pin 19 = MUTE ; /*Starts mute timeout by strobing one-shot *//** Declarations and Intermediate Variable Definitions **/field. ampstate + [Q2..0]; /* State variables */$define CH1wt `b` 000$define CH1 `b` 001$define CH2wt `b` 010$define CH2 `b` 011$define CH3wt `b` 100$define CH3 `b` 101$define ResetS `b` 111$define BadState `b` 110field switch = [SWA,SWB];toch1 = switch:[`b` 01]; /* Channel 1 */toch2 = switch:[`b` 10]; /* Channel 2 */toch3 = switch:[`b` 00]; /* Channel 3 *//** Logic Equations **/conditionif RESET out Q0.d out Q1.d out Q2.d out MUTE.d;sequence ampstatePresent ResetSif !RESET next CH1wt out MUTE.d out !DRIVE.d;if RESET next ResetS;present CH1wtOut !CHANN1.d out !CHANN2.d out !CHANN3.d;if (BUTTON # DELAY) next CH1wt;if !(BUTTON # DELAY) next CH1;present CH1out CHANN1.d out !CHANN2.d out !CHANN3.d;if BUTTON # toch2 next CH2wt out MUTE.d;if toch3 next CH3wt out MUTE.d;if !(BUTTON # toch2 # toch3) next CH1;present CH2wtout !CHANN1.d out !CHANN2.d out !CHANN3.d;if BUTTON # DELAY next CH2wt;if !(BUTTON # DELAY) next CH2;present CH2out !CHANN1.d out CHANN2.d out !CHANN3.d;if !CHA2DRIVE out Drive.d;if BUTTON # toch 3 next CH3wt out MUTE.d;if toch1 next CH1wt out MUTE.d;if !(BUTTON # toch1 # toch3 next CH2;Present CH3wtout !CHANN1.d out 1chann2.d out !CHANN3.d;if BUTTON # DELAY next CH3wt;if !(BUTTON # DELAY) next CH3;present CH3out !CHANN1.d out !CHANN2.d out CHANN3.d;if !CHA3DRIVE out DRIVE.d;if BUTTON # toch1 next CH1 wt out MUTE.d;if toch2 next CH2wt out MUTE.d;if !(BUTTON # toch1 # toch2) next CH.sub.3 ;______________________________________
FIG. 2 illustrates the input and first stage of the preamplifier. An input signal may be received at input jack 70 and/or a rear panel input 72, e.g., an auxiliary input for guitar or synthesizer. Such input is amplified in a solid state amplifier 74 (type TL074N QUAD AMP) whereupon a clamped output is derived on lead 76 for output to a tuner or other external means. Various types of external "effects" circuitry or devices may be utilized at this point for altering selected ones of sound characteristics. Signal is returned to the rear panel for input via lead 77 as it is applied as a clamped input to the positive terminal of a quad-amp 78 (type TL074N). The output of transistor amplifier 78 is then present on lead 80 for application to opposite inputs of amplifiers 82 and 84 (type TL074N) which function to amplify effects return signals from external equipment. A branch output 86 from amplifier 78 is applied to a FET switch 88 (CD4053) as the output lead 90 from effects return transistor 84 is applied to the other contact of FET switch 88 while a common output 92 is connected to a contact of an FET switch 94 (CD4053). The remaining contact of switch 94 is connected to output lead 95 from the remaining effects return amplifier 82. The control leads 96 and 98 receive respective inputs ASW1 and ASW2 to actuate the analog switches thereby to control input on a grid lead 100.
A first amplifier stage consists of dual triode 102a and 102b, a type 12AX7 vacuum tube. Output on lead 100 from analog switch 94 is applied to the grid of triode 102a as the cathode is connected to an R/C parallel combination to ground and the plate is connected through a load resistor 104, 106 to B+ voltage. Output from triode 102a is taken from junction 108 for application to the grid of triode 102b. Triode 102b is then connected as a cathode follower to provide a stage 1 output on lead 110.
Referring now to FIG. 3, there are shown the second and third gain stages as they interact with various switching and control circuitry. The stage 1 output present on lead 110 is applied in parallel through a CHANNEL 1 volume potentiometer 112, a CHANNEL 2 gain potentiometer 114 and a CHANNEL 3 gain potentiometer 116. Outputs from potentiometers 114 and 116 on respective leads 118 and 120 are controlled by opto-switches 122 and 124, respectively. The opto-switches are a type VT5C1. The respective light sources of the opto-switches 122 and 124 are controlled by current conduction on leads 126 and 128 which cause illumination of the unit light source.
Thus, it is in the second stage input circuitry where the audio signal is separately processed to bring about three audio channels, CHANNELS 1, 2 and 3, having different signal characteristics. The channels may select the following, for example:
CHANNEL 1--"clean" guitar sounds;
CHANNEL 2--"CRUNCH" sounds; and
CHANNEL 3--"lead/overdriven" sounds.
A front panel pushbutton switch 130 provides a BUTTON output which is applied as input to pin 3 of logic device 10 (FIG. 1). Front panel ganged button switches 132 and 134 provide control of CH2BOOST and CH3BOOST, respectively, and button switch 136 connects CHIISNK with lead 138 to actuate the opto-switch 140. The switches 132/134 are a ganged switch type K12214 SW.
The second and third gain stages are made up of respective halves 142a and 142b of a dual triode, a 12A×7 type vacuum tube. The CHANNEL 2 gain output lead 118 is applied to the grid 144 of triode 142a as the cathode is connected through an R/C bias network to ground. The plate is connected through load resistance 146 to the B+ supply and output is taken from plate junction 148 via lead 150. Second stage output from opto-switch 140 is applied to grid lead 152 of the third gain stage triode 142b. The grid lead 152 is also connected through an opto-switch 154 to a lead 156 which is the output of the CHANNEL 1 volume control potentiometer 112.
Analog switch output from logic device 10, viz. ASW3, is input at lead 158 to control actuation of a FET switch 160 (type CD4053) that changes the cathode to ground impedance of second gain stage triode 142a. Harmonic drive can be varied by control of pushbutton ganged switches 162 and 164 (type K12214 SW) as they function in conjunction with opto-switch 166 to decouple between the plate output lead 168 and the grid lead 152 of third gain stage triode 142b. Thus, the output lead 168 constitutes the stage 3 output.
Referring now to FIG. 4, stage 3 output on lead 168 is prepared for further logic coupling and input to a final power output amplifier consisting of triode halves 170a and 170b, a 12AU7 type vacuum tube. Signal on lead 168 is applied through series-connected tone control potentiometers 172, 174 and 176, treble, bass and mid-range, respectively. The output signal on wiper lead 178 is then subjected to volume control potentiometer 180 and applied on lead 182 to opto-switch 184.
A parallel portion of stage 3 output on lead 168 is conducted in a CHANNEL 3 mode where it is acted upon by tone control potentiometers 186, 188 and 190, treble, bass and mid-range, respectively. Tone adjusted output on lead 192 then passes through volume control potentiometer 194 and wiper output 196 is applied to opto-switch 198. Thus, with SLOSTART providing current return, the signal CHISNK (FIG. 1) activates opto-switch 184 and output signal is present on lead 200 to grid lead 202 and the grid of triode 170a to provide CHANNEL 1 output. Wiper output from volume control potentiometer 180 on a lead 204 is applied through an opto-switch 206, and application of a CHIISNK signal (FIG. 1) activates opto-switch 206 and provides CHANNEL 2 output on lead 200 and grid lead 202 for amplification in power output stage 170a. Finally, CHANNEL 3 output on lead 196 from volume control potentiometer 194 is switched through opto-switch 198 on application of the CHIIISNK signal (FIG. 1) to produce output on lead 208 to grid lead 202 and the grid of triode half 170a.
The power output amplifier 170 receives output of triode half 170a at plate lead 210 which is directly coupled to grid lead 212 of second half triode 170b, and the cathode of triode 170b is connected for cathode follower output via output lead 214.
The foregoing discloses a unique pre-amplifier design which melds the latterday solid state electronics and its superlative logic capability with the tried and true hard tube electronics which in some cases has been found superior to that which solid state has to offer. In particular, it has been found that the tonal characteristics of hard tube pre-amplifier and amplifier circuitry is often times very desirable as compared to solid state forms of a similar circuit. Therefore, the programmable circuitry functions with the hard tube amplifier stages to produce multiple channels of desirable sounding instrument signals while having the capability of offering greater diversity as regards effects loops, footswitch mixing and other synthesis modes of reproduction. The pre-amplifier also offers a speaker contour filter for simulating diverse response characteristics.
Changes may be made in combination and arrangement of elements as heretofore set forth in the specification and shown in the drawings; it being understood that changes may be made in the embodiments disclosed without departing from the spirit and scope of the invention as defined in the following claims.
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A pre-amplifier for musical instrument audio signals which utilizes a solid state programmable logic device to control a plurality of solid state switches for routing the audio signals in preselected manner through successive stages of vacuum tube amplification.
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The present invention relates to alloyed powders for dental amalgams and a method of producing them. The alloys consist of silver, copper, tin and, optionally, additives of indium, zinc, palladium, ceramic powder and/or glass powder. The method includes the steps of mechanically comminuting a pressed and sintered molded body. The powders obtained in this way are triturated with mercury and are used as amalgams for filling dental cavities.
BACKGROUND OF THE INVENTION
Silver amalgams have been used successfully for decades as filling material for teeth damaged by tooth diseases. They are especially useful for this purpose because of their high mechanical strength, long life and ease of use. The amalgam is produced at the dentist's office from a suitable alloyed powder and pure mercury. The alloyed powders normally consist of silver, copper and tin and frequently also of a little zinc. The silver content varies from 24 to 93% by weight (cf. for example published German Patent Specification DE-OS No. 25 11 194 and U.S. Pat. Nos. 3,985,885, 4,039,329, 3,975,192, 4,030,918, 3,762,917 and 3,871,876). Other additives are also used in some cases, such as indium (see e.g. U.S. Pat. No. 4,030,918) or palladium (U.S. Pat. No. 4,374,085).
The alloyed powders are normally produced using molten metallurgical techniques, either by spraying the melt or by machining a cast molded body (e.g. a bar or a billet).
When the spraying process is used, the powder is produced directly from the melt by passing the melt stream through a funnel and then through an annular nozzle loaded with water or gas, after which the stream is atomized. As a result of the high cooling speed which occurs in this process, the particles which are formed are primarily spherical. Also, the alloy phases, e.g. Ag 3 Sn and Cu 3 Sn, are present in a finely distributed fashion. Amalgams with great strength are obtained from such powders, especially in the case of low silver contents. On account of the spherical shape of the powder particles and the associated high bulk density, the amount of mercury required for producing a pasty tamping body is less than in the case of chip amalgams produced by machining; however, the working properties are not optimum since the individual particles slide past each other too easily during tamping and thus escape the tamping pressure. Moreover, the working properties of such so-called "ball amalgams" react in a considerably more sensitive manner to errors in measuring the proportions of alloy particles and mercury than do chip amalgams. Further, the manufacturing cost of the sprayed alloy is high, largely because of the low yield of utilizable powder.
On the other hand, when the alloying powder is made by machining, there are increases and a coarse distribution of the Ag 3 Sn and Cu 3 Sn phases in the molded body and in the alloyed powder. These arise because of the relatively low cooling speed during the production of the cast bar which is machined. This characteristic has a negative effect on the binding reaction with mercury. The technical properties such as e.g. binding expansion and strength are also adversely affected. In addition, the yield of utilizable powder at 30-50% is very low so that increased costs result due to subsequent grinding processes and any separated waste which occurs. An advantage of the chip amalgams over the ball amalgams is their very good workability.
Published German Patent Specification DE-PS No. 32 40 356 describes a method of producing an amalgam powder which uses sintering technology. First, a sprayed alloyed powder is produced from silver-tin-copper which is subsequently compacted and sintered. The porous, sintered, alloyed molded body is then machined. In this manner, an improvement in the quality of the amalgam is achieved. However, this method has the disadvantage of high production costs, which arise chiefly as a result of the production of the alloyed powder via spraying.
SUMMARY OF THE INVENTION
The object of the present invention is to provide a method of producing alloyed powders for dental amalgams consisting of silver, copper, tin and optionally additives of indium, zinc, palladium, ceramic powder and/or glass powder by means of mechanically comminuting a pressed and sintered molded body which method assures a very fine microstructure of the alloyed powder, can be performed with high yields of utilizable amalgam powder and is thus economical.
In accordance with the present invention these and other objects are achieved by mixing and pressing the elementary metal powders of silver, copper, zinc and, optionally, any additives into a molded body and then sintering it at a temperature between 150° C. and the solidus temperature of the alloy being produced until a homogeneous distribution of the tin has been achieved in the silver and copper particles. After cooling, the alloy is machined to form a powder.
In making the compact, the individual powders are intensively mixed so that an agglomerate-free mixture of powders is produced. This powder mixture is compacted in a suitable mold and press to a green compact and subsequently sintered. Then, the sintered body (bar, billet or the like) is machined e.g. in a milling machine and the required fraction separated off.
The sintering process is preferably performed in two stages. The first stage is performed by heating for 1 to 20 hours at a temperature below the melting point of tin (232° C.) and the second stage at temperatures between 232° C. and the solidus temperature of the alloy being produced until a homogeneous distribution of the tin is achieved in the silver and copper particles.
Metal powders with a particle size smaller than 70 μm have proven to be especially suitable since they assure a sufficiently fine phase distribution and also make possible a relatively short sintering time in which the entire tin content can diffuse into the copper and silver particles.
An even finer distribution of the individual silver and copper-rich phases is achieved if the powder mixture is subjected to a grinding process (e.g. in a high-speed attritor) before the pressing step. The phase size of the silver and copper-rich particles (primarily Ag 3 Sn and Cu 3 Sn) which can be achieved in this manner is in the range of a few micrometers and is comparable to that of sprayed powders in this respect.
If the grinding process is carried out in air, there is a danger of an elevation of the oxygen concentration in the alloyed powder due to the intensive working of the powder. This has a bad effect on the amalgam properties. Therefore, it is preferable to perform the grinding process under the protection of an inert gas atmosphere.
It is also advantageous to produce the molded body to be machined by means of isostatic pressing.
The selection of sintering temperatures depends on the composition of the particular powder or alloy. As already mentioned, the sintering process is preferably performed in two stages. In the first stage, the pressed green compact is sintered at a temperature below the melting temperature of tin (232° C.) for 1-20 hours to permit all of the elemental tin to diffuse into the silver-copper particles. Then the sintering temperature is raised to a temperature between the melting point of tin and the solidus temperature of the alloy and maintained there until a homogeneous distribution of the tin in the copper and silver particles has been achieved. Since the silver and copper particles do not melt during the one-stage nor during the two-stage sintering, their original particle size remains essentially preserved. A small particle size can be achieved more easily in the production of elementary metal powders than in the production of alloyed powders.
The technical properties of the amalgams produced with the alloyed powders produced in accordance with the invention meet or exceed the requirements of the ADA or ISO specifications, as follows:
______________________________________ADA: Dimensional change during binding: +2 μm/cm Creep 3.0% Resistance to compression after one hour 80 MPaISO: Dimensional change during binding: -10 to 20 μm/cm Creep 3.0%Resistance to compression after one hour 50 MPaResistance to compression after 24 hours 300 MPa______________________________________
The amalgams exhibit the good workability characteristic of chip amalgams. In some instances, especially in the range of low Ag contents, distinctly better amalgam properties are achieved with the alloyed powders produced in accordance with the invention than with an alloyed powder of the same composition produced with casting technology. The yield of milled powder which exhibits the particle size suitable for the production of amalgam is with 70-85% nearly twice as high compared to amalgam powders produced according to casting technology, so that an expensive grinding of the coarser, milled powder which influences the properties remains limited to very small amounts.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The following examples are intended to explain the method of the invention in more detail:
EXAMPLE 1
50% silver powder (smaller than 63 μm), 30% tin powder (from the firm - Merck, item No. 7807) and 20% copper powder (smaller than 63 μm) were mixed in a mixer for approximately 15 min., then filled into a tightly closable rubber mold (cylinder) and isostatically pressed at 1000 MPa to a billet. The blank was sintered for eight hours at 300° C. under an atmosphere of argon. According to the results of structural and microprobe tests, none of the elementary powders remained after the sintering. The intermetallic phases Ag 3 Sn and Cu 3 Sn had been produced by tin having diffused into the silver and copper. After machining in a filing machine, the powder fraction smaller than 63 μm was sieved off and annealed four hours under an inert gas atmosphere (N 2 /H 2 =80/20) at 180° C. The trituration with mercury was performed in a Duomat R (firm - Degussa) with a mixing ratio of alloyed powder to mercury of 1:1.2. The mixing time was 40 seconds. The properties of the amalgam produced with this alloyed powder are given in the table.
EXAMPLE 2
70% silver powder (smaller than 63 μm), 27% tin powder (firm - Merck, item No. 7807) and 3% copper powder (smaller than 63 μm) were mixed in a mixer for approximately 15 min., then filled into a tightly closable rubber mold (cylinder) and isostatically pressed at 1800 MPa to a billet. The blank was sintered for six hours at 300° C. under an atmosphere of argon. According to the results of structural and microprobe tests, none of the elementary powders remained after the sintering. After machining in a filing machine, the powder fraction smaller than 63 μm was sieved off and annealed for four hours under a gas atmosphere (N 2 /H 2 =80/20) at 240° C. Trituration with mercury was performed in a Duomat R (firm - Degussa) with a mixing ratio of alloyed powder to mercury of 1:1.2. The properties of the amalgam produced with this alloyed powder are given in the table.
EXAMPLE 3
Silver powder, copper powder and tin powder with a composition corresponding to that of Example 2 were mixed in the same manner and pressed (800 MPa). The sintering process was performed in two stages. In the first stage, the material was sintered for 6 hours at 230° C. and subsequently it was sintered for 2 hours at 400° C. under an atmosphere of argon. Further production steps were as described in Example 2. The properties of the amalgam are given in the table.
EXAMPLE 4
45% Ag powder (smaller than 20 μm), 24% copper powder (smaller than 20 μm) and 31% tin powder (from the firm - Merck, item No. 7807) were mixed as described in Example 1 and pressed (amount of pressure applied 120 MPa). The sintering was performed as in Example 3 in two stages at the same temperatures, but under an atmosphere of nitrogen and hydrogen (N 2 /H 2 =80/20). The structural tests in a light-optical microscope and in a microprobe showed that the alloy consists of a copper-tin phase and a silver-tin phase which were identified by means of X-ray microstructure investigation as Ag 3 Sn and Cu 3 Sn. The pure original metal powders no longer are found in the structure. The sintered alloy was milled with a solid cylindrical cutter. The yield of powder fraction smaller than 63 μm which could be utilized for the production of amalgam was 82%. The heat treatment of the sieved-out fraction smaller than 63 μm was performed for four hours at 80° C.under an inert gas atmosphere (N 2 /H 2 =80/20). The data of the amalgam produced with this alloyed powder is given in the table. The amalgam is free of γ 2 .
EXAMPLE 5
5% by volume glass powder (≦5 μm) was added to the silver, copper and tin powders corresponding to the composition in Example 4. Mixing, pressing, sintering and milling were performed in a manner which was analogous to Example 4. After the sintering, the glass particles were finely distributed in the matrix of Cu 3 Sn and Ag 3 Sn. The yield during milling was 76%. After the heat treatment of the powder fraction smaller than 63 μm (as in Example 4), the alloyed powder was triturated with mercury. The properties of this amalgam are given in the table.
EXAMPLE 6
A powder mixture corresponding to Example 4 (150 g) was triturated with zirconium oxide balls (600 g) in alcohol in an attritor whose grinding vessel consisted of zirconium oxide and which was water-cooled. The speed was 1200 revs/min., the grinding time being 4 hours. After separation of the grinding medium, the ground powder was filled into a rubber mold and further processed in a manner which was analogous to Example 4. After the sintering, a structure was present in which the Ag 3 Sn and Cu 3 Sn phases were present in an extremely fine distribution. The phase size was in the range of a few μm.
TABLE__________________________________________________________________________ Change inMixing Mixing Length During Resistance to CompressionRatio Time Hardening in MPa afterAlloy:Hg (sec) Creep (μm/cm) 1 h 24 h 7 d__________________________________________________________________________Example 1 1:1.2 40 0.45 +10 90 340 370Example 2 1:1.2 30 1.6 -11 85 290 310Example 3 1:1.2 30 1.2 -8 130 330 385Example 4 1:1.3 30 0.22 +4 126 385 450Example 5 1:1.3 30 0.25 +5 105 330 360__________________________________________________________________________
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An economical alloyed powder for dental amalgams exhibiting good working properties is obtained from pressed and sintered molded bodies by mechanical comminution. The formed body is produced by mixing and pressing powders of elemental silver, copper and tin with a subsequent sintering between 150° C. and the solidus temperature of the alloy being formed. The sintering is performed until a homogeneous distribution of the tin has been achieved in the silver and copper particles.
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This application claims priority under 35 U.S.C. §120 to U.S. provisional application serial No. 60/113,537, filed Dec. 22, 1998.
This invention relates to a metal-based cubane structure contained in an octanuclear complex which can be used as an electron transfer agent. More specifically, this invention is directed to a redox-active metal-based structure, protected inside an inert coating. This complex, which can be defined as M 8 (μ 4 -E) 4 (μ-L) 12 X 4 , is stable over several oxidation states. The present invention is also directed to a method of making this product from simple starting materials.
Thermodynamic stability is a desired property of materials to be used in most commercial applications. At the same time, however, chemical versatility is typically required for the manifestation of interesting properties or catalytic activity. A combination of these contrasting characteristics is typically achieved by the coating of large surfaces or particles with inert substances, at the macroscopic and microscopic scale, respectively. Such structures are known to naturally occur at the macromolecular level when, for example, metal active centers are protected inside the organic part of metalloproteins.
The complex encompassed by the present invention has a core, which is the source of redox properties, encapsulated in a protective shell. Such a complex provides an ideal building block for the construction of one-, two-, and three-dimensional materials. These materials can be constructed by connecting or bonding units of the complex made in accordance with the present invention by bridging atoms or groups. The bridges can be either bidentate ligands, which replace terminal atoms, or bifunctional substituents, which connect the units through substitution at the 3-, 4- or 5-position of their respective pyrazoles. The advantage of using the inventive complex for the construction of these materials, instead of a single metal atom, or other mono- or polynuclear products, is that the complex can withstand redox manipulation without significant geometrical changes, which would cause the structure of the material to collapse. The inventor has discovered that the structural integrity of the present complex is a function of the way it is composed. Specifically, the desired redox properties are a function of the metal core, while the connections required for the construction of the above proposed materials take place at the outer inert shell.
Accordingly, construction of the 1-, 2-, and 3-dimensional materials leaves the core unaffected. Similarly, redox changes in the core leave the outer structure unaffected. In addition, when the metal atoms employed are paramagnetic, the complexes encompassed in the invention are also paramagnetic, or can become paramagnetic in one of their oxidation states. The materials which will be prepared from the inventive complex will have all the magnetic and redox properties of this building unit, possibly even amplified.
The inventor has surprisingly and unexpectedly discovered that by encapsulating a redox active core inside an inert protective coating, the resulting material retains structural stability over several oxidation states. This result is achieved by separating the center of redox activity, the core, from the outer surface of the molecule, the coating. In some cases, the molecular symmetry of the complexes M 8 (μ 4 -E) 4 (μ-L) 12 X 4 allows the existence of optically active forms, which can be prepared as racemic mixtures or enantiomerically enriched or enantiomerically pure forms.
SUMMARY OF THE INVENTION
To achieve the beneficial properties of stability and versatility previously described, the present invention is directed to molecules having an active center coated with inert substances. More specifically, the present invention is directed to a complex comprising redox-active metal clusters protected inside a chemically inert shell. The invention is also directed to the generation of four additional forms of the complex through electrochemical reduction of the inventive complex. In addition, the present invention is directed to methods of using these structures as building blocks for the construction of durable supercluster assemblies having electron-transfer properties. The invention is further directed to uses of this complex as a dopant in materials, i.e., polymers to impart magnetic or electrical properties to the doped material. The inventive complex may also be used as a contrast agent in magnetic resonance imaging (MRI) applications, for example.
Pyrazolates are convenient bridging ligands or complexing agents for the synthesis of polynuclear products in which, due to the aromatic character of the ligand or complexing agent, the chemical activity is restricted to the metal centers.
The present invention is directed to a material represented by formula (I)
M 8 (μ 4 -E) 4 (μ-L) 12 X 4 (1)
where M is one or more transition metals, a lanthanide, an actinide and M is in the +2, +3, or +4 oxidation state, or two different oxidation states. Preferably, M is Fe 3+ , Mn 3+ or Co 3+ ;
μ represents a bridging group, i.e., a bridging ligand or a bridging chalcogenide;
E is a chalcogenide, preferably O, S or Se;
L is a bridging ligand such as a pyrazole, or a pyrazole substituted at any or all of the 3-, 4-, or 5-positions;
X is a terminal ligand, such as Cl, Br or an alkyl group.
The inventive complex can be in a racemic, an enantiomerically-enriched or an enantiomerically-pure form.
More preferably, formula (I) represents a Fe III-complex designated as
Fe 8 (μ 4 -O) 4 (μ-pz) 12 Cl 4
wherein pz represents a pyrazolato anion, C 3 H 3 N 2 , and
μ represents a bridging group, i.e., a bridging pz, or a bridging atom, such as an oxygen atom. The Fe (III) complex optionally has T-symmetry.
The inventor has unexpectedly discovered that the inventive Fe III complex contains a redox-active Fe 4 O 4 core, protected inside a Fe-pyrazolate coating, which is stable over five oxidation states. The Fe 4 O 4 -core of the Fe (III) complex is the first example of an all-ferric/oxygen cubane complex. Consistent with the +3 valence of this Fe III complex are the shorter Fe-O bonds of formula (I), i.e., 2.040(4) Å average, compared to those of its lower-valence analogues.
As stated, the inventor has also discovered that the complex defined by formula (I) is stable over several, preferably five, oxidation states. Stability is defined as the ability of the complex of formula (I) to retain the structure and stoichiometry of its neutral form when it is reduced by one, two, three or four, one-electron processes. In other words, the inventor has discovered that the species represented by (I), (I) −1 , (I) −2 , (I) −3 and (I) −4 are thermodynamically stable under the electrochemical reduction of the complex of formula (I).
The inventor has also discovered that manipulation of the solubility of the inventive complex is possible through substitution at the outer shell. This can be done through substitution at either the positions of the chlorine atoms, or the 3-, 4-, or 5-position of the pyrazoles. While the preferred form of the complex is hydrophobic, i.e., insoluble in water, but soluble in a large number of organic solvents, it can easily become water soluble by attaching hydrophilic groups to its surface through such substitutions. Water-soluble derivatives of the inventive complex may find medicinal use, either in therapeutic or diagnostic applications, for example, as MRI contrast enhancing agents.
The inventive complex, when manipulated in the above stated manner to make it water soluble, allows the complex to be used in a method of generating an image of a mammal. Such a method comprises administering to a mammal, in an amount effective to provide an image, a contrast agent comprising the complex of formula (I).
Additionally, the inventor has discovered that the complex defined by formula (I) can be assembled in a single reactor from simple starting materials that are commercially available.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 a ) illustrates a side view of the Fe 8 O 4 Cl 4 part of a complex of formula (I), and of three of the twelve pyrazolato groups therein.
FIG. 1 b ) illustrates the same as 1 a ), but is viewed down a C 3 -axis.
FIG. 2 illustrates the structure of a complex of formula (I) comprising spherical atoms of arbitrary radii. Hydrogen atoms are not shown.
FIG. 3 illustrates voltammetry of a complex of formula (I) in 0.1 M Bu 4 NPF 6 /PrCN, with a scan speed=100 mV/sec, T=223 K, Pt-disk working electrode, versus Fc/Fc+, wherein a) represents a cyclic voltammogram, and b) represents a cyclic AC-scan.
FIG. 4 illustrates an octanuclear complex containing a metal cubane core in an inert shell.
DETAILED DESCRIPTION OF THE INVENTION
Preparation of a Fe III Complex
The starting materials that can be used to prepare the Fe 8 (μ 4 -O) 4 (μ-pz) 12 Cl 4 complex defined by formula (I) include the following commercially available materials: anhydrous ferric chloride (FeCl 3 ), pyrazole (C 3 H 4 N 2 , pzH), and 3,5-dimethylpyrazole (C 5 H 8 N 2 , 3,5-Me 2 -pzH). Also, sodium pyrazolate (Na-pz), or potassium pyrazolate (K-pz) can be readily prepared from pyrazole and sodium hydride or potassium hydride. Either pyrazolate works equally well. Other common reagents can be used as pyrazolate-transfer agents in the preparation of formula (I).
In a typical preparation of a complex of formula (I), an ordinary reaction flask is charged with the starting materials, and a solvent under an inert atmosphere, such as N 2 or Ar. The flask is closed while the reaction proceeds. After about 1 hour, the reaction is completed and the flask is opened to the laboratory atmosphere. A pyrazolate is then added and the reaction flask is kept open for at least 24 hours. The reaction mixture is not placed under inert atmosphere again. Once the solvent volume is reduced to approximately ⅓ of its initial volume, a hydrocarbon such as hexane is added to precipitate a complex of formula (I) as an impure microcrystalline solid. The complex solid can be further purified using standard chromatographic techniques.
The invention is illustrated in greater detail in the following, non-limiting example.
EXAMPLE
Preparation
In a standard reaction flask, 3,5-Me 2 pzH (0.375 g, 3.90 mmol) was mixed with FeCl 3 (0.180 g, 1.11 mmol) in 15 ml CH 2 Cl 2 under N 2 . The flask was then closed. After about 1 hour, the flask was opened and K-pz (0.355 g, 3.30 mmol) was then added to the mixture, which product was exposed to an ambient environment for several days. A crystalline product of formula (I) was subsequently prepared by mixing the CH 2 Cl 2 solution of formula (I) with hexane. The slow mixing of CH 2 Cl 2 and hexane, along with gradual evaporation of the mixture, resulted in well formed dark-red crystals of formula (I). Specifically, the dark-red, air-stable complex defined by formula (I) was precipitated by the addition of hexane after the CH 2 Cl 2 solvent was reduced to a volume of approximately 5 ml. The above reaction yielded greater than 30% of a complex of formula (I).
Analysis of Resulting Precipitated Crystals
The larger crystals made according to the example were used for a single crystal X-ray structure determination, while the smaller ones were used for all other analyses. Analyses performed on the crystals grown from the CH 2 Cl 2 /hexane solution of formula (I) produced the following results.
A. Elemental Properties
The precipitated crystals exhibited a melting point of approximately 565 K, as determined by DTA analysis. The analyses for C, H, N, and Cl were performed gravimetrically by an elemental analyzer. The analysis for Fe was done by Atomic Absorption spectroscopy (flame atomization). The analyses of all five elements show the w/w % of the element in a sample of formula (I)-½ hexane. The first number reported is the measured weight percent of the element, averaged from duplicate runs, while the second number is the theoretically calculated value for formula (I)-½ hexane. The fact that the measured value is so close to the theoretical value evidences the correctness of the characterization given below:
Results:
C=31.14 (31.19),
H=2.81 (2.87),
N=21.59 (22.39),
Cl=9.62 (9.45),
Fe=29.43 (29.76).
B. Spectroscopic Properties
1. Electronic spectroscopy: The electronic spectrum of formula (I) in a CH 2 Cl 2 solution, recorded in the UV/Vis/NIR region, revealed a λ max =359 nm, consistent with the red color of the material.
2. Infrared spectroscopy: A powdered sample of formula (I) formed into a KBr pellet showed the following IR absorption peaks (where the peak intensity was denoted as vs=very strong, s=strong, m=medium and w=weak) in cm −1 , using a KBr disk: 1490 m, 1417 m, 1362 s, 1268 s, 1169 s, 1145 m, 1078 w, 1045 vs, 963 w, 915 w, 894 w, 763 s, 615 m, 555 m and 476 s. With a polyethelene pellet of formula (I), three additional IR absorption peaks were observed at 349 s, 331 s, and 308 s.
3. Mass spectroscopy: The mass spectrum of formula (I) was recorded by the Fast Atom Bombardment technique and the following m/z peaks were observed (the fragment to which they are attributed in parenthesis): 1457.6 (M+), 1420.6(M-Cl+), 1388.5(M-pz+), 1353.6(M-Cl,pz+), 1321.5(M-2pz+), 1286.5(M-2pz,Cl+).
C. Magnetic Properties
Magnetic moment: u eff =6.52 B.M., calculated from a Faraday balance susceptibility measurement at 290 K.
D. Crystallographic Properties
Red parallelepiped crystals appropriate for X-ray diffraction study were grown from the CH 2 Cl 2 /hexane solution of formula (I). A Rigaku-A-FC6S diffractometer employing a Mo−Kα=0.71069 Å beam source showed the following cell parameters for the primitive triclinic cell, P{overscore (I)}(No.2), characteristic of the crystals (with the standard deviation in parenthesis): a=12.367(5), b=12.508(5), c=20.794(4) Å, α=77.45(3), β=80.80(3), γ=70.27(3)°, V=2942(2) Å 3 , Z=2, d calc =1.694 g/cm, μ=21.53 cm −1 .
FIG. 1 illustrates the crystal structure for the Fe 4 O 4 -cube. Specifically, the bond lengths were found to be (with the standard deviation in parenthesis): Fe—O=2.022(4)-2.056(4) Å; Fe—Fe=3.059(1)-3.088(1) Å; Fe—N=2.048(5)-2.070(5) Å; Fe—O—Fe=97.1(2)-98.7(2) Å; O—Fe—O=81.1(2)-82.4(1) Å; For the outer Fe—atoms: Fe—O=1.944(4)-1.963(4) Å; Fe—Cl=2.267(2)-2.276(2) Å; Fe—N=2.007(5)-2.025(5) Å; N—Fe—N=114.2(2)-124.6(2)°; Fe—N—N=119.1(4)-121.6(4)°.
The crystallographic characterization of formula (I) was performed using well-established procedures. In analyzing the crystal structure data, corrections were made for Lorentz and polarization effects using an empirical absorption factor based on azimuthal scans, which resulted in a reliability factor of R=0.036, and a goodness-of-fit indicator of 1.73.
The eight Fe-atoms associated with formula (I) were located on C 3 -axes at positions defining two concentric tetrahedra with average Fe—Fe edges of 3.074(2) and 5.853(4)°, respectively. The μ 4 -O atoms, which connected the eight-Fe-atom network, were expected to be efficient mediators of antiferromagnetic coupling and expected to account for the relatively low effective magnetic moment of 6.52 B.M. of formula (I). Within each (μ 4 -O)Fe 4 group, the O-atoms were displaced from the centers towards the bases of the Fe 4 -trigonal pyramids.
While the Fe 8 O 4 Cl 4 skeleton of formula (I) was in tetrahedral arrangement, the propeller-like rotation of the μ-pz groups eliminated the mirror planes of T d symmetry, thus reducing the overall symmetry of formula (I) to that of the T-point group. A consequence of this symmetry was that formula (I) occurred in two enantiomeric forms; first co-crystallized as a racemic mixture (i.e., a 50/50 mixture of the two possible enantiomeric forms), the interconversion of which requires the rearrangement of all twelve pyrazolato bridges by simultaneous rotation about the four C 3 -axes of 1. The arrangement of twelve pyrazole rings in the outer part of formula (I) gave this molecule an approximate appearance of a sphere of approximately 12 Å diameter and a hydrophobic surface responsible for its high solubility in non-polar solvents (FIG. 2 ). FIG. 2 shows one enantiomeric form, while the other form is its mirror image.
E. Electrochemical Properties
The electrochemical properties of the complex of the invention were studied by Cyclic and AC Voltammetric techniques, in CH 2 Cl 2 solvent, 0.5 M terabutylammonium hexafluorophosphate supporting electrolyte, in a voltammetric cell with the standard three-electrode configuration, employing a platinum working electrode. The electrochemical study, from −2.00 to +2.20 V, showed three reversible reductions at −0.43, −0.78, and −1.07 V vs. Fc/Fc+. A fourth reduction at −1.38 V was irreversible at 285 K, but became chemically reversible and electrochemically quasi-reversible in chilled solution. (FIG. 3 ).
As no oxidation was observed, it was evident that the complex of formula (I) retained its structural integrity, in its neutral or some anionic form, over the measured 4.20 V window, i.e., −2.00 to +2.20 V. The complete electrochemical reversibility of the first three reductions, at ambient or low temperature, indicated that no significant structural rearrangement accompanied those electron-transfer processes. The unusual stability of formula (I) over five oxidation states can be accounted for by the encapsulation of the Fe 4 O 4 -core inside the outer shell of four interlocked Fe(μ 4 -pz) 3 Cl groups forcing its structural integrity, in a fashion similar to the wrapping of apoferritin around the Fe/O cluster of ferritin. The spontaneous assembly from mononuclear precursors, as well as the stability and rich electrochemistry of formula (I), indicate the likelihood of developing an electron-transfer protein based on a Fe 4 O 4 active center described in formula (I).
The four tetrahedrally arranged chlorine atoms at the outer shell of formula (I) were readily substituted by anionic or neutral ligands in simple metathesis reactions providing a convenient means by which to manipulate the size and solubility of the octanuclear cluster, as well as to connect octanuclear units by bridging ligands into covalent supramolecular assemblies. Such derivatives of formula (I) retained the redox characteristics of their parent compound with minimal variations of the E ½ values. These results indicate that the Fe 4 O 4 -core was the site of the redox activity.
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The present invention is directed to a complex comprising a redox-active metal cluster in a chemically inert shell. The inventive complex has the formula M 8 (μ 4 -E) 4 (μ-L) 12 X, where M is chosen from a transition metal, a lanthanide, an actinide and mixtures thereof; E is a chalcogenide; L is a bridging ligand; and X is a terminal ligand. The chemically inert shell enables the complex to exhibit structural stability over several oxidation states, and to exhibit reversible electrochemical reduction properties. A single reactor method of making this complex from simple starting materials is also disclosed. The active center further allows the octanuclear complex to be used in making supercluster assemblies that have electron transfer properties or in making contrasting agents for MRI applications, for example.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to fourdrinier papermaking by which a continuous web is formed from a jet of fibrous slurry flowing through a slice opening in a headbox. More particularly, the present invention relates to a gauge or tool for measuring the three interdependent dimensions of a papermachine headbox slice opening.
2. Description of the Prior Art
In the continuous, fourdrinier method of manufacturing paper, a slurry of aqueously suspended fiber jets from the elongated slice opening of a headbox onto a traveling drainage screen. The fiber constituency of the slurry is retained on the screen surface to form an accumulated mat or web while the aqueous vehicle drains through the screen pores.
One of the more highly sought quality characteristics of paper made by this method is a uniform cross-directional basis weight: i.e. a uniform weight of dry fiber per unit area across the width of web so formed. A significant basis weight profile control parameter is the headbox slice profile. This profile is essentially defined by three, interrelated dimensions: (1) the slice opening, (2) the slice lip projection and (3) the apron length.
The slice apron is that structural component of a headbox serving as the lower support element for the slurry as it flows across the headbox slice opening. The slice lip is that structural component of a headbox having a very thin longitudinal lower edge which defines or delineates between the headbox interior and exterior. A headbox slice beam is the front wall of the headbox to which the slice lip is structurally secured albeit accommodation is given to adjustment of the slice lip in the vertical plane by means of numerous, uniformly spaced slice adjusting rods or screws.
From these components, the slice opening is that distance between the lower edge of the slice lip to the upper surface plane of the slice apron. The slice lip projection is that distance between the lower edge of the slice beam and the lower edge of the slice lip. The slice apron length is that distance between the terminal end of the slice apron and the vertical plane of the slice lip.
Interdependence of these slice dimensions arises from the complex structure of the headbox slice beam and automatic control over the beam and lip profiles. There are two dominant stress sources upon the beam. Thermal stress due to temperature differences between the slurry and the ambient atmosphere surrounding the headbox may warp or bow the beam in a large, shallow arc from deckle to deckle. The resulting geometric consequence of these stresses on the slice profile normally is not planar-parallel with the slice apron plane, i.e. the bow causes a slice lip having a uniform lip projection to yield a slice opening in the slice center different from that at the deckle edges. Another source of stress on the headbox beam having slice opening profile consequences is the hydraulic head of the slurry therewithin. If uncorrected, a basis weight gradient in the web may result.
Correction of such a beam bow usually takes the form of automatic slice lip adjustment by which the electronically scanned basis weight profile is translated to motorized rotation of the slice lip adjusting rods. If properly calibrated, this slice lip adjustment will level the slice opening relative to the apron notwithstanding the beam bow. Simultaneously, profiled differentials will arise in the lip projection and apron length dimensions.
To a certain degree, such profiled differentials in the slice lip and apron length dimensions are acceptable. When the acceptable limits are exceeded, however, other control forces must be brought to bear on the slice beam itself. For these reasons, it is essential that the slice lip be correctly calibrated relative to the slice beam and slice apron. Such correct calibration requires that the three slice lip dimensions hereto described begin from uniform or at least known settings when the headbox is empty and at a stable ambient temperature. This requires a very careful, consistent, and extremely precise manual measurement of the dimensions at approximately 30 locations across the slice width: many of which must be made from an awkward position.
It is, therefore, an object of the present invention to provide a light and easily manipulated gauge that is adapted for measuring all three of the critical slice opening dimensions.
SUMMARY OF THE INVENTION
This and other objects of the invention, as will be apparent from the following description, are served by a substantially rectangular base plate having two parallel reference fences and dial micrometers. One reference fence is on the bottom of the plate for following the terminal end of the slice apron. The other reference fence has a beveled face for planar alignment with the underside of the headbox beam. Both micrometers are post mounted on an axis perpendicular to the base plate at one end thereof. One micrometer is of the plunger type that is mounted with the plunger axis perpendicular to the fence plane. The other micrometer is of the swinging stylus type; also mounted with the stylus swing plane perpendicular to the fence plane.
The slice apron length and slice opening dimensions are taken across the entire slice width by holding the bottom fence firmly against the terminal end of the slice apron and adjusting the micrometers to convenient reference position against the slice lip engaging the outer vertical face and lower edge, respectively. Relative dimensional changes along the slice width are reported on the micrometer dials as the gauge is manually slid along the apron edge length. These dimensional measurements are usually noted relative to the most proximate adjusting rod position.
Slice lip projection dimensions are also measured with a sliding motion as the gauge is held with the upper, beveled fence face flat against the beam face and pulled into contact with slice lip backside face. Relative dimensional changes are read from the swinging stylus micrometer which engages the slice lip lower edge.
BRIEF DESCRIPTION OF THE DRAWING
Relative to the drawing wherein like reference characters designate like or similar elements throughout the several figures of the drawing:
FIG. 1 is a sectional schematic of a papermachine headbox slice region.
FIG. 2 is a plan view of the invention.
FIG. 3 is a side elevation of the invention.
FIG. 4 is an end elevation of the invention.
FIG. 5 is a schematic of the invention as used to measure slice opening and apron length.
FIG. 6 is a schematic of the invention as used to measure slice lip projection.
DESCRIPTION OF THE PREFERRED EMBODIMENT
To facilitate subsequent explanation of the invention utility and novelty; reference is made to FIG. 1 for definitions of relevant structures and dimensions. Therein, a headbox slice beam 10 is represented as having a front wall 11 and a back wall 12. Firmly clamped against the front wall 11 is a profile bar 15 having a lip edge 16. Opposite from the slice edge 16 and across the slice opening O is a horizonal slice apron 17 having a terminal edge 18. The projection distance A of the apron edge 18 beyond the vertical plane of the lip edge 16 is the apron length.
The slice lip edge 16 also projects downwardly toward the apron 17 below the intersection of the beam 10 back wall plane 12 and the vertical plane 13 of the profile bar 15 backside. This projection is designated the slice lip projection L.
Although the absolute values of the dimensions A, O and L are important to the papermaker, it is the minute variations in a predetermined dimensional combination that concern him most frequently. For calibration purposes, therefore, it is the relative variations in these dimensions that must be identified respective to cross-machine position stations. The need to quickly and accurately identify these variations and their corresponding coss-machine location is served by the gauge shown in detail by FIGS. 2, 3 and 4.
Structurally, the present gauge comprises a generally rectangular base plate 20 having an upper face 20' and a lower face 20". This base plate is fabricated of brass, aluminum or other soft metal to protect the finish of the headbox lip structure. Rigidly secured to the base plate 20, along a reference edge 29 thereof are end bars 21 and 22. Topside end bar 21 is an end boundary fence for the beveled face fence 23. Preferably, the topside bar 21 is of soft metal like the base plate 20 while the beveled fence 23 is of a relatively soft, low friction material such as Teflon (polytetrafluoroethylene) or nylon.
The bottom side end bar 22 is a balancing slide shoe surface corresponding to the shoe surface portion 26 of the apron fence block 24. Fence step portion 25 of the fence block projects below the horizonal face of the shoe surface 26 to provide a fence edge 25" which abuts the apron terminal edge 18. End bar 22 and fence block 24 are both of relatively soft, low friction material such as Teflon or nylon to prevent scratching of the headbox slice elements and facilitate sliding movement of the gauge along the apron 17 surface.
For flexibility of use, the fence block 24 is positionally adjustable along base plate slots 27. Thimble nuts 28 threaded onto machine screws passing through the fence block 24 clamp the block in a desired position against the baseplate.
To support the plunger micrometer 30, a post 31 is provided for threaded insert into one of several aligned sockets 32 in the base plate whereby the post 31 axis is perpendicular to the base plate plane. A post clamp 33 secures the micrometer to the post 31. The micrometer 30 face dial is actuated by reciprocal displacement of the plunger element 34.
Swing arm micrometer 40 is actuated by arcuate displacement of the wand 41. Positionment of the swing arm micrometer is alongside the base plate from a lateral bracket 42 which includes an integral post clamp 43. The micrometer supporting post 44 align with its axis perpendicular to the base plate 20 plane.
To measure variations in the apron length A and the slice opening O, the present gauge is adjusted and positioned as shown by FIG. 5 with the lower faces of shoe surfaces 22 and 26 firmly against the upper face of apron 17. Simultaneously, the stepped edge of fence block 24 firmly engages the terminal edge 18 of the apron. In this position, the micrometer support post 44 is axially aligned in the clamp 43 for substantial arcuate displacement of the swinging wand 41. The micrometer dial face is then rotated for reference alignment with the indicator needle.
Similarly, an appropriate socket 32 is selected for the plunger micrometer mounting post 31 to provide an initial displacement of the plunger 34 against the slice lip face of profile bar 15. As before, the dial face is rotated for needle reference alignment.
In this configuration, the gauge is manually slid along the apron edge with notation given to the variations in apron length projection, measured by plunger micrometer 30, and slice opening, measured by swing arm micrometer 40. These variations are correlated to a cross-machine location address for subjective evaluation.
Additive to that subjective evaluation are the slice lip projection variations as measured in the manner of FIG. 6. For this purpose the gauge is held upwardly with beveled face fence 23 firmly against the slice beam back wall 12 and the profile bar backside 13. The mounting post height of swing arm micrometer 40 is adjusted for mid-range displacement of the wand 41 against the lip edge 16 and the dial face rotated for needle reference alignment.
In this configuration, the gauge is slid along the length of profile bar and the dimensional variations reported by the micrometer 40 are correlated to the corresponding crossmachine location address.
Having fully described my invention.
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Complete definition of a papermachine headbox slice opening requires the measurement of three interdependent dimensions including (1) the projection distance of the slice lip edge below the slice beam, (2) the projection distance of the slice apron edge beyond the plane of the slice lip edge and (3) the slice opening distance between the slice lip edge and the upper face plane of the slice apron. A single gauging tool is provided for measuring all three headbox slice dimensions.
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BACKGROUND
Field of Invention
[0001] This invention relates to golf putting practice devices and, more particularly, to golf putting practice devices of the type embodying a feature to return a ball back to the person executing a putt.
[0002] Various putting practice devices, which use mechanisms to return the ball to a person, have been heretofore known in the art. Some of these devices use spring loaded or solenoid operated catapult type ball return systems. Another version employs a sliding carriage assembly mounted on a track and equipped with a paddle. An electric motor using a pulley and belt assembly drives carriage assembly with the attached paddle that sweeps the ball forwardly to the end of the track where a pivoting action of the paddle flips the ball back to the person executing the putt. All previous variations of the putting practice devices require large shells to accommodate the interior space required for the various catapulting systems to retract and then move forward to eject the ball as well as huge ball trays to create oversized targets to prevent missed putts. The aforementioned produces large and bulky putting practice systems.
OBJECTS AND ADVANTAGES
[0003] It is the primary object of the present invention to afford a novel putting practice device that is substantially smaller in size than existing prior art.
[0004] Another object is to afford a novel putting practice device, which, after receiving the ball, will return the same substantially to the place from which it was putted.
[0005] A further object of the present invention is to afford a novel putting practice device that is highly portable.
[0006] Other objects and advantages of the present invention are to afford a putting practice device with a ball tray that can be repositioned or detached for storage.
[0007] Another object of the present invention is to afford a more realistic putting target that more simulates the size and shape of the actual hole on the golf course.
[0008] A further object of the present invention is to afford a putting practice device with a ball tray that has a floor with a substantially shallow slope rearward, thereby affording a more flattened ball tray entrance.
[0009] Another object of the present invention is to provide a substantially flattened ball tray and eliminate the extra force needed in the stroke when putting the ball to overcome the steep incline of the ball tray ramp of conventional putting practice devices and afford a more natural putting action for stroking the ball.
[0010] Another object of the present invention is to provide a golf putting practice device that is battery powered for convenience and high portability.
[0011] Other objects and advantages of the present invention are a means to deactivate the practice putting device by means of a switch to disconnect the power to prevent unintentional activation during transporting or storage.
[0012] Another object of the present invention is to provide a golf putting practice device with an indicator that warns when the power to the unit is turned on and the putting practice device is ready for operation.
[0013] Other and further objects of the present invention will be apparent from the following description and claims and are illustrated in the accompanying drawings, which, by way of illustration, show the preferred embodiment of the present invention and the principles thereof and what are considered to be the best mode in which to apply these principles. Other embodiments of the invention embodying the same or equivalent principles may be used and structural changes may be made as desired by those skilled in the art without departing from the present invention and the purview of the appended claims.
SUMMARY OF THE INVENTION
[0014] The present invention provides a golf putting apparatus with a ball tray for receiving a golf ball putted therein. The ball tray may be repositioned or detached for convenient storage of the apparatus. A flipper device, disposed along the rear face of the ball tray, is used to eject the ball from the tray. The flipper device is provided with a mechanical means for pivoting about a pivot axis between a normal position disposed along the rear face of the ball tray to the extended position in such a manner to eject the ball from the tray and return the ball to the person making the putt.
DESCRIPTION OF THE DRAWINGS
[0015] In the drawings:
[0016] [0016]FIG. 1 is the front perspective view of a golf putting practice device embodying the principles of the present invention;
[0017] [0017]FIG. 2 is a front perspective view similar to FIG. 1 with a portion of the shell cut away to show in more detail the ball return flipper device;
[0018] [0018]FIG. 3 is a longitudinal sectional view taken substantially along the line 3 - 3 in FIG. 2;
[0019] [0019]FIG. 4 is a fragmentary sectional view taken generally along line 4 - 4 of FIG. 3 in the direction of the arrows, with the outline of the shell of the device show in dashed lines for simplicity;
[0020] [0020]FIG. 5 is a front perspective view similar to FIG. 1 with the ball receiving tray in the raised position and also when the ball tray is detached; and
[0021] [0021]FIG. 6 is an exploded, perspective view of the ball return flipper device embodied in the golf putting practice device shown in FIG. 1, FIG. 2, FIG. 3, and FIG. 4.
[0022] [0022] REFERENCE NUMERALS IN DRAWINGS 10 putting practice device 12 main housing 14 base 16 ball tray 17 ball tray floor 18 ball retard rib 20 pivot arm 22 pivot socket 24 pivot rod 26 pivot hole 28 flipper device 30 switch arm 31 switch opening 32 trigger 34 trigger stop 36 axle 38 tension spring 40 fixed anchor 42 pivotal anchor 44 anchor support 46 cog wheel 48 cog wheel arm 50 resilient movable contactor 52 retractor switch 54 release switch 56 resilient movable contactor 58 side support member 60 top support member 62 ball 64 ball pocket 66 outline of shell 68 motorized mechanism 70 outline of ball tray 72 light emitting diode (led) 74 main switch 76 motorized mechanism
DETAILED DESCRIPTION OF THE INVENTION
[0023] A game device in the form of a golf putting practice device 10 , embodying the principles of the present invention, is shown in FIGS. 1 - 6 , inclusive, of the drawings, to illustrate the presently preferred embodiment of the present invention.
[0024] The golf putting practice device 10 embodies, in general, a main housing 12 to enclose the ball return apparatus, a ball tray 16 for receiving the ball, a base 14 , a ball return flipper device 28 disposed longitudinally to the tray 16 for returning a ball from the ball tray 16 to the person putting the ball therein.
[0025] The present invention is characterized by a ball return mechanism which automatically ejects the ball from the ball tray 16 each time the ball is putted therein and returns it to the person making the putt. The ball return mechanism includes a flipper device 28 positioned longitudinally about the rear face of the ball tray 16 . The flipper device 28 has a flat front surface with the open recessed to form the ball pocket 64 .
[0026] The flipper device is normally biased by the cog wheel arm 48 into a rearward retracted position so as to retain the flipper 28 at its retreated position longitudinally along the rear face of the ball tray 16 as shown by solid lines in FIG. 3 but, when the cog wheel arm 48 advances by rotation of the cog wheel 46 about axle 36 , shown by broken lines in FIG. 3, and against the force of the spring 38 , the trigger 32 is disengaged and the flipper device 28 is rotated about the pivot rod 24 as the center substantially to a horizontally disposed position perpendicular to the ball tray 16 as shown by broken lines in FIG. 3.
[0027] Referring to FIG. 6 in particular, the flipper device 28 is pivotally secured at 26 at the top support member 60 and the base 14 by the pivot rod 24 passing throughout which provides a vertical axis about which the flipper device 28 may pivot relative to the top support member 60 and base 14 . Alternative designs may secure the described flipper device 28 with pivot pins axially aligned and secured at 26 at the top support member 60 and base 14 . The flipper device 28 is retreated against the tension force created by spring 38 by attachment to the fixed anchor 40 and pivotal anchor 42 , and further referenced in FIG. 3 and FIG. 4.
[0028] In the ball return means of the above arrangement, the motorized mechanism 76 rotates the cog wheel 46 about the axle 36 , as shown in FIG. 3, and the cog wheel arm 48 engages the trigger 32 of the flipper device 28 to cause, with further rotation of the cog wheel 46 , the flipper device 28 to rotate rearwardly against the tension force of the spring 38 . Referring to FIG. 3 and FIG. 4, when the flipper device 28 is fully retreated to the predetermined position, the switch arm 30 on the flipper device 28 engages the resilient movable contactor 50 of the retractor switch 52 and thereby interrupts the power to the motorized mechanism 76 and further causing the rearwardly rotating of the flipper device 28 to terminate. When the ball 62 is rolled into the ball tray 16 and comes to rest against and depresses the resilient movable contactor 56 of the release switch 54 located at the switch opening 31 of the flipper device 28 , power is restored to the motorized mechanism 76 and the cog wheel 46 further rotates about the axle 36 causing the cog wheel arm 48 to disengage the trigger 32 whereby the flipper device 28 is caused to be quickly returned to the rotated position by the resilient force of the spring 38 . Although the present invention describes the resilient movable contactor 56 and the release switch 54 as located at the switch opening 31 of the flipper device 28 , resilient movable contactor 56 and the release switch 54 may be located at various positions in proximity to the flipper device 28 rendering the switch opening 31 of the flipper device 28 to be removed and still remain within the scope of the herein described invention.
[0029] The present embodiment of the putting practice device 10 is also characterized by a ball tray 16 that is pivotally secured at pivot arm 20 at pivot socket 22 to the base 14 . The invention contemplates the provision of pivot sockets 22 that allow the pivot arms 20 to become dislodged from their position therein in the event of extreme force applied to the pivot arms 20 against the pivot socket. The distance along the longitudinal center line of the putting path as identified by the letter C in FIG. 3 from the entrance of the ball tray 16 to the flipper device 28 is sufficiently shallow and represents about one-half of the diameter of a regulation golf hole, thereby requiring only a slight sloping of the ball tray floor 17 to direct the ball 62 into the ball pocket 64 therein. This gives the ball tray floor 17 a low interior profile at the front entrance, which provides a correspondingly flatter surface for a ball 62 to roll therein. This affords the practice putting device 10 with a ball tray 16 closely related to the regulation hole in the game of golf. The herein described ball tray 16 of the present invention may be connected in various other means to the putting practice device 10 that allow the ball tray 16 to be physically detached from the putting practice device 10 for storage and transporting and reattached to use the device for the herein intended purpose.
[0030] Referring to FIG. 3 and FIG. 4, the invention also contemplates the provision of a ball retarding rib 18 at the entrance to the ball tray 16 to check the speed of a ball travelling into the ball tray 16 and further to aid in retaining a ball 62 inside the parameter of the ball tray 16 once it has entered thereto, unless said ball is directed thereto at excessive speed.
[0031] Referring to FIG. 3, the device 10 of the present embodiment is further provided, as mounted in the main housing 12 part, with a light emitting diode (LED) 74 to indicate when power is turned on to the unit which is connected by an electrical connector (not shown) to the main switch 72 that turns on and shuts off power to the device 10 .
[0032] The operation of the putting practice device according to the present invention shall be described next as summarized. Referring to FIG. 3, when the putted ball successfully enters the ball tray 16 , the ball comes to rest in the ball pocket 64 and against the resilient movable contactor 56 , shown in FIG. 2, of the release switch 54 located at the switch opening 31 of the flipper device 28 which is disposed in a retracted position against the tension force created by spring 38 longitudinally along the rear face of the ball tray 16 by the cog wheel arm 48 of the rotating cog wheel 46 about the axle 36 engaging the trigger 32 of the flipper device 28 . Referring to FIG. 4, in this retreated position, the switch arm 30 of the flipper device 28 engages the resilient movable contactor 50 of the retractor switch 52 and thereby shuts off the power to the motorized mechanism 76 that rotates the cog wheel 46 . Referring to FIG. 2, FIG. 3, and FIG. 4, when the ball rests against the resilient movable contactor 56 of the release switch 54 , the motorized mechanism 76 is energized and rotates the cog wheel 46 about axle 36 and dislodges the cog wheel arm 48 from the trigger 32 of the flipper device 28 causing the flipper device 28 to return quickly to the rotated position by the resilient force of the spring 38 , shown by broken lines in FIG. 3, where the forward motion of the flipper device 28 is halted by the trigger stop 34 , thereby ejecting the ball from the ball tray 16 and returning the ball back to the person making the putt.
[0033] Referring again to FIG. 2 and FIG. 3, concurrently, with the forgoing ball return operation, the switch arm projection 30 of the rotated flipper device 28 disengages the resilient movable contactor 50 of the retractor switch 52 thereby providing power to the motorized mechanism 76 and causing the cog wheel 46 to rotate about the axle 36 to a position where the cog wheel arm 48 engages the trigger 32 of the flipper device 28 and rotates the flipper device 28 against the tension of the spring 38 to a longitudinally retreated position along the rear face of the ball tray 16 . With the above arrangement of ball returning means, it will be readily appreciated that the intended ball return operation can be realized by the energy of a battery or batteries accommodated in the device which requires no connecting to any external commercial power source which further enhances the extreme portability of the device.
[0034] Referring to FIG. 4, the ball tray 16 is pivotally secured at pivot arm 20 at pivot socket 22 to the base 14 of the putting practice device 10 and is characterized by a sufficiently shallow depth measured along the longitudinal center line of the putting path as identified by the letter C in FIG. 3 from the entrance of the ball tray 16 to the ball pocket 64 of the flipper device 28 , representing substantially one-half of the diameter of a regulation golf hole. Henceforth, this requires only a minimal slope in the ball tray floor 17 to direct the ball 62 into the ball pocket 64 formed by the intersection of the flipper device 28 and the face of the main housing 12 . Thusly, the incline at the entrance of the ball tray 16 is substantially low and allows the putted ball to enter the ball tray without the aid of a ramp. Referring to FIG. 5, the ball tray 16 of the present invention may be rotated in an upward direction from the normal flat position for ball retrieval in the intended use to fold substantially against the main housing 12 to store the device 10 . The current embodiment also contemplates the provision of pivot sockets 22 that allow the pivot arms 20 of the ball tray 16 to detach and breakaway from the from the pivot sockets 22 when a force is exerted to the pivot arms 20 in a direction pulling away from the pivot sockets 22 .
[0035] Notwithstanding the forgoing, it is obvious that numerous changes may be made in the form, construction and arrangement of the several parts without departing from the spirit or scope of the invention, or sacrificing any of its attendant advantaged, the form herein disclosed being a preferred embodiment for the purpose of illustrating the invention and not intended in a limiting sense.
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A golf putting practice device ( 10 ) having a main housing ( 12 ), a substantially flattened ball tray ( 16 ) to receive putted balls that is retractable and removable, and a flipper device ( 28 ) disposed in a position along the rear face of the ball tray ( 16 ) to automatically return the putted balls from the ball tray ( 16 ) back to the person making the putt.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The tracked cable guide assembly of this invention improves the capability for storage of electrical conductor cable in a drill pipe. Twisting is prevented or reduced in the overlapped portion of cable which is looped between upper and lower cable guides. This invention also simplifies the placement of the storage apparatus within the drill pipe.
2. Description of the Prior Art
Telemetry is a major focus for research in the drilling of oil, gas, or similar boreholes into subterranean formations. Enhanced transmission of data concerning downhole conditions could improve drilling safety and efficiency. Sending coded electrical impulses to disclose subsurface conditions is one method of telemetry. Measuring conditions and transmitting data while drilling, however, is complicated. To develop a reliable electrical transmission means has been a major goal. In conventional rotary drilling, thirty (30)-foot sections of drill pipe are added to the drill string as drilling proceeds. To maintain an electrical circuit to the surface, additional conductor cable must be available when pipe is added. Sections of cable may be added at the surface or additional cable may be stored within the drill pipe and threaded through each additional pipe section. This invention relates to an improved apparatus to store excess conductor cable within the drill pipe.
Earlier telemetry operations required that an instrument package be lowered into the drill pipe or wellbore when measurements were desired. Drilling had to stop to collect downhole data. It could not proceed until the instrument package was removed from the well. Thus, telemetry was a slow process which greatly disrupted the drilling operation.
To reduce the disruption caused by the earliest telemetry system, an electrical conductor was incorporated into the drill pipe. A circuit was formed through the pipe with special connections at each joint. U.S. Pat. Nos. 3,518,608 and 3,518,609. The incorporated conductor system was undesirable for at least three reasons. One, junctions at each joint greatly increased the circuit resistance. Greater power was required to transmit electrical impulses. Two, the junctions often short-circuited because insulating them from the drilling mud was difficult. Three, drill pipe had to be modified significantly. This modification either greatly increased the cost of telemetry, or induced operators not to use this system.
Another suggested improvement over the earliest telemetry system was to run a conductor cable inside the drill pipe from a downhole instrument package to the surface and to add additional sections of cable at the surface when additional drill pipe was connected to the drill string. In U.S. Pat. No. 2,748,358, sections of cable somewhat longer than the section of pipe added were connected to the existing conductor line. As with the modified drill pipe, however, this system proved undesirable in many circumstances. Again, the multitude of connections required increased power to transmit electrical signals. The cable connections tended to erode under the abrasive action of drilling mud. Erosion led to system failure. The excess length of cable could snarl and tangle with itself during the drilling operations, either impeding withdrawal of the cable or leading to telemetry system failure.
In U.S. Pat. No. 3,807,502, an attempt was made to reduce the twisting and snarling problem of storing excess conductor cable within the drill pipe. At the beginning of a drill bit run, a continuous length of cable was suspended from the surface to a subsurface instrument. Additional lengths of conductor cable were added for each section of pipe added during the bit run. The improved system provided a clamp to remove slack between the instrument and the surface. This system, however, was still inefficient. One, it still required a number of cable sections and connections. Two, it consumed large amounts of cable because a new length of continuous cable had to be payed out at the beginning of each bit run.
A second system to reduce twisting and snarling was disclosed in U.S. Pat. Nos. 3,825,079 and 3,918,537. Instead of a clamp to remove slack in the conductor cable within the drill pipe, these patents disclosed an apparatus to store the excess conductor cable in an overlapped configuration. A rigid track extended between an upper and a lower cable guide to permit axial motion of the lower cable guide, but to prevent relative angular movement. Typically about sixty (60) feet of excess cable could be stored in this overlapped configuration. The system contemplated adding sections of conductor cable with each, additional pipe section.
Further improvements were developed to store a continuous segment of conductor cable within the drill pipe. These improvements eliminated the multitude of connections. In one system, additional lengths of cable were withdrawn from a cable storage reservoir as pipe sections were added. U.S. Pat. Nos. 3,825,078 and 3,913,688 typically, cable was stored in an overlapped configuration between upper and lower cable guides.
In U.S. Pat. No. 4,098,342, use of a constriction in the pipe joints limited rotation of the lower cable guide. A long weight was added to the lower guide, and checks were added to each pipe joint to limit the twisting of this weight. Two design criteria of this system may limit its suitability in some circumstances. The checks have to be added at each joint and be aligned so that twisting will be prevented. The weight has to be long enough (typically about thirty-six (36) feet) so that it will continually contact at least one of the checks.
Excess conductor cable may be wrapped around a spool which is then suspended in the drill pipe. U.S. Pat. No. 4,153,120. To add pipe, additional sections of cable may be manually unwound from the spool after withdrawing the spool from the drill pipe. By necessity, this system requires slacked cable within the pipe, equal in length at least to the length of the spool plus the desired pipe length. This excess cable would tend to tangle during drilling operations.
A further development of the overlapped cable system disclosed a means to tension the segment of cable extending from the subsurface location up to the upper cable guide. U.S. Pat. No. 3,957,118. Suspending the weighted lower cable guide on a looped portion of the cable eliminated slack in the overlapped segments of the conductor cable, but did not sufficiently tension this segment of cable. The gripping means allowed a tension to be placed on this segment and maintained thereon.
This invention continues the development of the overlapped conductor cable system. It presents further improvements.
SUMMARY OF THE INVENTION
The apparatus of this invention stores a continuous, electrical conductor cable between a subsurface instrument package and the surface. Excess cable shaped in an overlapped configuration is stored to prevent or to impede snarling or twisting. The conductor cable extends upwardly from a subsurface location to an upper cable guide. Preferably this segment of conductor cable is anchored at the subsurface location to an instrument package useful for well drilling telemetry. Furthermore, this segment is preferably held in tension by means for gripping which are associated with the upper cable guide. The conductor cable extends from the upper cable guide down to a lower cable guide which is suspended on a looped portion of the cable. From the lower cable guide, the conductor cable extends up to the surface. The lower cable guide is free to move axially within the drill string as conductor cable is payed in or payed out. The upper cable guide is mounted in the drill pipe. The cable guides define an overlapped portion of cable where excess cable may be stored.
A novel feature of this invention is the use of a flexible, elongated member, preferably a cable, which is attached to the inside of the drill pipe between points substantially at the upper cable guide and substantially at the subsurface location. Upon tensioning, the elongated member serves as a guide track for the axial motion of the lower cable guide. One or more connector arms attach the lower cable guide to the substantially vertical, elongated member which extends along the length of the drill pipe. These connector arms allow axial motion, but they impede or prevent rotation of the lower cable guide relative to the upper cable guide and to the drill string. To control the rotation further, the lower cable guide may preferably be connected to the tensioned portion of the conductor cable which extends from the subsurface location up to the upper cable guide.
The tracked cable guide assembly of this invention is an improvement over prior art systems because it is more efficient and more reliable. Installation of the assembly is simplified because flexible members are preferably used instead of rigid members. Preferably a cable is fastened to the inside of the drill pipe to form a substantially vertical track which becomes rigid upon tensioning. Thus, the cumbersome handling problems of using initially rigid members are reduced.
The tracked cable guide assembly offers greater improvements than merely installational efficiency. Entanglement of the stored cable is reduced so that drilling operations are not often disrupted. Telemetry is facilitated. The system allows nearly instantaneous communication of downhole conditions to the surface throughout all phases of drilling. The system eliminates the need to align constrictions at each section of pipe--only the location of a single pin is important to installing the apparatus of this invention. Furthermore, the system of this invention allows for easier removal of that apparatus placed within the drill pipe which would impede emergency operations. The upper and lower cable guides are preferably releasably attached to the drill pipe. The upper guide is releasably attached to a spider mounting; the lower guide is releasably connected to the track which is attached to the inside of the drill pipe. Thus, by remote action at the surface, the drill pipe may be quickly cleared of all constrictions which will interfere with passage of tools down the well. Preferably, all that need be done is to apply a force to the conductor cable at the surface to extract it and the two cable guides from the drill pipe.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic illustration of the preferred embodiment of this invention. It shows an upper and a lower cable guide disposed in a drill string to store electrical conductor cable. The axial motion of the lower cable guide is tracked on two tracks. One track constitutes that segment of the conductor cable which extends between the upper cable guide and a subsurface location. The other track constitutes an elongated member attached to the inside of the drill string.
FIG. 2 is a detailed, design drawing showing the particulars of the preferred embodiment of the upper and lower cable guides.
FIG. 3 is a drawing of the lower connection of the elongated member which forms the track along the inside of the drill string.
FIG. 4 is a drawing of the grooved surface on the lowest portion of the connection shown in FIG. 3. This groove allows remote attachment and detachment of the connection.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
1. Introduction
This invention is an improved means for storing electrical conductor cable inside a drill string. An overlapped portion of cable is looped around upper and lower cable guides positioned in a drill string to store cable between surface and subsurface locations. The lower cable guide is weighted to maintain tension in those segments of conductor cable that loop on the two cable guides. The lower cable guide is movable in an axial direction within the drill string to allow storage of various lengths of cable. Its axial motion is guided by one or more tracks established inside the drill string.
This invention may be used in both conventional rotary drilling and in specialized drilling. Rotary drilling applications are preferred. A typical example of specialized drilling is use of a turbo-drill and a positive displacement hydraulic motor to drill a slightly deviated or directional wellbore. The customary apparatus of conventional rotary drilling and specialized drilling is discussed in U.S. Pat. No. 4,098,342 (Robinson et al.). This patent also discusses the process of drilling a wellbore. The information disclosed in this patent is incorporated by reference into this specification.
2. The Parts of the Apparatus
FIG. 1 schematically shows the three (3) major components of the apparatus. Inside a drill string 10, an elongated member 52 guides a lower cable guide 14 between an upper cable guide 12 and a point substantially at a subsurface location 16 to store electrical conductor cable in an overlapped configuration.
The upper cable guide 12 preferably comprises:
(1) a centralizer 21;
(2) an upper sheave 22;
(3) a means 23 for mounting the upper cable guide in the drill string 10;
(4) a means 24 for gripping the conductor cable; and
(5) a connection 25 for the upper end of the elongated member 52 which forms a track inside the drill string 10.
The lower cable guide 14 preferably comprises:
(1) a lower sheave 41;
(2) one or more cable weights 42;
(3) one or more connector arms 43 to join the lower cable guide 14 to that portion of the conductor cable which extends between the upper cable guide and the subsurface location; and
(4) one or more connector arms 44 to join the lower cable guide 14 to the elongated member.
At a subsurface location 16, an electrical connector 61 joins the conductor cable 51 to an instrument package which preferably comprises:
(1) a receiver package 62 to receive commands from the surface, to activate downhole measuring devices, to store and to multiplex signals and to transmit coded, electrical signals back to the surface representative of the measured phenomenon;
(2) a measurement package 63 to record downhole conditions in response to commands; and
(3) transducers 64 to measure downhole conditions in terms of equivalent electrical impulses.
Typical phenomena of interest include temperature, pressure, inclination, weight-on-bit, bit wear, radioactivity, and the like.
Also, illustrated in FIG. 1 are incidental apparatus. The elongated member 52 which forms a track inside the drill pipe 10 is preferably releasably connected to the drill pipe 10 by a lower connection 54 which preferably attaches to the drill string 10 on a pin 55 and groove (not shown). Furthermore, a stop guide 53 is preferably placed in the drill string 10 at a point above the bit to check the downward motion of equipment associated with the conductor cable storage system. If equipment were to fall in the drill pipe, it would be stopped by the stop guide 53 before it were to fall into the bit.
Throughout this specification the terms "drill pipe" and "drill string" will be used interchangeably to mean that portion of tubular goods which extends into the wellbore when one drills into a subterranean formation. Conventional distinctions between the terms are irrelevant for purposes of the discussion in this specification.
3. The Operation of the Apparatus
Because this invention comprises a number of individual elements, this application will sequentially discuss each element and its relationship of each to the whole. First, the track guide will be discussed. Second, the cable storage assembly will be discussed. Third, a summary of the operation of the entire apparatus will be discussed.
A. The Track Guide
Preferably a flexible, elongated member 52 extends from a point substantially at the lower end of the upper cable guide 12 downwardly to a point substantially at, although somewhat slightly above, a subsurface location 16. The elongated member is substantially vertical. By the term "substantially vertical," it is meant that the elongated member is essentially parallel to the centerline of the drill string 10 in the plane which would contain both the centerline and the elongated member if they were truly parallel. "Substantially vertical" is used in this application to describe this spatial relationship; it should not be used to mean vertical in a gravitational frame of reference. The substantially vertical, elongated member 52 preferably is releasably fastened to the drill string 10. Once fastened at its lower end, preferably the member is tensioned. At its upper end, a connection 25 is preferably fastened to the spider mounting 23 for the upper cable guide 12. Preferably, the connection 25 is a steel set-plate to press against the cable. At its lower end, a lower connection 54 preferably seats on a pin 55 in the drill string 10. As shown in FIG. 3, the connection 54 preferably comprises three (3) segments. The upper segment 301 is designed to be the connection for the elongated member 52. Preferably, this upper segment 301 is a cut-away portion of steel tubing to which is soldered a cable fastener (not shown) similar to that used for the upper end of the elongated member 52. The tubing is preferably cut-away to allow easier passage of tools, such as an electrical connector 61, through the lower connection 54 for the elongated member 52. Typically the clearance will be low. The cut-away portion gives slightly greater leeway.
The second segment 302 of the lower connection 54 preferably comprises a section of steel tubing threaded to mate respectively with the upper and lower segments 301 and 303. This segment eases machining of the working ends of the connection 54. Design modifiations are more readily handled with the three-fold device.
The lower segment 303 preferably is a steel tubing with a tapered point 401. Along its outer surface, the lower segment has a groove shaped in the pattern described in FIG. 4. The tapered point 401 or surface 402 or 403 contact a pin 55 on the drill string 10. The connection 54 is rotated as the pin slides upon the surface of the taper. The pin enters the groove system when the taper is complete at 404. Further lowering of the connection 54 ensues until lowering is impeded by the end of the groove 405. Tensioning the elongated member 52 causes the connection 54 to rise and to rotate as the groove is followed into the long tongue portion 406. With the connection 54 seated in this position, the elongated member 52, preferably a steel cable usually of 9.5 mm (0.375 in.) diameter, is tensioned to a pull of approximately 227 kg (500 lbs.) and is fastened at its upper end.
The lower connection may be released from its pin seat by releasing the tension in the elongated member 52. The lowering of the connection 54 will cause the pin 55 to move out of the tongue 406. The connection 54 will rotate along the groove to another lowering stop 407. Tensioning the elongated member 52 will cause the connection 54 to rotate so that the pin 55 will ultimately disengage the groove at the point where it entered 404. In such a fashion, the connection 54 may be connected and disconnected remotely.
B. The Cable Storage System
In FIG. 2, the upper cable guide 110 and lower cable guide 120 preferred in this invention are depicted in a drill pipe 100. The insulated, electrical conductor cable extends from the subsurface location (not shown) up to and around the upper cable guide 110 in a first segment 235. Preferably this first segment of cable follows a groove formed in the cable weights 245 and the lower cable guide 120. In one embodiment of this invention, one or more connector arms (not shown) may be used to hold the cable in this groove. The connector arms preferably are flaps of rubber or some other elastomeric material which clip on buttons on the lower cable guide 120 and the cable weights 245 to form loops which enclose the cable. Connector arms of this nature impede or prevent rotation of the cable weights 245, but they permit axial movement of the lower cable guide 120 as conductor cable is payed in or out.
Preferably the first segment of the conductor cable 235 is maintained in tension. To accomplish this tensioning, means for gripping the cable 210 are mounted on the upper cable guide 110. These means are described in U.S. Pat. No. 3,957,118 (Barry et al.), which is incorporated by reference in this specification. The first segment of cable 235 is preferably connected at its lower end to an instrument package which preferably is fastened to the drill pipe 100. In this circumstance, an electrical connector 61 may be releasably attached by remote action to the instrument package. Means for tensioning the first segment of cable 235 (such as a winch) may be maintained at the surface. When the electrical connector 61 is attached to the instrument package, the means for tensioning stress the cable preferably to about 454 kg (1000 lbs.). The means for gripping 210 maintain this tension within the first segment 235.
The conductor cable passes around an upper sheave 205, which is mounted on the upper cable guide 110. In a second segment 225, the cable extends from the upper cable guide 110 down to and around the lower cable guide 120. Mounted on the lower cable guide 120, a lower sheave 230 and a sheave guard 250 keep the cable in order. The lower cable guide 120 is suspended on a loop in the conductor cable between the second segment 225 and a third segment 220. Slack is removed in these two segments, 220 and 225, by adding cable weights 245 to the lower end of the lower cable guide 120. The third segment 220 extends from the lower cable guide 120 up to the surface. Preferably, it passes through a centralizer 200 mounted on the upper cable guide 110 as it passes upwardly in the drill string.
Preferably the upper cable guide 110 is releasably mounted in the drill pipe 100. A spider preferably is shaped as a cut-away piece of tubing and is fastened to the drill pipe 110 to serve as a means for mounting. Grooves in the tubing are designed to accept retractable pins on the unshown side of the upper cable guide 110. The pins retract upon removal from the grooves. Withdrawing the cable above the upper cable guide 110 moves the lower cable guide 120 upward to reduce the length of stored cable. When the upper cable guide 110 and the lower cable guide 120 contact (as shown in FIG. 2), the minimum length of cable is stored in the well. Further withdrawal of the cable 220 will tend to raise both the upper and the lower cable guides, 110 and 120 respectively. The upper cable guide 110 will extract from the spider mounting. The entire storage apparatus can be removed then from within the drill string. The elongated member will be left attached to the inside of the drill pipe.
Associated with the spider mounting, a set plate 215 forms the cable fastener for the upper end of the elongated member 240. Preferably a cable extends upwardly from the releasable lower connection (not shown), and passes through the set plate 215. Screws may be tightened to fasten the cable between the spider mounting and a metal plate. Preferably, the cable is pretensioned to about 227 kg (500 lbs.) tension before the set plate 215 is screwed down.
The lower cable guide 120 and the cable weights 245 are preferbly grooved to accept the elongated member 240 as a track guide for the axial movement of the lower cable guide 120 as cable is payed in or out from the surface. One or more connector arms (not shown) for the elongated member 240 preferably are connected to the lower cable guide 120 and cable weights 245. These arms preferably comprise elastomeric fasteners which button on the lower cable guide 120 and on the cable weights 245. These connector arms impede or prevent rotation of the lower cable guide 120, but they permit axial movement of the lower cable guide 120. Rotation of the lower cable guide 120 relative to the upper cable guide 110 or to the drill pipe 100 may be further limited by guiding the axial movement of the lower cable guide 120 on both the first segment of cable 235 and on the elongated member 240. Twisting and snarling may be substantially prevented by tracking on both of these guides. Some rotation of the lower cable guide 120 relative to the upper cable guide 110 is allowable without creating serious entanglement problems. Rotation of less than about 30° of arc has been found to be tolerable, although it is much preferred to limit rotation as much as possible. Therefore, tracking on both the first segment of cable 235 and the elongated member is preferred.
To prevent excessive corrosion to the insulated conductor cable, especially around the upper sheave 205 and the lower sheave 230, covers (not shown) should be attached to the upper and lower cable guides to eliminate drilling mud flow from these elements.
C. Operation of the System
The lower cable guide moves axially upward and downward in the drill pipe as cable is payed in or payed out. Typically thirty (30)-foot segments will be withdrawn from the overlapped configuration as drilling proceeds. Thus, the lower cable guide will rise approximately fifteen (15) feet. Should the storage capacity be exhausted, more cable may be stored by connecting the upper end of cable to a new lead and paying out cable from the surface. The lower cable guide will lower within the drill string to store this new length. The resistance to signal transmission will be increased only by one, additional connection over that resistance of the desired length of cable.
To operate the system, the drill pipe is suspended in the well. The pipe should be long enough to store the desired length of cable between the lower pin and the surface. The lower connection for the elongated member is lowered into the drill pipe. It is fastened to the pin. A tension is placed in the elongated member. It is fastened to the upper end on the spider mounting to form a substantially vertical, track guide.
An electrical connector preferably is lowered through the lower connection to join with an instrument package at a subsurface location. The electrical connector preferably is releasably connected to the package, but it is anchored sufficiently that a tension may be placed in a first segment of cable which extends from the subsurface location up to and around the upper cable guide.
The upper cable guide is releasably mounted in the drill pipe by way of the spider mounting. The upper cable guide preferably has a means for gripping the cable to maintain a tension in the first segment of cable, which extends downwardly to the instrument package. The conductor cable is looped around upper and lower sheaves, and the lower cable guide is allowed to descend into the drill pipe as cable is payed out. Preferably the lower cable guide tracks on both the first segment of cable and the elongated member. The lower cable guide should be releasably joined to the elongated member so that the electrical connector cable, and the upper and lower cable guides may be removed from the drill pipe by exerting an upward pull on the conductor cable. The lower cable guide is lowered to store the desired amount of cable for a bit run. Typically about 1000 to 1500 feet (305-458 m) of cable may be stored in an overlapped configuration by lowering the lower cable guide.
Based upon the description contained in this specification, those skilled in the art will be capable of substituting parts while maintaining the features which distinguish this apparatus from the prior art systems. The description provided is not meant to restrict the invention except as is necessary by an interpretation of the prior art and by the spirit of the appended claims.
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An improved apparatus to store an insulated electrical conductor cable in a overlapped configuration within a drill pipe includes a track attached to the drill pipe to guide a lower cable guide so that the overlapped portions of conductor cable will not snarl or twist during rotary drilling operations. To insure against entanglement, further restriction of rotation may be gained by additionally tracking the lower cable guide on a tensioned portion of the conductor cable which extends from a subsurface instrument package upwardly to an upper cable guide. A method for installing this improved apparatus is also disclosed.
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BACKGROUND OF THE INVENTION
The present invention generally relates to a lock plates inserting machine for key cylinder and a method for inserting lock plates into a key cylinder. More specifically, the present invention concerns the method and machine for automatically and mechanically inserting the lock plates into a plurality of respective lock plate receiving openings defined at regular intervals on the key cylinder in the axial direction thereof, in combination with such an operation that the required lock plates to be inserted are mechanically detected so as to correspond to respective serrations of a key.
In a well-known key cylinder, as shown in FIG. 1, a plurality of spaced serrations 2 having different widths are formed in parallel with each other on a key 1 in the longitudinal direction thereof and as many spaced lock plate receiving openings 4 as the key serrations 2 are defined on a key cylinder 3 in the axial direction thereof at the positions corresponding to the serrations 2 of the key 1 to be inserted. Since a plurality of lock plates 5 are inserted through springs 6 into the lock plate receiving openings 4 so as to correspond to the widths of respective key serrations 2, various kinds of key cylinders are produced by changing the arrangement of the key serrations 2.
Conventionally, although the springs 6 are automatically inserted into the lock plate receiving openings 4 of the key cylinder 3, the work for inserting the lock plates 5 corresponding to the key serrations 2 into respective lock plate receiving openings 4 of the key cylinder 3 is generally carried out through such a handwork that upon eye-measurement of the key serrations 2 by a worker, the lock plates 5 corresponding to respective key serrations 2 are inserted into the lock plate receiving openings 4 of the key cylinder 3 by being manually picked up. The foregoing work has been repeated six times by the worker owing to the fact that the key 1 generally has six rows of the serrations 2.
According to the above described handwork, however, not only the worker is required to be superior in skill and occasionally makes a mistake in measuring the key serrations 2 with his eyes, but also there exist considerable individual differences. Furthermore, on account of the handwork, it takes approximately thirteen seconds for the worker to insert all of the lock plates into one key cylinder, even in the fastest work by a skilled worker. Such being the circumstances, the aforementioned handwork is inferior in working efficiency, and as a result, the key cylinders have been undesirably produced at high cost.
Recently, there has been developed an electrically driven automatic inserting machine for automatically inserting the lock plates into the lock plate receiving openings of the key cylinder corresponding thereto in accordance with a result obtained by electrically detecting the key serrations one by one, through an optical sensor. However, the aforementioned electrically driven inserting machine includes such drawbacks that it is extremely complicated in construction and is formed into a large size and furthermore, it is unsuitable for incorporation into a production line, thus resulting in that the key cylinders have been produced at high cost. In addition, since the inserting machine of the above described type further includes such problems that it can not easily deal with the cases where a faulty detection of the key serrations, faulty insertion of the lock plates or the like has taken place and it can not be easily repaired in case of accident, it has a drawback that it has not been suitable for practical use.
SUMMARY OF THE INVENTION
Accordingly, the present invention has been developed with a view to substantially eliminating the above described disadvantages inherent in the conventional handwork or in the prior art inserting machine, and has for its essential object to provide an improved and substantially mechanically driven automatic inserting machine of small size which is capable of being readily incorporated into a production line and manufactured at low cost.
Another important object of the present invention is to provide an automatic inserting machine of the above described type which can be easily handled in case of its malfunction and can be readily repaired in case of accident.
A further object of the present invention is to provide a method for mechanically inserting lock plates into a key cylinder, which substantially eliminates a troublesome and time consuming handwork by a worker.
In accomplishing these and other objects, according to one preferred embodiment of the present invention, there is provided a lock plates inserting machine which is capable of mechanically detecting serrations of a key and automatically mechanically inserting the lock plates into respective appointed lock plates receiving openings defined on the key cylinder in organic combination with the aforementioned detection of the key serrations.
More specifically, the present invention is characterized in that in a lock plates inserting machine for key cylinder for inserting the lock plates corresponding to respective key serrations into a plurality of lock plate receiving openings defined at regular intervals on the key cylinder in the axial direction thereof, said lock plates inserting machine includes a key holder having a plurality of grooves defined thereon and corresponding to respective serrations of the key to be inserted, at least one key serrations detecting member having one end freely pivotally mounted on a fulcrum disposed on a base and a key serrations detecting convex portion in the vicinity of the fulcrum, while resiliently urged by a spring for inserting the key serrations detecting convex portion into either of the grooves of the key holder, at least one slide member disposed on the base slidably together with pivotal movement of the key serrations detecting member and having as many concave portions as the kinds of sizes of the key serrations defined at regular intervals thereon in its sliding direction, with slide amount of the slide member varying in accordance with the sizes of the key serrations, a plurality of first push members, corresponding to respective concave portions of the slide member, resiliently urged by a spring and positioned so that either one of the first push members is inserted into its corresponding concave portion of the slide member in accordance with the slide amount thereof, a plurality of lock plates support members securely mounted on the base at the positions respectively corresponding to the first push members for supporting thereon the lock plates of different sizes, an elevating member having a plurality of lock plate receiving grooves corresponding to the lock plate receiving openings of the key cylinder, while the lock plates pushed out by the first push members are sequentially inserted into the lock plate receiving grooves, and a plurality of second push members operated by a drive means and inserted into respective lock plate receiving grooves of the elevating member from one end thereof for inserting the lock plates placed in regular order in the lock plates receiving grooves into the lock plate receiving openings of the key cylinder disposed in the vicinity of the other end thereof.
Moreover, in another aspect of the present invention, there is provided a method of inserting the lock plates for key cylinder, wherein the lock plates respectively corresponding to the key serrations are inserted into a plurality of lock plate receiving openings defined at regular intervals on the key cylinder in the axial direction thereof. The method includes the steps of inserting the key into a key holder, inserting a key serrations detecting convex portion formed on the key serrations detecting member urged by a spring into one of grooves defined on the key holder for detecting the key serrations so as to operate the key serrations detecting member in accordance with the size of one of the key serrations, sliding a slide member together with operation of the key serrations detecting member, inserting one of push members corresponding to the size of the key serration into either one corresponding thereto of a plurality of concave portions formed on the slide member, with push members being urged by respective springs and so disposed as to correspond to respective concave portions of the slide member, pushing out one of the lock plates corresponding to the size of the key serration by one of the push members, with said lock plates being supported by one of support members, inserting the lock plate into one of a plurality of grooves defined on an elevating member and corresponding to as many lock plate receiving openings defined on the key cylinder, inserting required lock plates into respective grooves of the elevating member in accordance with the sizes and alignment of the key serrations by repeating aforementioned operation, and inserting required lock plates into corresponding lock plate receiving openings of the key cylinder disposed on one end of the elevating member by simultaneously inserting a plurality of second push members into respective grooves of the elevating member from the other end thereof so as to advance the lock plates together with the second push members within the elevating member.
BRIEF DESCRIPTION OF THE DRAWINGS
These and other objects and features of the present invention will become apparent from the following description taken in conjunction with the preferred embodiment thereof with reference to the accompanying drawings, throughout which like parts are designated by like reference numerals, and in which:
FIG. 1 is an exploded perspective view of a conventional key cylinder (already referred to);
FIG. 2 is an exploded view showing the relationship between serrations of a key and lock plates, both of which are used in a preferred embodiment of the present invention;
FIG. 3 is a front elevational view of a lock plates inserting machine according to the present invention;
FIG. 4 is a top plan view of FIG. 3;
FIG. 5 is a fragmentary perspective view of a main portion of FIG. 3;
FIG. 6a is a fragmentary plan view, on an enlarged scale, showing the relationship between concave portions of a slide comb and push levers, both of which are employed in the present invention;
FIGS. 6b through 6e are fragmentary plan views, on an enlarged scale, each showing the relationship between a travelling amount of the slide comb and one of the push levers inserted into the corresponding concave portion of the slide comb;
FIG. 7 is a side elevational view, on an enlarged scale, of an elevating mechanism employed in the present invention for moving an elevator upwardly and downwardly; and
FIG. 8 is a top plan view showing the relationship between the slide comb and a limit switch for desirably operating the lock plate inserting machine of FIG. 3.
DETAILED DESCRIPTION OF THE INVENTION
Referring now to the drawings, there is shown in FIG. 2, a key 1 having six rows of serrations of four different widths, to which the present invention is applied. The widths of the key serrations No. I, II, III and IV are 4 mm, 5 mm, 6 mm and 7 mm respectively, that is, there are differences by 1 mm each in whole width and by 0.5 mm each in half width among the serrations No. I to IV. Lock plates 5 (5-I, 5-II, 5-III and 5-IV) corresponding to respective key serrations No. I to IV are inserted through springs 6 into lock plate receiving openings 4 defined at regular intervals of 2.5 mm on a key cylinder 3 in the axial direction thereof. The springs 6 are inserted in advance into the lock plate receiving openings 4 by an automatic inserting device (not shown) before the process for inserting the lock plates 5.
In FIGS. 3 through 5, there is shown a lock plates inserting machine according to one preferred embodiment of the present invention, which is provided with a key holder 10 for receiving the key 1 to be detected thereinto, a pair of key serrations detecting levers 11 for detecting the serrations 2 of the key 1 inserted into the key holder 10, a pair of slide bars 12 movable together with respective key serrations detecting levers 11, a pair of slide combs 13 each having a shape similar to the teeth of a comb and movable together with respective slide bars 12, a pair of push lever units 14 each of which includes four pieces of puch levers 14A to 14D respectively inserted into four concave portions 13a to 13d defined on one side of the slide comb 13 in compliance with a travelling distance thereof, a pair of push plate units 15 each of which includes four pieces of first push plates 15A to 15D connected to respective push levers 14A to 14D at one ends thereof, a pair of lock plates holding bar units 16 each of which includes four pieces of lock plates holding bars 16A to 16D so disposed as to correspond to the positions where tips of the first push plates 15A to 15D are located for holding a large number of respective lock plates 5-IV to 5-I piled one upon another thereon, an elevator 17 for receiving the lock plates 5-I to 5-IV pushed thereinto by the first push plates 15A to 15D, six pieces of second push plates 18 for pushing the lock plates 5 placed within the elevator 17 into the lock plate receiving openings 4 of the key cylinder 3, an air cylinder 19 for pushing the second push plates 18, a pair of guide plates 20A and 20B disposed on opposite ends of the elevator 17, a base 23 and a cam mechanism 21 for vertically moving the key holder 10 together with the elevator 17.
The elevator 17 is so disposed at the center of the base 23 as to be freely movable in three steps in the vertical direction by a cam mechanism which is explained in detail hereinafter and a pair of guide plates 20A and 20B are fixedly mounted on the base 23 on opposite ends of the elevator 17. Furthermore, a jig 24 suitable for the key cylinder 3 into which the lock plates 5 are inserted is placed in position immediately before the front guide plate 20A and the key holder 10 corresponding to the key 1 is set in front of the jig 24 so that the key holder 10 is capable of moving up and down together with the elevator 17 by the cam mechanism 21. The second push plates 18 are disposed at the back of the rear guide plate 20B so as to be moved back and forth by the air cylinder 19. Pairs of the slide combs 13, push lever units 14, push plate units 15 and lock plates holding bar units 16 are symmetrically disposed on respective sides of the elevator 17 and likewise, not only a pair of the key serrations detecting levers 11 but also a pair of slide bars 12 capable of sliding in combination therewith for sliding respective slide combs 13 are also symmetrically disposed in front of the key holder 10 and on both sides thereof respectively.
By the above described construction, upon detection of two of the upper and lower adjacent serrations 2 of the key 1 set vertically at a time, two of the required lock plates 5 are simultaneously inserted, through the slide bars 12, slide combs 13, push levers 14A to 14D and first push plates 15A to 15D from both sides of the elevator 17 into two of lock plate receiving grooves 17a to 17f which are defined vertically in six stages on the elevator 17. Thereafter, both of the key holder 10 and the elevator 17 are moved upward or downward in three steps and upon repetition of the aforementioned operation three times, each one of six required lock plates 5 is inserted into each of six staged lock plate receiving grooves 17a to 17f of the elevator 17 and subsequently, all of the lock plates 5 are inserted into respective lock plate receiving openings 4 defined on the key cylinder 3 at one time, in a manner that the lock plates 5 placed in the lock plate receiving grooves 17a to 17f are simultaneously pushed out by the second push plates 18.
In the next place, the construction and function of each member will be explained in detail hereinafter.
The key holder 10 is provided with six stages of key serrations detecting grooves 10a to 10f vertically defined thereon at regular intervals of 2.5 mm so that each of the grooves 10a to 10f is formed at the position corresponding to each one of the serrations 2 of the key 1 to be inserted.
Each of the pair of key serrations detecting levers 11 arranged on both sides and in front of the key holder 10 has one end freely pivotally mounted on a fulcrum 30 disposed on the base 23 and the other end securely connected to one end of a spring 31 for urging the key serrations detecting lever 11 towards the direction indicated by the arrow A in FIG. 5 by holding the other end thereof on a first spring holder 32 projecting upwards on the base 23. Each key serrations detecting lever 11 is provided with a convex portion 11a formed in the vicinity of the fulcrum 30 for being inserted into the grooves 10a to 10f of the key holder 10 and a slide bar contact portion 11b formed in the vicinity of a connecting portion between the other end thereof and the spring 31, and is so designed that a distance between the fulcrum 30 and the convex portion 11a and a distance between the former and the slide bar contact portion 11b is in the ratio of one to six. The convex portion 11a of the key serrations detecting lever 11 varies in its insertion amount into one of the grooves 10a to 10f of the key holder 10 in accordance with the widths of the key serrations 2, that is, since the insertion amount of the convex portion 11a is small in the case where the key serration No. IV having a broader width gets in contact therewith, the slide bar contact portion 11b travels towards the direction indicated by the arrow A in a small amount but on the contrary, since the insertion amount of the convex portion 11a is large in the case where the key serration No. I having a narrower width gets in contact therewith, the slide bar contact portion 11b travels in a large amount.
Each slide bar 12 is provided with a front end in contact with the slide bar contact portion 11b of the key serrations detecting lever 11 and a rear end having an elongated guide opening 12a in the longitudinal direction thereof. Furthermore, the slide bar 12 is freely reciprocable along a guide pin 33 which is projected upwards on the base 23 and held in the guide opening 12a of the slide bar 12, with the rear end surface thereof getting in contact with the slide comb 13. A spring 36 is arranged between a second spring holder 34 disposed on the front end of the slide comb 13 and a third spring holder 35 disposed on the base 23 for urging both the slide comb 13 and the slide bar 12 frontwards towards the direction indicated by the arrow B.
The aforementioned slide bar 12 and slide comb 13 slide backwards in compliance with the movement of the key serrations detecting lever 11 and at this moment, they are controlled by the movement which magnifies the difference of the key serrations 2 by six times in terms of the relationship of the aforementioned ratio of the key serrations detecting lever 11 of one to six. More specifically, since the difference of the key serrations No. III and No. IV is 0.5 mm in half width to be detected, the difference of the travelling amount of the slide comb 13 is 0.5 mm×6=3 mm, and likewise, that of the key serrations No. II and No. IV is 1 mm×6=6 mm and that of the key serrations No. I and IV is 1.5 mm×6=9 mm.
As shown in FIG. 6a, four concave portions 13a to 13d are formed on each slide comb 13 at regular intervals and the push levers 14A to 14D to be inserted thereinto in compliance with the travelling amounts thereof are positioned by employing a vernier means utilized in such a measuring tool as slide caliper or the like in consideration of the aforementioned difference of the travelling amounts. In other words, as shown in FIGS. 6b through 6e, since the slide comb 13 is caused to stop at either of four positions respectively located 3 mm, 6 mm, 9 mm and 12 mm away from its frontmost position at intervals of 3 mm each, a distance S1 between the center of the frontmost concave portion 13a and that of the push lever 14A, a distance S2 between the center of the concave portion 13b and that of the push lever 14B, a distance S3 between the center of the concave portion 13c and that of the push lever 14C, and a distance S4 between the center of the rearmost concave portion 13d and that of the push lever 14D are 3 mm, 6 mm, 9 mm and 12 mm respectively by adding 3 mm each. Accordingly, for example, when the key serration No. IV is detected, upon movement of the slide comb 13 by 3 mm, only the push lever 14A completely faces the concave portion 13a with each other and is inserted thereinto, thus resulting in that only the first push plate 15A is caused to move towards the elevator 17 so as to insert one of the lock plates 5-IV corresponding to the key serration No. IV into the appointed lock plate receiving groove 17a in accordance with the order of the key serrations 2 within the elevator 17, with the lock plates 5-IV being supported by the lock plates holding bar 16A. In a similar manner in other cases, only one of the push levers 14A to 14D is inevitably inserted into one of the grooves 13a to 13d corresponding thereto, but not inserted into either of the other grooves.
As described above, the lock plates 5-IV to 5-I corresponding to the push levers 14A to 14D are respectively held on the lock plates holding bars 16A to 16D which are hung down from a holding frame 38 securely mounted on the base 23, and in a large number of the lock plates 5-IV to 5-I piled one upon another on respective lock plates holding bars 16A to 16D, the lowermost ones are separated therefrom so as to be capable of being pushed out by respective first push plate 15A to 15D.
As shown in FIG. 7, each of the push levers 14A to 14D protrudes downwards from the base 23 through an opening 23a defined thereon and has a lower end freely pivotally mounted on a fulcrum 37. Each pair of the push levers 14A to 14D arranged on both sides of the base 23 are urged inwardly towards the slide combs 13 at the upper portion thereof by a tension spring 39 connectively disposed therebetween. An inwardly protruding roller 40 is disposed at the lower portion of each push lever 14A to 14D so as to get in contact with a push cam 41 securely mounted on a cam shaft 43 of a cam mechanism 21. The push cam 41 is provided with three concave portions 41a defined on the periphery thereof at regular intervals and having a diameter smaller than that of other portions in order that when the rollers 40 get in contact with one of the concave portions 41a, the push levers 14A to 14D are allowed to move towards the direction indicated by the arrow C by the spring 39 and only one of the push levers 14A to 14D completely facing its corresponding groove 13a to 13d of the slide comb 13 is inserted thereinto. Subsequently, after one of the lock plates 5 has been inserted into the elevator 17 through the first push plate 15A to 15D, the rollers 40 come in contact with one of large diameter portions 41b of the push cam 41 so as to be moved outwards against the springs 39, thus resulting in that the push lever 14A to 14D inserted into its corresponding groove 13a to 13d is restored to its previous position.
As clearly indicated in FIG. 7, the elevator 17 is provided with vertically defined six stages of grooves 17a to 17f in a manner that they are caused to open towards opposite sides alternately. Two of the lock plates 5 are simultaneously inserted into adjacent two rows of the grooves 17a to 17f of the elevator 17 from opposite sides thereof through the push plates 15A or the like so as to be placed in position in the respective grooves 17a to 17f. As these grooves 17a to 17f are penetrated in the longitudinal direction of the elevator 17, the second push plates 18 driven by the air cylinder 19 are inserted thereinto from the rear openings thereof through the guide plate 20B. The lock plates 5 are moved forwards within the grooves 17a to 17f, while pushed by the second push plates 18 and are inserted, through the guide plate 20A arranged immediately before the elevator 17, into the lock plate receiving openings 4 of the key cylinder 3 which is securely held by the jig 24.
Both of the elevator 17 and the key holder 10 are set to be freely movable in three steps in a vertical direction together with openings 23b and 23c defined on the base 23. More specifically, there are arranged below the base 23, a cam shaft 43 freely rotatable by a motor (not shown) through gears 42a and 42b, an elevator cam 44 fixedly mounted on the cam shaft 43 and an elevating plate 45 freely movable up and down by the elevator cam 44. The key holder 10 is placed in position on the elevating plate 45 and the elevating plate 45 is fixedly connected to the lower surface of the elevator 17 through rods 46. The elevator cam 44 is so shaped as to move the elevating plate 45 up and down in three steps by 5 mm each during one rotation thereof.
When the elevating plate 45 is located in its uppermost position by the elevator cam 44, the key serrations detecting levers 11 are inserted into lower two of the key serrations detecting grooves 10e and 10f of the key holder 10 so as to detect the key serrations 2 and in compliance with the result detected, the required lock plates 5 are inserted into lower two of the grooves 17e and 17f of the elevator 17 through slide bars 12, slide combs 13, push levers 14A to 14D and first push plates 15A to 15D. Likewise, after the elevating plate 45 has been moved downwards in one step, upon detection of the key serrations 2 in the grooves 10c and 10d of the middle two stages of the key holder 10, the required lock plates 5 are inserted into the lock plate receiving grooves 17c and 17d of the middle two stages of the elevator 17. Lastly, the elevating plate 45 is further moved downwards in one step so as to detect the key serrations 2 in the grooves 10a and 10b of the upper two stages of the key holder 10 and thereafter, the required lock plates 5 are inserted into the lock plate receiving grooves 17a and 17b of the upper two stages of the elevator 17. The cam shaft 43 is provided with a one cycle cam 47 fixedly mounted thereon for detecting one rotation thereof and when the lock plates 5 have been completely placed in a required order within the elevator 17 during one rotation of the cam shaft 43, not only the cam shaft 43 is caused to stop its rotation through the function of the one cycle cam 47, but also the second push plates 18 are moved forwards by the air cylinder 19 as stated hereinbefore so as to automatically insert the lock plates 5 into the key cylinder 3.
The lock plates inserting machine of the present invention is further provided with a mechanism for detecting a poor insertion of the lock plates and in the case where the poor insertion is detected, the inserting machine is brought to a halt so that the lock plates 5 are manually inserted into the key cylinder 3 and thereafter, upon restarting of the inserting machine, the automatic operation thereof for automatically inserting the lock plates is caused to follow. That is, since there are arranged a timing cam 48 fixedly mounted on the cam shaft 43 for detecting the poor insertion of the lock plates 5 and a first limit switch 50 having a roller 51 protruding therefrom in the vicinity of the timing cam 48, the roller 51 engages with one of notches 48a defined on the periphery of the timing cam 48 in the timing when the lock plates 5 are to be inserted so that the first limit switch 50 is turned off. In the case where the first limit switch 50 is not turned off, a signal having detected the poor insertion is sent from the first limit switch 50 so as to bring the cam shaft 43 to a halt in rotation thereof. Furthermore, a stopper 52 is disposed in the vicinity of each of the first push plates 15A to 15D and is in contact therewith at the time when the lock plate 5 is inserted into the groove of the elevator 17 in position through the movement of the push plate 15 towards the elevator 17. A contact switch 56 is disposed between each stopper 52 and each push plate 15 so that the cam shaft 43 is brought to a halt in rotation thereof by a signal informing an abnormal insertion of the lock plate 5, unless the contact switch 56 is turned on.
Moreover, since the lock plates inserting machine of a present invention is designed for the key having six rows of the serrations, in case of the key having five or less rows of the serrations, an abnormal signal is sent so as to undesirably bring the inserting machine to a halt, without any detection of the key serrations. In order to avoid the aforementioned inconvenience, a second limit switch 55 is disposed in the vicinity of the slide comb 13 so as not to bring the inserting machine to a halt by a signal sent therefrom, unless the slide comb 13 travels at the timing when it ought to do.
It is to be noted that in the above described embodiment, although a pair of push lever units and the like are disposed on both sides of the elevator, it may be so modified that they are disposed only on one side of the elevator and the lock plates are inserted one by one into the grooves of the elevator.
It is also to be noted that not only each push lever may be so modified as to be integrally formed together with each first push plate, but also it may be so modified that the slide comb can be directly slid by the key serrations detecting lever, with the slide bar being omitted.
It should be further noted that in the foregoing embodiment, although both of the elevator and the key holder are so disposed as to be moved up and down by the cam mechanism, one of other suitable mechanisms may be employed for this purpose.
As is clearly seen from the foregoing description, by the lock plates inserting machine of the present invention, the serrations of the key are sequentially mechanically detected by the key serrations detecting lever so that in compliance with the result obtained, the lock plates corresponding to respective key serrations are sequentially inserted into the appointed grooves within the elevator through mechanically combined movement of the slide bar, slide comb, push levers and first push plates with the key serrations detecting lever. Subsequently, upon completion of the aforementioned process for inserting the lock plates into the elevator, since the lock plates are respectively inserted into the appointed lock plate receiving openings of the key cylinder, while pushed by the second push plates driven by the air cylinder, the following effects can be obtained.
(1) The detection of the key serrations and insertion thereof into the key cylinder are automatically carried out and six lock plates can be inserted into one key cylinder in approximately six seconds, thus resulting in the work efficiency being extremely improved by the present invention owing to the fact that it takes approximately thirteen seconds so far for the worker to manually insert the lock plates into the key cylinder.
(2) Since an unskilled person can carry out the work which fully depends on a skilled person so far and the workers can be extremely reduced in number, the key cylinders can be produced at low cost.
(3) Since none of the keys can be wrongly detected in reading out the serrations thereof, there never occurs such a mistake in assembling process as the wrong insertion of the lock plates.
(4) Since the automatic insertion of the lock plates is mechanically carried out, the lock plates inserting machine of the present invention can easily deal with the poor operation thereof and can be easily repaired in case of accident, as compared with an electrically driven inserting machine.
(5) Since the whole of the lock plates inserting machine of the present invention can be easily miniaturized, it can be not only incorporated into a production line, but also extremely reduced in production cost thereof.
Although the present invention has been fully described by way of example with reference to the accompanying drawings, it is to be noted here that various changes and modifications will be apparent to those skilled in the art. Therefore, unless otherwise such changes and modifications depart from the scope of the present invention, they should be construed as being included therein.
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A lock plates inserting machine and a method of automatically and mechanically inserting a plurality of lock plates into corresponding openings defined in the key cylinder. The lock plates inserting machine includes a key holder having a plurality of grooves corresponding to respective serrations of a key to be inserted. At least one key serrations detecting member having a key serrations detecting convex portion is inserted into one of the grooves of the key holder. At least one slide member is slidable upon pivotal movement of the key serrations detecting member and upon concave portions equal in number to the different sizes of the key serrations. A plurality of first push members corresponding to respective concave portions of the slide member are positioned so that a proper one of the first push members is inserted into its corresponding concave portion of the slide member in accordance with the slide members's position. A plurality of lock plates support members are provided for supporting lock plates of different sizes. An elevating member sequentially receives the lock plates into grooves defined on it, and a plurality of second push members are provided for inserting the lock plates placed in regular order in the elevating member into the openings of the key cylinder.
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BACKGROUND OF THE INVENTION
The present invention relates to poppet valves, and more particularly to poppet valves for water faucets.
Poppet valves are well known and have been extensively developed for the control of liquid flow, for example, in water faucets. A poppet valve closes with the assistance of fluid pressure. The typical valve includes a valve seat, a stem, and an elastomeric seal on the end of the stem. The valve is opened by moving the stem in a direction opposite to that of the water flow to permit fluid to flow between the seal and the seat. When the stem is released, the fluid flow and pressure assist in returning and retaining the seal against the seat.
A typical prior art poppet valve construction is illustrated in FIG. 5 and generally designated 110. The valve includes a housing 112, a valve stem 114, and a primary seal 116. The housing includes a valve seat 118 selectively engaged by the primary seal. A coil spring 120 is mounted about the stem to urge the primary seal into engagement with the valve seat. A secondary seal 122, typically an O-ring, seals the stem within the housing. The stem 114 is typically lubricated to prevent wear, to assure smooth action, and to retain the integrity of the seal.
Unfortunately, the secondary seal is a frequent location for product failure because of the exposure of this seal to water and water flow. Lubrication of the stem/seal relationship is essential to ensure the integrity of the seal. However, lubrication is constantly flushed away from this area by flowing water and eventually washed out. Additionally, exposure of the typically metal stem to water often results in corrosion or liming, further contributing to eventual sticking and wear, which can result in leaking at the primary and/or secondary seals.
Consequently, prior art poppet valves are subject to leaking, relatively short lives, and continual servicing; and such valves have not been widely used in water faucets.
SUMMARY OF THE INVENTION
The aforementioned problems are overcome in the present invention wherein a one-piece valve seal both provides the primary and secondary seals within a poppet valve and prevents water from coming into contact with the valve stem within the seal.
More particularly, the poppet valve includes a housing, a stem, and the valve seal. The housing defines a valve seat. The seal is a sleeve or boot fitted over the valve stem. The sleeve includes an open base end and a tip end. The open end is sealed to the housing to provide the secondary valve seal. The tip end fits over the valve stem to provide the primary seal.
The one-piece seal efficiently and effectively provides both the primary and secondary seals within the valve. Consequently, the valve stem within the seal is isolated from fluid contact and is thus permanently lubricated and protected against corrosion and liming.
In a preferred embodiment of the invention, the valve seal includes an integral bellows portion biasing the primary seal on the tip end into engagement with the valve seat. The bellows acts as the return spring and eliminates the need for a separate conventional return spring.
These and other objects, advantages, and features of the invention will be more fully understood and appreciated by reference to the detailed description of the preferred embodiment and the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a water faucet incorporating the poppet valve of the present invention;
FIG. 2 is a side elevational view of the faucet;
FIG. 3 is an enlarged sectional view of the base assembly of the faucet;
FIG. 4 is an enlarged sectional view of the poppet valve of the present invention; and
FIG. 5 is a schematic sectional view of a prior art poppet valve.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
A poppet valve assembly constructed in accordance with a preferred aspect of the invention is illustrated in FIGS. 1-2 and 4 and generally designated 10. As illustrated in FIG. 1, the poppet valve assembly 10 is used in conjunction with a water faucet 12 of the type generally known as a ledge faucet otherwise of generally conventional design. The ledge faucet 12 includes a base assembly 14 for mounting the faucet within a sink or counter top S, a spout 16, and the poppet valve assembly 10. Ledge faucets are widely used in conjunction with under counter water purification systems and under counter water heaters. While the present poppet valve assembly 10 is described in conjunction with a ledge faucet 12, the valve has widespread applicability in water faucet and other fluid control fields.
The base assembly 14 is of generally conventional construction and is illustrated in greatest detail in FIG. 3. The assembly includes a threaded inlet shank 18 extending through the sink or counter top S (see FIG. 1) and a shank nut 20 threadedly secured thereon for retaining the inlet shank in position. A flange 22 fits over the upper end of the inlet shank 18 and is secured in position by the inlet nut 24, which is threadedly secured on the inlet shank. The flange and nut together provide an aesthetically trimmed appearance to the installed faucet.
The lower end of the spout 16 extends into and is supported by the inlet shank 18 and is sealed by an O-ring 26 within an annular groove in the spout 16. A split retaining ring 28 fits within an annular groove in the spout 16 and an annular groove defined together by the inlet shank 18 and the inlet nut 24.
The spout 16 (FIGS. 1-2) is also of conventional construction and is a single tubular piece. Generally speaking, the spout includes a vertical portion 30 supported by the base assembly 14, a bend portion 32, and a generally horizontal portion 34. The physical configuration of the spout 16 will vary widely depending primarily on aesthetics.
The poppet valve assembly 10 is the basis of the present invention and is illustrated in greatest detail in FIG. 4. Generally speaking, the valve assembly 10 includes a housing assembly 36, a stem assembly 38, and a valve seal 40.
The housing assembly 36 (FIG. 4) includes a body 42, a retaining cap 44, a seal support 46, and a button cam 48. The body 42 defines a water inlet 50, a water outlet 52, and a fluid chamber 54 interconnecting the inlet and outlet. The inlet 50 is fired into the spout 16, and an O-ring 56 seals the inlet 50 within the spout 16. The spout is dimpled at 58 to interlock the two pieces. The inlet includes and defines a valve seat 57. A stream former 60 is press-fitted within the outlet 52 and supports a disk of filtering material 62 and a screen 64. The stream former materials are conventional.
The retaining cap 44 secures the seal support 46 and the button cam 48 within the body 42. The flange 84 of the valve seal 40 is entrapped between the seal support 46 and the button cam 48 (further discussed below) to provide a water-tight seal between the valve seal and the valve stem assembly 38.
The valve stem assembly 38 (FIG. 4) includes a valve stem 66, a stem guide 68, and a button 70. The stem 66 is metal and includes a base portion 72, an extended portion 74, an enlarged portion 76, and a barbed tip 77. The base portion 72 and enlarged portion 76 are generally identical in diameter. The extended portion 74 and the barbed tip have a smaller diameter.
The stem guide 68 fits over the base portion 72, and the button 70 snap-fits over the stem guide 68. The face 78 of the button 70 may include the manufacturer's logo, an on/off graphic, or other information. Preferably, the stem guide 68 includes a bayonet mounting (not specifically shown) with the button cam 48 so that partial rotation of the depressed button 70 locks the valve in the "on" position.
The valve seal 40 (FIG. 4) is a boot or sleeve having a tip end 80 and an opposite open end 82. A circumferential flange 84 extends about the entire periphery of the open end 82 and is entrapped between the seal support 46 and the button cam 48. Consequently, water within the chamber 54 is prevented from contacting the valve stem assembly 38 and specifically the valve stem 66. A bellows portion 86 is integrally formed in the valve seal 40 intermediate between the closed and open ends. The end of the base portion 72 of the stem 66 engages the end of the bellows portion 86. The bellows 86 biases the valve into the closed position illustrated in FIG. 4. Consequently, the need for a separate return spring is eliminated.
The tip end 80 of the valve seal is enlarged to provide a valve portion selectively engaging the seat 57. This tip end 80 defines a pocket 88 which receives the enlarged portion 76 of the valve stem 66. The tip end also defines an aperture 89 through which the barbed tip 77 extends. The enlarged portion 76 and the barbed tip 77 provide a snap-fit between the valve stem 66 and the valve seal 40 to interlock the two components. Water pressure within the inlet 34 actually enhances this interlock/seal. Alternatively, the seal could be closed at the tip end so as to completely encapsulate the tip 77. The enlarged portion 76 also provides structural support for the valve portion 80 against the valve seat 57.
Operation
The assembled valve 10 is illustrated in the closed position in FIG. 4. The valve portion 80 of the valve seal 40 engages the valve seat 57 to prevent water flow through the valve. The bellows 86 provide a biasing force to return the valve portion 80 against the valve seat 57. Additionally, water within the inlet 50 aids in maintaining the valve portion 80 against the valve seat 57.
The valve is opened by depressing the button 70, i.e., toward the housing assembly 36 or to the right as illustrated in FIG. 4. The button depression moves the valve guide 68 and valve stem 66 to the fight as illustrated in FIG. 4 pushing the valve portion 80 off the valve seat 57 and permitting water flow therebetween. Water flows through the open valve, through the inlet 50, the chamber 54, the stream former 60 to exit the valve. The entrapment of the flange 84 within the housing assembly 36 provides a leak-tight secondary seal, preventing water from exiting the valve body 10 other than through the outlet 52. The valve seal 40 also prevents water from contacting the metal valve stem 66 within the seal 40, thereby assuring retention of lubrication and minimizing corrosion or liming. While water can contact the barbed tip 77, such contact does not adversely impact lubrication, corrosion, or liming.
The bayonet of the valve stem assembly 38 enables the valve to be locked in the open position with a simple partial mm of the button 70.
The valve is returned to the closed position illustrated in FIG. 4 by releasing the button 70. The biasing force of the bellows portion 86 and the pressure of water within the inlet 50 return the valve portion 80 to the left as illustrated in FIG. 4 to contact the valve seat 57, thereby closing the valve.
The above description is that of a preferred embodiment of the invention. Various alterations and changes can be made without departing from the spirit and broader aspects of the invention, which are to be interpreted in accordance with the principles of patent law including the doctrine of equivalents.
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A poppet valve assembly wherein the valve stem is protected from water contact. The valve includes a housing, a valve stem reciprocable within the housing, and a valve seal over the stem. The seal is a boot or sleeve having a base end and a valve end. The base end is open and sealed about its entire periphery to the housing. The valve end seals against the end of the valve stem. The housing defines a valve seat, and the valve end of the seal includes a valve portion selectively engaging the seat. Preferably, the seal further includes a bellows portion along its length to bias the valve portion into engagement with the valve seat.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to a digital signal composing circuit and more particularly is directed to a digital signal composing circuit which is suitable for being used in smoothly connecting or mixing a plurality of digital information signals.
2. Description of the Prior Art
In a scrambling system for audio frequency signals and so on in which an audio signal, for example, is divided into blocks, each block being formed of a plurality of segments, the plurality of segments are rearranged on a timebase in a predetermined order at every block and upon reception, these segments are re-arranged in the original arrangement order to restore the original audio signal, if a system such as a VTR (video tape recorder) and the like having a timebase fluctuation exists in the transmission path thereof, when these segments are rearranged at the receiving side, the connected portion between the ends of the segments is displaced so that the original audio signal is distorted, a noise is superimposed upon the original audio signal and so on, thus the quality of the audio signal being deteriorated.
Therefore, as a method for solving the above problem, there is proposed a so-called cross-fade signal processing system in which as, for example, shown in FIG. 1, when digital data X and Y having different contents A and B are connected to each other, near the connection point, one digital data X is gradually decreased in level, while the other digital data Y is gradually increased in level over a predetermined interval (cross-fade period) t so as to connect both the data with each other smoothly.
By the way, a conventional circuit employing such cross-fade signal processing system requires a multiplier to apply the cross-fade so that the construction of the circuitry becomes large in structure. Particularly when this circuit is formed as an IC (integrated circuit), the manufacturing cost thereof is greatly affected so that the circuit becomes very expensive.
OBJECTS AND SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide an improved digital signal composing circuit which can obviate the above defects inherent in the conventional digital signal composing circuit.
It is another object of the present invention to provide a digital signal composing circuit which can smoothly connect or mix digital data of different contents without using a multiplier.
It is still another object of the present invention to provide a digital signal composing circuit which can suitably be applied to a digital volume, digital signal mixing processing, digital fade-in/-out signal processing system, digital linear interpolation and so on.
It is further object of the present invention to provide a digital signal composing circuit which can be made simple in construction and inexpensive at manufacturing cost.
It is still further object of the present invention to provide a digital signal composing circuit which is quite advantageous particularly when it is formed as an integrated circuit.
According to one aspect of the present invention, there is provided a digital signal composing circuit comprising:
a first selecting means for selecting a plurality of digital data;
a second selecting means for selecting one of the digital data and a feedback signal;
a control means for controlling the switching of the first and second selecting means; and
an adding means for adding outputs of the first and second selecting means and supplying the added output to the second selecting means as the feedback signal wherein a final output is derived from the adding means.
The other objects, features and advantages of the present invention will become apparent from the following description taken in conjunction with the accompanying drawings through which the like references designate the same elements and parts.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagram useful for explaining a so-called cross-fade signal processing;
FIG. 2 is a systematic block diagram showing an embodiment of a digital signal composing circuit according to the present invention; and
FIGS. 3A-I to 3P-I and FIGS. 3A-II to 3P-II are respectively signal waveform diagrams used to explain the operation of the digital signal composing circuit of the present invention shown in FIG. 2, with each of the Figures identified with a Roman numeral II representing a continuation of the corresponding Figure identified with a Roman numeral I.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Before describing an embodiment of a digital signal composing circuit according to the present invention, a fundamental principle of the present invention will be described briefly. To make the digital signal composing circuit of the present invention, a weighted mean value between two digital data X and Y is calculated as ##EQU1## where K is a constant value and n is an arbitrary integer. And, when the weighted coefficient is added with the condition K/2 n , a signal processing which can satisfy the above equation (1) is made possible not by the use of a multiplier but by a combination of substantially an adder and selectors described later.
When, now, n is taken as 3, the above equation (1) is extended as follows: ##EQU2##
As seen in the above, the above equation (1) is expressed by the operation of the addition and the multiplication of 1/2 (without using the multiplier, this operation can be carried out by only shifting one bit of the data). In the case where n is selected as an integer other than 3, the above equation (1) can be expressed similarly.
The calculation based on the above equation (2) can be realized by switching the inputs to the adder by a selector and by repeatedly using one adder. The practical repeating number thereof is n and the switching of the inputs is carried out by a predetermined switching control signal.
Now, in embodiment of the digital signal composing circuit according to the present invention will hereinafter be described in detail with reference to FIG. 2 and FIGS. 3A-I to 3P-I and 3A-II to 3P-II, for the case where two digital data are processed by a cross-faded with seven samples, by way of example.
FIG. 2 is a systematic block diagram showing a circuitry of this embodiment according to the present invention. In FIG. 2, reference numeral 1 designates a data input terminal to which two digital data X and Y are supplied sequentially or serially. The digital data X and Y from this input terminal 1 are supplied to and latched in latch circuits 4 and 5 at every sample in response to latch clock signals supplied from a timing circuit (not shown) through latch terminals 2 and 3 to the latch circuits 4 and 5. For example, each time when the clock signal from the latch terminal 2 is supplied to the latch circuit 4, the digital data X in the digital data X and Y from the input terminal 1 is latched in the latch circuit 4, while each time when the clock signal from the latch terminal 3 is supplied to the latch circuit 5, the digital data Y of the digital data X and Y from the input terminal 1 is latched in the latch circuit 5. Regarding the latch clock signals supplied to the latch circuits 5 and 4, the former preceeds by one clock the latter. Of course, when the data X and Y supplied to the latch circuits 4 and 5 are respectively supplied through independent data lines, it is possible that the clock signals from the latch terminals 2 and 3 are the same in timing.
The output signal from the latch circuit 5 is supplied to a selector 7, while the output signal from the latch circuit 4 is supplied to both of the selectors 6 and 7. The selector 6 is supplied with as a feedback signal the output signal from a latch circuit 9 provided at the output side of a half (1/2) adder 8 which adds the output signals from the selectors 6 and 7 to each other. As the latch clock signal for the latch circuit 9, there is used a clock signal which is supplied to a clock terminal 10. These selectors 6 and 7 are operated to switch the signals appearing at their input sides in response to the logic level of the switching control signal which will be described later. By way of example, the selector 7 delivers the output data Y of the latch circuit 5 when the level of the switching control signal to be supplied to its control terminal Y/X is "1", while the selector 7 delivers the output data X of the latch circuit 4 when the level of the switching control signal is "0". On the other hand, the selector 6 delivers the output data L of the latch circuit 9 when the level of the switching control signal to be supplied to its control terminal L/X is "1", while the selector 6 delivers the output data X of the latch circuit 4 when the level of the switching control signal is "0".
A latch circuit 11 is provided at the output side of the latch circuit 9, and a clock signal same as the clock signal supplied to the latch terminal 2 is used as the latch clock of this latch circuit 11. Then, from the output side of the latch circuit 11 is led out an output terminal 12.
As a control means for controlling the switching operation of the selectors 6 and 7, there is employed a circuitry which is formed of, for example, a binary counter 13, a switching circuit 14 and a JK flip-flop circuit 15. The latch clock signal from the latch terminal 2 is supplied to a clear terminal CLR of the binary counter 13 as the clear signal at every sample, while the clock signal from the clock terminal 10 is supplied to a clock terminal CK thereof. The clock signal from the above latch terminal 2 is supplied to a clear terminal CLR of the JK flip-flop circuit 15 as the clear signal, while the clock signal same as that of the binary counter 13 is supplied to a clock terminal CK of the JK flip-flop circuit 15.
The switching circuit 14 is supplied at its input terminals Q 1 to Q n with switching information signals corresponding to the signal processing mode of the circuit of this embodiment. By the way, this embodiment is used for the signal processing mode in which the cross-fade mode is carried out. If, for example, the cross-fade period is taken as a duration of 7 samples, the switching signal of at least 3 bits is supplied from a binary counter 16 to the input terminal Q (Q 1 to Q 3 ) of the switching circuit 14. This switching information signal is supplied to a control terminal a (1a to ma) of the switching circuit 14. The switching information signal is sequentially selected in response to the output signal from the binary counter 13 (where 2 bits to be supplied to the control terminals 1a and 2a are employed) and then supplied through the output terminal Qa to the control terminal Y/X of the selector 7 as the switching control signal. The same clock signal as the clock signal from the latch terminal 2 is used as the clock signal of the binary counter 16, while a cross-fade start signal Sc (FIGS. 3K-I and 3K-II) generated when the cross-fade processing is started is used as the clear signal of the binary counter 16. The input terminal Q 4 of the switching circuit 14 corresonding to an output 2 3 from the binary counter 16 is fixed to either "1" or "0", for example, "0" in this embodiment.
The switching control signal from the switching circuit 14 is also supplied to an input terminal J of the JK flip-flop circuit 15. Since an output terminal Q of this JK flip-flop circuit 15 is "0" level at the initial setting mode, the selector 6 is controlled so as to deliver therefrom the output data X derived from the latch circuit 4 in response to the switching control signal. On the other hand, under the state that the switching control signal from the switching circuit 14 is "1", namely, the level of the input signal at the input terminal J of the JK flip-flop circuit 15 is "1", if the clock signal is supplied from the clock terminal 10 to the clock terminal CK of the JK flip-flop circuit 15, the level of its output terminal Q becomes "1" so that at this time, the selector 6 is controlled by the switching control signal so as to deliver therefrom the output data L of the latch circuit 9. The state under which the level of the output terminal Q of the JK flip-flop circuit 15 is "1" is maintained until the clear signal supplied from the terminal 2 at each sample is applied to the clear terminal CLK thereof.
The operation of the digital signal composing circuit shown in FIG. 2 will be described with reference to the signal waveforms shown in FIGS. 3A-I to 3P-I and 3A-II to 3P-II.
Two digital data X and Y respectively shown in FIGS. 3L-I, 3L-II, and 3M-I, 3M-II are supplied through the input terminal 1 to the latch circuits 4 and 5, while to the clock terminals CK of these latch circuits 4 and 5 are respectively supplied from the latch terminals 2 and 3 the latch clock signals are shown in FIG. 3A-I and FIG. 3A-II, which are delayed by one clock at each sample (the latch clock signal at the terminal 3 side is ahead of that at the terminal 2), and in response to these clock signals, first, the content of the digital data Y is latched in the latch circuit 5 and subsequently the content of the digital data X is latched in the latch circuit 4. The clear signal similar to the clock signal as shown in FIG. 3A-I and FIG. 3A-II is supplied through the latch terminal 2 to the clear terminals CLR of the binary counter 13 and the JK flip-flop circuit 15 so that the binary counter 13 and the JK flip-flop circuit 15 are cleared at each sample.
From the clock terminal 10, for example, three clock signals in one sample as shown in FIG. 3J-I, 3J-II are supplied to the clock terminal CK of the binary counter 13 so that in synchronism with these clock signals two bit signals as shown in FIGS. 3H-I, 3H-II and 3I-I, 3I-II are supplied to the control terminals 1a and 2a of the switching circuit 14.
On the other hand, the switching circuit 14 is supplied at its input terminal Q with switching information signals of 3 bits as shown in FIGS. 3B-I, 3B-II to 3D from the binary counter 16. These switching information signals of 3 bits are selected by the output signal from the binary counter 13 and then supplied through the output terminal Qa of the switching circuit 14 to the control terminal Y/X of the selector 7 as a switching control signal as shown in FIG. 3F-I, 3F-II. Namely, when the output (2 bits) from the binary counter 13 is 0 [0 0] as shown in FIGS. 3H-I, 3H-II and 3I-I, 3I-II, of the switching informations [2 0 , 2 1 , 2 2 ] shown in FIGS. 3B-I, 3B-II, to 3D-I, 3D-II supplied to the input terminals Q 1 to Q 3 of the switching circuit 14 from the binary counter 16, the information of 2 0 is delivered from the switching circuit 14, when 1 [1 0], the information of 2 1 delivered from the switching circuit 14 and when 2 [0 1], the information of 2 2 is delivered from the switching circuit 14. As a result, the switching control signals of 3 bits [2 0 , 2 1 , 2 2 ] in one sample are generated from the switching circuit 14. Namely, in one sample, the calculations are carried out three times (which means the state of n=3 in the above equation (1)). This switching control signal from the switching circuit 14 is also supplied to the input terminal J of the JK flip-flop circuit 15 so that in response to the supply of the clock signal from the clock terminal 10 to its clock terminal CK, which is same as that supplied to the binary counter 13, the switching control signal is delivered through its output terminal Q to the selector 6 as the switching control signal as shown in FIGS. 3G-I and 3G-II.
Accordingly, during a period from time point t 0 to that t 1 as shown in FIG. 3A-I and FIG. 3A-II in which the cross-fade period is not yet reached, the switching information signal to be supplied to the switching circuit 14 is [0 0 0] as will be clear from FIGS. 3B-I, 3B-II to 3D-I, 3D-II. As a result, the switching control signal to be supplied to the selector 7 is also [0 0 0] as shown in FIG. 3F-I and FIG. 3F-II so that during this period the selector 7 generates the data X latched in the latch circuit 4. Meanwhile, since the level of the output terminal Q of the JK flip-flop circuit 15 is normally "0" and the switching control signal to the selector 6 is [0 0 0] as shown in FIG. 3G-I and FIG. 3G-II, also the selector 6 selects and delivers the data X latched in the latch circuit 4 during this period. The data X from the selectors 6 and 7 are added in the half adder 8 and then latched in the latch circuit 9 as the data X. If, now, the contents of the data X and Y are respectively taken as those shown in FIG. 3L-I, FIGS. 3L-II, and 3M-I, FIG. 3M-II, during this calculation period, the content A(n-1) of the data X is latched in the latch circuit 9. FIGS. 3N-I, 3N-II and 3P-I, 3P-II respectively show the sequential orders of three calculations carried out during each sample period and the contents in the latch circuit 9 in correspondence therewith. During the period from time points t 0 to t 1 , the content A(n-1) of the data X is latched sequentially in the latch circuit 9 at each of the first ○1 , second ○2 and third ○3 calculations and then fed back to the other input side of the selector 6 at every calculation as the data L. Then, at time point t 1 when the clock signal from the latch terminal 2 is supplied to the latch circuit 11, the final result in the latch circuit 9 is latched in the latch circuit 11. Accordingly, at the output terminal 12 appears an output data A(n-1) corresponding to the data X at that time as shown in FIG. 30-I, FIG. 30-II. Namely, during this period, one digital data X are all delivered to the output terminal 12.
During the period from time points t 0 to t 1 , the cross-fade start signal Sc as shown in FIG. 3K-I, FIG. 3K-II is produced and supplied to the clear terminal CLR of the binary counter 16, and hence the content thereof is cleared as shown in FIG. 3E-I, FIG. 3E-II. At time point t 1 , similarly as above, in response to the latch signals as shown in FIG. 3A-I, FIG. 3A-II from the latch terminals 2 and 3, the digital data X and Y from the input terminal 1 are respectively latched in the latch circuits 4 and 5 and the content of the binary counter 13 is cleared by the clock signal from the latch terminal 2 as shown in FIG. 3H-I and FIG. 3H-II and also the content of the JK flip-flop circuit 15 is cleared by the same clock signal.
During the period from time points t 1 to t 2 , the switching information signal [1 0 0] is supplied to the input terminal Q of the switching circuit 14 as will be clear from FIGS. 3B-I, 3B-II to 3D-I, 3D-II. Then, in response thereto, from the output terminal Qa thereof, the switching control signal of [1 0 0] as shown in FIG. 3F-I and FIG. 3F-II is supplied to the control terminal Y/X of the selector 7. The JK flip-flop circuit 15 is supplied at its input terminal J with the signal of "1" from the switching circuit 14 when the level of the output terminal Q of the JK flip-flop circuit 15 is "0" in the initial state as described above. After the level of the output terminal Q thereof is changed to "1" in response to the clock signal supplied from the clock terminal 10, this state is maintained until the succeeding clear signal is applied thereto. As a result, during the period from time points t 1 to t 2 , the switching control signal [0 1 1] as shown in FIG. 3C-I and FIG. 3C-II is supplied to the control terminal L/X of the selector 6.
Consequently, the calculation processing at that time is considered for each bit. In the least significant bit (LSB), the switching control signals supplied to the selectors 6 and 7 are respectively "0" and "1" as will be clear from FIGS. 3G-I, 3G-II and 3F-I, 3F-II so that the selectors 6 and 7 respectively select and deliver the data X and Y latched in the latch circuits 4 and 5. These data X and Y are added by the succeeding half adder 8 so as to become the data 1/2[Y+X] and then latched in the latch circuit 9. Namely, at that time, in the latch circuit 9 is latched the data of 1/2[B(0)+A(n)] as will be clear from FIGS. 3N-I, 3N-II, and 3P-I, 3P-II. In the more significant bit (or second order bit), the switching control signals supplied to the selectors 6 and 7 are respectively "1" and "0" so that at this time the selector 6 delivers the data 1/2[Y+X] latched in the latch circuit 9, while the selector 7, this time, delivers the data X latched in the latch circuit 4. These data 1/2[Y+X] and X are added together by the half adder 8, made as 1/2[X+1/2[Y+X]] and then latched in the latch circuit 9. In other words, at this time, data 1/2[A(n)+1/2[B(0)+A(n)]] is latched in the latch circuit 9 as will be clear from FIGS. 3N-I, 3N-II and 3P-I, 3P-II. In the next more significant bit (or third order bit), similarly as the second order bit, the switching control signals supplied to the selectors 6 and 7 are respectively "1" and "0" so that the selector 6 delivers the data of 1/2[X+1/2[Y+X]] latched in the latch circuit 9, while the selector 7 delivers the data X latched in the latch circuit 4. These data are added together by the half adder 8, made as data of 1/2[X+1/2 [X+1/2[Y+X]]], namely, data of 7/8X+1/8Y and then latched in the latch circuit 9. At this time, in the latch circuit 9 is latched data of 1/2[A(n)+1/2[A(n)+1/2[B(0)+A(n)]]] as will be seen from FIGS. 3N-I, 3N-II, and 3P-I, 3P-II. Accordingly, the final result of the latch circuit 9 at this time is latched in the latch circuit 11 by the next latch signal at time point t 2 . Therefore, at this time, at the output terminal 12 appears data of 7/8A(n)+1/8B(0) as shown in FIG. 30-I and FIG. 30-II.
In this way, the calculation processing of one sample period during the period from time points t 1 to t 2 is carried out.
During the period from time points t 2 to t 3 , the switching control signals for the selectors 6 and 7 are respectively [0 0 1] and [0 1 0]. Thus, when the calculation processing same as above is carried out while sequentially switching the selectors 6 and 7, the calculated result during this sampling period is latched in the latch circuit 9 as the data of (6/8)X+(2/8)Y. As a result, at that time, the data of (6/8)A(n+1)+(2/8)B(1) and appears at the output terminal 12 as shown in FIG. 30-I and FIG. 30-II.
Only the switching control signals for the selectors 6 and 7 during each sampling period and the data appearing at the output terminal 12 will be shown hereinafter. As will be clear from FIGS. 3F-I, 3F-II and 3G-I, 3G-II and FIGS. 30-I, 30-II, during the period from time points t 3 to t 4 , [0 1 1], [1 1 0] and 5/8A(n+2)3/8B(2), during the period from time points t 4 to t 5 , [0 0 0], [0 0 1] and (4/8)A(n+3)+(4/8)B(3), during the period from time points t 5 to t 6 , [0 1 1], [1 0 1] and 3/8A(n+4)+5/8B(4), during the period from time points t 6 to t 7 , [0 0 1], [0 1 1] and (2/8)A(n+5)+(6/8)B(5) and during the period from time points t 7 to t 8 which is the final sampling period immediately before the last data X is switched to the data Y, [0 1 1], [1 1 1] and 1/8A(n+6)+7/8B(6). The content of the data latched in the latch circuit 9 at every calculation processings during each sampling period will be considered with reference to especially the period from time points t 4 to t 5 and the period from time points t 6 to t 7 . As will be understood from FIGS. 3L-I, 3L-II, and 3P-I, 3P-II, during the former period, ○1 =A(n+3), ○2 =A(n+3) and ○3 =1/2[B(3)+A(n+3)], while during the latter period, ○1 =A(n+5), ○2 =1/2[B(5)+A(n+5)] and ○3 =1/2[B(5)+1/2[B(5)+A(n+5)]].
At time point t 8 when the cross-fade period is ended, the switching information signal supplied to the input terminal Q of the switching circuit 14 becomes [0 0 0] as shown in FIGS. 3B-I, 3B-II to 3D-I, 3D-II so that the switching control signal to the selector 7 becomes [0 0 0] as shown in FIG. 3F-I and FIG. 3F-II. In association therewith, the switching control signal to the selector 6 also becomes [0 0 0] as shown in FIG. 3G-I and FIG. 3G-II with the result that both the selectors 6 and 7 deliver the data latched in the latch circuit 4. After the interpolation processing of data is ended, the latch circuit 4 is operated in such a manner that of the two digital data A and B supplied thereto from the input terminal 1, the digital data B is latched as the data X. Accordingly, after time point t 8 , the data X is supplied through the selectors 6 and 7 to the half adder 8, added together therein and then latched in the latched circuit 9 as the data X. The content of the data X latched in the latch circuit 9 during the period from time points t 8 to t 9 is presented all as B(7) through three calculations as will be seen from FIGS. 3L-I, 3L-II, and 3P-I, 3P-II. This final result is latched in the latch circuit 11 in response to the next clock signal so that at the output terminal 12 appears the output data B(7) as shown in FIG. 30-I, FIG. 30-II.
As described above, the digital data having different contents can be connected smoothly and then delivered.
While in the above embodiment the present invention is applied to the case of the cross-fade signal processing, the present invention is not limited to the above application but can be applied to other example such as digital volume, digital mixing, digital fade-in/fade-out processing or digital linear interpolation processing and so on. Namely, in the case of the digital volume processing, the amplitude of the signal can be adjusted to as high as K/2 n times. In that case, if the data X is selected to be zero, the signal sample is set in the data Y, the information regarding K is set in the input terminal Q of the switching circuit 14 and after the binary counter 13 is cleared the clock signal is applied n times, at the output terminal 12 appears the signal data which is multiplied by K/2 n . The above operation is repeated for each signal sample. In the case of the digital mixing processing, if one more signal sample is added to the data X which is set to zero in the digital volume, the data X and Y can be mixed with each other with the ratio of (1-K/2 n ):K/2 n . Moreover, in the case of the digital fade-in/fade-out processing, the switching information is set in the input terminal Q of the switching circuit 14 and although in the cross-fade operation, the signal samples are set in both the data X and Y, in this case, the signal sample is set in only the data Y and the data X is made zero. Thus, the fade-in signal processing is presented. Further, in the case of the digital/linear interpolation, if the values at both ends of the interpolation interval are set in the data X and Y, respectively, and the switching information supplied to the input terminal Q of the switching circuit 14 is sequentially selected by the binary counter 13, it is possible to obtain a value which is provided by linearly interpolating the data X and Y.
As set forth above, according to the present invention, in the case of the signal processing such as connecting the plurality of digital data X and Y and so on, the weighted mean value Z=(K/2 n )X+(1-K/2 n )Y is obtained. At that time, the weighted coefficient is taken as K/2 n and the addition of data can be performed by the multiplication of 1/2. Therefore, a multiplier which causes the structure of the circuit to be made large in the prior art can be removed. As a result, the circuitry can be made simple in construction and inexpensive at manufacturing cost, bringing about a great advantage particularly when the digital signal composing circuit is formed as the integrated circuit (IC).
The above description is given on a single preferred embodiment of the invention, but it will be apparent that many modifications and variations could be effected by one skilled in the art without departing from the spirit or scope of the novel concepts of the invention, so that the scope of the invention should be determined by the appended claims only.
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A digital signal composing circuit includes a first selector for selecting a plurality of digital data, a second selector for selecting one of the digital data and a feedback signal, a control circuit for controlling the switching of the first and second selectors and an adding circuit for adding outputs of the first and second selectors and supplying the added output to the second selector as the feedback signal wherein the final output is derived from the adding circuit. Thus, without using any multiplier, the signal processing can be widely used in the digital signal processing such as digital volume, cross-fade, fade-in/-out, mixing, linear interpolation and the like.
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This application is a continuation of application Ser. No. 894,742 filed Aug. 11, 1986, now abandoned, which in turn is a continuation of application Ser. No. 623,338, filed June 22, 1984, now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a printer which can print particular characters in the positions designated.
2. Description of the Prior Art
In conventionally known printers, a tabulation function to align the print start positions is provided so that the print start positions may be easily designated.
However, to print the particular characters in desired positions, it is necessary to confirm the length of the character string and the positions of the particular characters and to key them in.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a printer which can print characters or the like designated in the positions designated in consideration of the above-mentioned point.
It is a specific object of the invention to provide a printer in which particular characters are printed in the position designated without considering the length of character string and the positions of the particular characters.
To accomplish the above objects, a printer according to the invention comprises first input means for instructing predetermined characters and second input means for instructing the particular positions, whereby the characters instructed by the first input means in the particular positions are printed.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a block diagram showing one embodiment of the present invention;
FIG. 2 is an explanatory diagram showing an example of printing according to the present embodiment;
FIG. 3 is an explanatory diagram showing the positions designated in the example of printing shown in FIG. 2;
FIG. 4 is a flowchart showing a method of designation by a printer;
FIG. 5 is an explanatory diagram showing the indication and the progressive state of printing; and
FIGS. 6A to 6C are flowcharts showing a control unit in the present embodiment.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The present invention will now be described in detail hereinbelow with reference to the drawings.
FIG. 1 is a block diagram showing one embodiment of the invention, in which a keyboard KB is provided with: numeric value keys K0 to K9; arbitrary character key group KC; a control key KS to designate the particular characters; a control key KP to designate the particular positions; an instruction key KD to instruct the start of inputting of a character string; an instruction key KE for allowing the particular characters to be printed in accordance with the positions designated; and other control keys (not shown).
KR denotes a register to store key information from the keyboard KB; DSP is a numeric value display; and CPU is a central processing unit.
A printer PRT moves from left to right relative to print paper P and performs printing using a serial print head H. Also, a memory M stores information from the CPU.
FIG. 2 shows an example of printing according to this embodiment. As shown in FIG. 3, the positions which are designated are specified P1 and P2 and it is assumed that the character of decimal point "." is designated. A method of designating the print positions and a method of designating the print characters in the above-mentioned particular positions will be explained in accordance with FIGS. 3 and 4.
Firstly, the print head H is moved to the first desired position P1 (step S2) and the position designation control key KP is depressed (step S4). Thus, the CPU stores the position P1 into the memory M (step S6) in accordance with this operation.
Subsequently, the print head H is moved to the position P2 (step S8) and the position designation control key KP is depressed (step S10), then the position P2 is stored into the memory M (step S12) similarly to the storage of the position P1.
Next, by depressing the particular character instruction key KS and the decimal point key "." in the character key group (steps S14 and S16), the decimal point "." is stored as the particular character information into a latch L1 (step S18).
Due to the above operations, the designated positions P1 and P2 are stored into the memory M and the particular position print character information "." is stored into the latch L1.
FIG. 5 shows the indication and the progressive state of printing.
The operation of this embodiment will now be described hereinbelow in conjunction with FIGS. 5 and 6A to 6C. In this case, as shown in FIGS. 3 and 4, the designated positions P1 and P2 and the designated character "." are preset. First of all, the print head H is moved to a desired position (to the left end) (step S20). Then, the depression of the character string input start instruction key KD (step S22) allows the CPU to read out the position P1 designated adjacent the right side of the print head H from the memory M and to calculate the position number "6" from the position of the print head H to the designated position P1 (steps S24 and S26). The result calculated is stored into a latch L2 in the CPU (step S28.)
By depressing the numeric value key K1 (step S30), a numeric value "1" is stored into the register KR (step S32) and is indicated in the display DSP (step S34). At this time, the CPU compares the numeric value "1" represented by the key depressed with the contents of the latch L1 (step S36); however, since it is not the designated character, the number of "1" of depressions is stored into a counter C for storing the number of times of depression of the numeric value key (step S38).
Subsequently, by depressing the numeric value key K2 (step S40), a numeric value "2" is stored into the register KR (step S42) similarly to the depression of the numeric value key K1 and "2" is indicated in the display DSP (step S44). In addition, at this time, the count value of the counter C for counting the number of times of depression becomes "2" (steps S46 and S48).
Next, by depressing the decimal point key of "." as the designated character (step S50), a decimal point "." is stored into the register KR (step S52) similarly to a numeric value "12", so that "12." is displayed in the display DSP (step S54) as shown in II of FIG. 5. The CPU also compares "." the contents of the latch L1 similarly to the cases of numeric values "1" and "2" (step S56). When the content of the key depressed coincides with the designated character, the CPU stops the counting operation of the counter C (step S58).
Further, by inputting numeric values "34" by use of the numeric value keys, "12.34" is displayed in the display DSP as shown in III of FIG. 5 (steps S60 to S70).
Thereafter, by depressing the instruction key KE (step S72), the CPU performs the processing to subtract the contents "2" of the counter C from a numeric value "6" stored in the latch L2 and calculates "4" as the subtracted result (step S74). The CPU moves the print head H from the present position to the fourth position and allows it to print a numeric value "1" in that position. Then, the CPU moves the head H to the right by one position, thereby printing a numeric value "2". It further moves the head to the right by one position, thereby printing the designated character "." in the designated position P1. Similarly, the print head H is moved to the right by one position at a time, so that "3" and "4" are sequentially printed (step S76). Although the contents of the counter C and latch L2 are cleared due to this (step S78), the contents "." of the latch L1 are still maintained.
Subsequently, by depressing the character string input start instruction key KD (step S80), the CPU reads the designated position P2 on the right side of the head H from the memory M (step S82) and calculates the position number "12" from the position of the print head H to the designated position P2 (step S84). The result of the calculation is stored into the latch L2 in the CPU (step S86).
By depressing the numeric key K1 (step S88), a numeric value "1" is stored into the register KR (step S90) and is displayed in the display DSP (step S92). At this time, the CPU compares "1" represented by the key depressed with the contents of the latch L1 and "1" is stored into the counter C (step S94) on the basis of the result of the comparison.
Further, when numeric values "2345" are input using the numeric value keys (step S98), the CPU performs the comparision regarding each numeric value with the contents of the latch L1 and stores the numeric values into the register KR (step S100). Then, the CPU displays those numeric values in the display DSP (step S102) and stores "5" into the counter C (step S104). By depressing the decimal point "." as the designated character (step S106), the CPU stores the decimal point "." into the register KR (step S108); displays it in the display DSP (step S110); performs the comparison processing with the contents of the latch L1; and stops the operation of the counter C on the basis of the result of the comparision (step S112). Subsequently, when numeric values "67" are input (step S114), the numeric values are indicated as shown in IV of FIG. 5 (step S116 and S118).
Now, the depression of the instruction key KE (step S120) allows the CPU to perform the processing to subtract the contents "5" of the counter C from numeric values "12" stored in the latch L2 and to calculate "7" as the subtracted result (step S122). The CPU moves the print head H from the present position (the position of "4" where the printing was previously done) to the seventh position, thereby printing a numeric value "1" in this position. Then, the CPU moves the head to the right by one position to print a numeric value "2". Similarly, numeric values "345" are printed and the designated character "." is printed in the designated position P2. Numeric values "67" are also similarly printed, so that the print as shown in V of FIG. 5 is obtained (step S124). At this time, although the contents of the latch L2 and counter C are cleared similarly to the case where "12.34" was previously printed (step S126), the contents of the latch L1 are still maintained.
By depressing some control keys thereafter, the print paper P is fed by only one line and the print head H is moved to the left end.
Subsequently, when the character string input start instruction key KD is depressed and the character information "7654.32" which is printed is input, the CPU reads out P1 from the memory M and sets it into the designated position in the same manner as in the case where "12.34" was printed and sets the characters maintained in the latch L1 into the designated characters, then the CPU executes the similar processings as the above. In addition, by depressing the instruction key KE, the CPU performs the processing to subtract the contents "4" of the counter C from the content "6" of the latch L2; calculates "2" as the subtraction result; moves the print head H from the present position to the second position; and allows the head to print "7654.32" in the manner as described above.
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A printer comprises input keys for instructing predetermined characters and input keys for instructing the particular positions, wherein the instructed characters are printed in the particular positions.
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FIELD OF INVENTION
[0001] The present invention provides inhibitors of the oncogenic tyrosine kinase ALK and of the Bcr-Abl mutant T315I Bcr-Abl, pharmaceutical compositions containing the same and their use for the treatment of hyper-proliferative diseases such as cancer, in particular for the treatment of ALK fusion protein positive cancers, such as anaplastic large cell lymphoma (ALCL), diffuse large B cell lymphoma (DLBCL) and inflammatory myofibroblastic tumours (IMT), as well as T315I Bcr-Abl positive cancers such as Chronic Myeloid Leukemia (CML) and Ph+ Acute lymphoblastic leukemia (ALL).
BACKGROUND OF THE INVENTION
[0002] Cancer results from the subversion of processes that control the normal growth, location and mortality of cells. This loss of normal control mechanisms arises from the acquisition of mutations that lead to the oncogenic activation of protein kinases. For example, structural alterations in ALK produced by the chromosomal rearrangement t(2q23,5q35) generates the NPM/ALK oncogenic fusion protein associated with ALCL. 1 Whereas, structural alterations in Abl produced by the chromosomal rearrangement t(9q34,22q11) generates the Bcr-Abl oncogenic fusion protein associated with CML and ALL. 2 Within the kinase domain of Bcr-Abl the mutations T315I is critical for the resistance of the tumour towards molecularly targeted therapy. 3
[0003] Protein kinases are enzymes that catalyse the transfer of phosphate from adenosine-5′-triphosphate (ATP) to specific amino acid residues in many proteins. Generally, the phosphorylation of a protein changes its functionality, from inactive to active in some cases, and from active to inactive in others. Protein kinases are thus involved in the regulation of many aspects of cell function, as most of the signal transduction pathways, such as cellular proliferation, are mediated by phosphorylation. Abnormal activity of protein kinases has been implicated in many cancers as well as in other diseases. Tyrosine kinases, which phosphorylate the phenolic hydroxyl of tyrosine, are particularly involved in these processes.
[0004] Large cell lymphomas represent about 25% of all non-Hodgkin's lymphomas; about one-third of these tumors are anaplastic large cell lymphoma (ALCL). In turn, more than half the patients with ALCL possess a chromosomal translocation that leads to the expression of the NPM/ALK fusion protein. It has been extensively demonstrated that constitutively active NPM/ALK is a potent oncogene with transforming and tumorigenic properties. 4 The high level of expression of NPM/ALK and other ALK fusion protein variants in lymphoma cells and their direct role in lymphomagenesis, combined with the fact that normal ALK is expressed at low levels in the human body, suggests that ALK could potentially be an ideal target for therapy.
[0005] Chronic Myeloid Leukemia (CML) is a myeloproliferative disease, characterized by the presence of a modified chromosome, named Ph-chromosome. In the eighties, the molecular defect associated with this cytogenetic abnormality was identified and it was established that the Ph-chromosome results in the formation of a hybrid gene BCR-ABL coding for the oncogenic fusion protein Bcr-Abl showing tyrosine kinase activity. In the late 1980s, the data accumulated on the role of BCR-ABL in onset and progression of CML indicated BCR-ABL as the most attractive target for molecularly targeted therapy approaches. Therefore attempts to inhibit the TK activity of the oncoprotein were initiated and this process finally ended with the discovery and the development of imatinib mesylate. Imatinib has been under clinical investigation for almost 8 years (50.000 patients) with remarkable results in terms of durable remissions. During the successful clinical trials, resistance to imatinib emerged particularly in patients with acute leukemias, but it is a potential issue also in patients in chronic phase. The molecular mechanism of resistance has been identified in Bcr-Abl gene amplification and mutations in the catalytic kinase domain of the gene 3 . The mutation of the gatekeeper amino acid threonine into a isoleucine (T315I) has been depicted as the predominant one in patients 3 . This has prompted intense research to find new compounds able to overcome the resistance problem, such as Dasatinib 5 , SKI-606 6 and Nilotinib 7 . Despite the increased potency compared to imatinib none of them is able to inhibit efficiently the imatinib-resistant Bcr-Abl T315I mutant. These facts indicate that Bcr-Abl T315I mutant is indeed a target for therapy.
[0006] The disclosed inhibition of ALK and Bcr-Abl mutant T315I has been demonstrated using an ELISA-based in vitro kinase assay that has been previously developed (EP1454992). Furthermore cellular activity of the compounds on NPM/ALK transformed cells has been demonstrated by tritiated thymidine based cell proliferation inhibition assay.
DESCRIPTION OF THE INVENTION
[0007] In a first aspect, the invention provides a compound of formula (I):
[0000]
[0008] wherein Q, T, W, K, J, Y, X, Z are independently selected from C, N, S, O, provided that the corresponding rings are (hetero)aromatic;
[0009] n=0 or 1;
[0010] q=1 or 2;
[0011] R1 is selected from:
[0000] halogen, —NH2,
[0000]
[0012] R2 is hydrogen or halogen,
[0013] R3 is selected from:
[0000]
[0000] or the moiety
[0000]
[0014] present in formula (I) forms a group
[0000]
[0015] wherein A is —CH2— or —NH—.
[0016] In a first preferred embodiment, the invention provides a compound of formula (Ta):
[0000]
[0017] wherein
[0018] R1 is selected from
[0000]
[0019] R3 is selected from:
[0000]
[0020] W, T, Q, Y, K, J and Z are as defined above.
[0021] In a further preferred embodiment, the invention provides a compound of formula (IIa):
[0000]
[0022] wherein:
[0023] R1 is selected from
[0024] Halogen,
[0000]
[0025] —NH 2 ,
[0000]
[0026] R2 is halogen,
[0027] R3 is selected from:
[0028] —NH 2 ,
[0000]
[0029] T, W, Y, K, J, Z are as defined above.
[0030] In a yet further preferred embodiment, the invention provides a compound of formula (IIIa)
[0000]
[0031] wherein A is —CH2— or —NH—,
[0032] R3 is selected from:
[0000]
[0033] X, Z, J and K are as defined above.
[0034] The compounds of the invention can be in the form of free bases or as acid addition salts, preferably salts with pharmaceutically acceptable acids. The invention also includes separated isomers and diastereomers of the compounds, or mixtures thereof (e.g. racemic mixtures).
[0035] In a further aspect the invention provides a compound selected from the group consisting of (a) to (n)—the identifier (MDL number) is reported under each compound—for use as a therapeutic agent:
[0000]
[0036] In a yet further embodiment, the invention provides a pharmaceutical composition containing a compound as above described, including compounds (a) to (n), in association with physiologically acceptable carriers and excipients.
[0037] The compositions can be in the form of solid, semi-solid or liquid preparations, preferably in form of solutions, suspensions, powders, granules, tablets, capsules, syrups, suppositories, aerosols or controlled delivery systems. The compositions can be administered by a variety of routes, including oral, transdermal, subcutaneous, intravenous, intramuscular, rectal and intranasal, and are preferably formulated in unit dosage form, each dosage containing from about 1 to about 1000 mg, preferably from 1 to 500 mg of active ingredient. The principles and methods for the preparation of pharmaceutical compositions are described for example in Remington's Pharmaceutical Science, Mack Publishing Company, Easton (Pa.).
[0038] In a yet further embodiment, the invention relates to a compound or a pharmaceutical composition as herein provided, including compounds (a) to (n) identified above, for use in the treatment of tumors, especially of Anaplastic Lymphoma Kinase-associated or Bcr-Abl-associated tumors. In a preferred embodiment, the compounds or compositions according to the invention are used in the treatment of anaplastic large cell lymphoma, diffuse large B cell lymphoma, inflammatory myofibroblastic tumors, chronic myeloid leukemia or Ph+ acute lymphoblastic leukemia. In a further preferred embodiment, the compounds or compositions are used for the treatment of chronic myeloid leukaemia (CML) resistant to Imatinib or Dasatinib or Nilotinib or Bosutinib.
[0039] General Synthesis Strategies
[0040] Compounds were designed as a series of three unsaturated rings: two aromatic or heteroaromatic and a terminal five-membered with two heteroatoms. These molecules will be the core for the synthesis of other derivatives; the introduction of a new moiety on the meta position on the five membered ring is considered to be promising way to achieve high affinity for the ALK active site.
[0041] In order to generate a panel of terminal groups starting from common precursors, the synthetic approach begins from the cross coupling of unsubstituted five-membered rings. In this case the C2 position of the five membered ring is left open to undergo derivatisation after the construction of the polyaromatic scaffold. There are many examples of such reactions, generally based on the different acidity among the proton of the ring: in an 1,3 heteroarmatic structure the C2 position is by far the most acidic, and can be easily and selectively litiated. Amino, alkyl and sulfanyl moieties are examples of the terminal groups that can be attached to the core structure using this approach.
[0000]
[0042] The optimised synthetic path is based on a first Stille coupling between the five-membered metallorganic ring and an aromatic moiety. This has been accomplished using in turn a single aromatic ring with two halogens of different reactivity or a double aromatic ring with a single halogen. In the former case, the second halogen acts as a leaving group in a following carbon-carbon coupling reaction performed using Suzuki or Stille procedure with the appropriate organometallic partner. As already mentioned, the functionalisation of the terminal group is carried out at the end of the synthetic line.
[0043] First, the five-membered rings of the terminal moiety were synthesized;
[0044] the literature methods followed were originally developed by Cliff and Pyne for the stannyl-derivatives of imidazole and by Dondoni for the organometallic thiazoles. The approach towards the functionalization of the C4/C5 position of the two heterocyclic rings is quite different: while for imidazole the metallation happens via metal-halogen exchange after halogenation/reductive dehalogenation steps, thiazole can be directly lithiated in C2, protected with trimethylsilyl chloride, and metallated again in C5.
[0000]
[0045] Once obtained these precursors, their reactivity towards coupling and functionalisation in C2 has been tested. The functionalisation of thiazole with tosyl azide was unreported, but has proven to be feasible. In a test reaction standard addiction of TsN 3 to thiazole after lithiation, followed by hydride reduction of the azide afforded 2-amino thiazole; similarly, also the introduction of a thioether group was quite straightforward:
[0000]
[0046] The organo-heterocycles were then used in the Stille coupling. First the adducts of 2-Iodo-5-Chloro pyridine was synthesised, then the 5-Bromine analogue, which was more suitable to undergo a second coupling. Yields were satisfactory for the thiazoles, far worse for the imidazole, probably for the lability of the MOM protecting group under the reaction conditions.
[0000]
[0047] The regioselectivity of this first Stille reaction is remarkable, as can be expected by the presence of a better leaving group (I vs. Br) on a more electron-poor position, which favours the oxidative insertion of Pd on the carbon-halogen bond. In any case, the α-nitrogen adduct was isolated without trace of other diastereoisomers, as shown by NOE's analysis.
[0048] The second addiction could be accomplished via Stille or Suzuki coupling by a tin or boron-aryl compound; we started with 1,2-dichloro-3-methoxybenzene derivatives, which can be synthesised easily both as boronic acid and as stannyl compounds (Perec et al., J. Org. Chem., 2001, 2104-2117). The following Stille reaction was too slow (no appreciable product formation after 3d), but the Suzuki was satisfactory.
[0000]
[0049] With the same approach, terminal moieties such as the 2-pyridine, 3-pyridine and 2-bromobenzene groups have been introduced coupling them as organo-tin compounds with Stille procedure (2- and 3-pyridine) or as organo-bromic ones with Suzuki (2-bromobenzene, 3-pyridine). Once assessed the reaction conditions, it has been possible to combine the two couplings in a single pot, two step reaction simply adding at the reaction mixture the second organometallic once the first addiction was complete; this allows to spare the use of new catalyst and a chromatographic separation, speeding up considerably the synthetic line.
[0050] The derivatization to amide of the terminal amino moiety was studied on 5-(9H-fluoren-7-yl)thiazol-2-amine as a test compound.
[0051] Typical coupling procedures were the reaction of acyl chlorides with the amine in solvent mixtures (THF/DMF or DCM/DMF) with triethylamine as base, and reaction with acids assisted by coupling agents such as DCC, HTBU, DIEA and PyBOP with diisopropyl ethylamine or triethylamine as bases. Using these methods the following compounds have been synthesized:
[0052] N-(4-(9H-fluoren-2-yl)thiazol-2-yl)-2-(4-methylpiperazin-1-yl)acetamide
[0053] N-(4-(9H-fluoren-2-yl)thiazol-2-yl)-7-(diethylamino)heptanamide
[0054] N-(4-(9H-fluoren-2-yl)thiazol-2-yl)-4-hydroxybutanamide
[0055] N-(4-(9H-fluoren-2-yl)thiazol-2-yl)nicotinamide
[0056] N-(4-(9H-fluoren-2-yl)thiazol-2-yl)-5-bromofuran-2-carboxamide
[0057] N-(4-(9H-fluoren-2-yl)thiazol-2-yl)-3-(4-methylpiperazin-1-yl)propanamide
[0058] 5-[4-(4-Methyl-piperazine-1-carbonyl)-phenyl]-furan-2-carboxylic acid[4-(9H-fluoren-2-yl)-thiazol-2-yl]-amide
[0059] N-(4-(9H-fluoren-2-yl)thiazol-2-yl)-4-((4-methylpiperazin-1-yl)methyl)benzamide
[0060] N-(4-(9H-fluoren-2-yl)thiazol-2-yl)-3,4,5-triiodobenzamide
[0061] As already mentioned, the synthesis of tin-substituted thiazoles by literature methods was plagued by low yields; this was mainly due to the low solubility of the anions at low temperature: to obtain the complete formation of the carbanion at −78 C we had to raise the dilution to 1 mmol (85 mg) every 10 ml THF- this procedure is not suitable for large scale preparations, so a one-pot, two steps procedure with sequential addition of the metal chlorides on the C-2 and C-5 carbanions was chosen, raising the temperature after every addiction of BuLi in order to accomplish the formation of the carbanions. In our expectation, the first addition/quench sequence was intended to protect with a TMS group the most acidic C-2 position, while the second one had the aim to introduce the trimethyltin group on the mildly acidic C-5. Through rearrangement the C5-silyl, C2-tin adduct was obtained in really high yield, i.e. the thiazole ring behaved as the C5 position was the most acidic one.
[0000]
[0062] The most straightforward rationale of such behaviour takes into account the different thermodynamic stability of the carbanions: being the conjugate base of the stronger acid, the C2 anion is more stable than the C5 one, and raising the temperature to −20° C. is sufficient to have the base rearranged. Re-equilibration between the 4 and the 2 position of the imidazole anion has been reported (Groziak, M. P., Wei, L., J. Org. Chem., 1991, 4296-4300).
[0063] On the basis of our experimental data, we propose for this rearrangement the mechanism illustrated in Scheme.
[0000]
[0064] Thus, by controlling the reaction temperature it is possible to functionalise directly the C5 position of the thiazole ring avoiding the use of protection/deprotection procedures.
[0065] The rearrangements on 2-trimethyltin and 2-trimethylsilyl thiazole were both effective and afforded the corresponding C5 compounds in high yield.
[0066] The same adduct was effective without further purifications in the above described Stille reactions.
EXAMPLES
1. Synthesis of Compounds
1) N,N′-(5,5′-(1,4-phenylene)bis(1H-imidazole-5,2-diyl))diacetamide (r114)
[0067]
[0068] To a solution of acetylguannidine (400 mg, 4 mmol) in DMF (5 mL) 1,1′-(1,4-phenylene)bis(2-bromoethanone) (320 mg, 1 mmol) was added. The reaction mixture was stirred at RT for 96 h, then evaporated, re-taken in water and dried under high vacuum to give 50 mg (15% yield) N,N′-(5,5′-(1,4-phenylene)bis(1H-imidazole-5,2-diyl))diacetamide.
[0069] 1H-NMR (DMSO, 400 MHz), δ (ppm): 11.72 (bs 1H); 11.28 (bs, 1H); 7.64 (s, 4H); 7.20 (s, 2H); 2.05 (s, 6H).
2) 4,4′-(1,4-phenylene)dithiazol-2-amine (precursor of r218)
[0070]
[0071] 2-Bromo-1-[4-(2-bromo-acetyl)-phenyl]-ethanone (0.28 g, 0.9 mmol) was added at room temperature to a stirred solution of thiourea (0.12 g, 1.6 mmol) in hot ethanol (25 mL). The reaction mixture was stirred at 70° C. for 3 h. After evaporation of the solvent under reduced pressure, the crude was purified by flash chromatography (94:5:1, CHCl 3 :EtOH:Et 3 N) giving 190 mg (77%) of 4,4′-(1,4-phenylene)dithiazol-2-amine.
[0072] 1 H NMR (DMSO, 400 MHz), δ (ppm): 7.80 (s, 4H), 7.19 (s, 2H), 3.51 (bs, NH 2 ).
3) N,N′-(4,4′-(1,4-phenylene)bis(thiazolle-4,2-diyl))bis(4-((4-methylpiperazin-1-yl)methyl)benzamide) (r218)
[0073]
[0074] 4-(4-Methyl-piperazin-1-ylmethyl)-benzoic acid (0.38 g; 1.6 mmol) was dissolved in CH 2 Cl 2 (20 mL), and N,N-diisopropylethylamine (0.30 mL, 2.0 mmol). After 10 min, HBTU (0.26 g, 0.7 mmol) and 4,4′-(1,4-phenylene)dithiazol-2-amine (0.19 g, 0.7 mmol) were added. The reaction was stirred at room temperature overnight. After evaporation of the solvent under reduced pressure, the crude was purified by flash chromatography (94:5:1 CH 2 Cl 2 :EtOH:Et 3 N) giving 200 mg (40%) of N,N′-(4,4′-1,4-phenylene)bis(thiazole-4,2-diyl))bis(4-4((4-methylpiperazin-1-yl)methyl)benzamide
[0075] 1 HNMR (DMSO, 400 MHz), δ (ppm): 8.00 (d, 4H, J=8.2 Hz), 8.02 (s, 4H), 7.73 (s, 2H), 7.48 (d, 4H, J=8.2 Hz), 3.59 (s, 4H), 2.50 (bs, 16H), 2.45 (s, 6H)
4) 1,4-di(furan-3-yl)benzene (r236)
[0076]
[0077] Palladium tetrakistryphenilphosphine (0.20 mmol, 0.24 g) was added to a solution of 1,4-dibromobenzene (1.0 g, 4.4 mmol), furan-3-yl boronic acid (0.40 g, 3.6 mmol) and cesium carbonate (4.2 g, 13 mmol) in dimethoxyethane/water (15/5 mL), and the resulting mixture degassed and refluxed under argon for 14 h.
[0078] The resulting suspension was cooled, filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (95: 5 hexane ethyl acetate) to give 100 mg (13%) of 1,4-di(furan-3-yl)benzene as a white solid.
[0079] 1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 7.75 (dd, 2H, J=1.0 Hz, J=1.5 Hz) 7.49 (m, 6H) 6.72 (dd, 2H, J=0.9 Hz, J=1.9 Hz).
5) 5-Bromo-furan-2-yl)-(4-methyl-piperazin-1-yl)-methanone
[0080]
[0081] 5-Bromo-furan-2-carboxylic acid (2.0 g, 10 mmol) was suspended in thionyl chloride (10 mL). The reaction mixture was heated to 100° C., two drops of DMF were added, and the resulting solution was refluxed for 1 h. After cooling, thionyl chloride was removed under reduced pressure, and the residue was re-taken in Et 3 N (3 mL) and anhydrous THF (25 mL). The solution was filtered and 1-methyl-piperazine (1.55 mL, 14 mmol) was added. The reaction mixture was heated to 70° C. overnight After evaporation of the solvent under reduced pressure, the crude was purified by flash chromatography (97:2:1 CHCl 3 :EtOH:Et 3 N) giving 2.20 g (80%) of (5-Bromo-furan-2-yl)-(4-methyl-piperazin-1-yl)-methanone.
[0082] 1 HNMR (CDCl 3 , 400 MHz), δ (ppm): 6.98 (d, 1H, J=3.6 Hz), 6.42 (d, 1H, J=3.6 Hz), 3.83 (bs, 4H), 2.36 (s, 3H), 1.80 (bs, 4H).
6) (5-{4-[5-(4-Methyl-piperazine-1-carbonyl)-furan-2-yl]-phenyl}-furan-2-yl)-(4-methyl-piperazin-1-yl)-methasone (r237)
[0083]
[0084] Palladium tetrakistryphenilphosphine (40 mg, 36 μmol) was added to a stirred solution of (5-Bromo-furan-2-yl)-(4-methyl-piperazin-1-yl)-methanone (0.40 g, 1.4 mmol) and 1,4-phenylene diboronic acid (0.12 g, 0.7 mmol) in degassed dioxane (15 mL) and saturated aqueous sodium carbonate (8 mL). The reaction mixture was refluxed overnight under Argon atmosphere. After evaporation of the solvent, the crude was purified by flash chromatography (89:10:1 CHCl 3 : EtOH: Et 3 N,) giving 260 mg (80%) of (5-{4-[5-(4-Methyl-piperazine-1-carbonyl)-furan-2-yl]-phenyl}-furan-2-yl)-(4-methyl-piperazin-1-yl)-methanone.
[0085] 1 H NMR (CDCl 3 , 400 MHz), δ (ppm): 7.70 (s, 4H), 7.26 (d, 2H, J=3.6 Hz), 6.78 (d, 2H, J=3.6 Hz), 3.94 (bs, 8H), 2.40 (s, 6H), 1.85 (bs, 8H).
7) 5,5′-(1,4-phenylene)difuran-2-carboxylic acid. (r239)
[0086]
[0087] Palladium tetrakistryphenilphosphine (0.10 mmol 0.30 g) was added to a solution of 1,4-phenylenediboronic acid (0.40 g, 2.5 mmol), cesium carbonate (3.20 g, 10 mmol) and 5-bromofuran-2-carboxylic acid (0.95 g, 5 mmol) in dimethoxyethane/water (10/5 mL); the resulting mixture was degassed and refluxed under argon. After 24 h the solvent was evaporated in vacuo and the crude product purified by flash chromatography (98:2 CH 2 Cl 2 CH 3 OH) to give 0.15 g (20%) of 5,5′-(1,4-phenylene)difuran-2-carboxylic acid (0.15 g, 0.5 mmol) as a white solid.
[0088] 1 H NMR (d6-DMSO 400 MHz) δ (ppm): 7.85 (m, 4H) 7.20 (m, 2H) 7.16 (d, 2H, J=3.5 Hz).
8) 5-chloro-2-(1-(methoxymethyl)-1H-imidazol-4-yl)pyridine
[0089]
[0090] Pd(PPh 3 ) 4 (110 mg, 0.1 mmol) was added portiowise to a stirred solution of 1-(methoxymethyl)-4-(trimethylstannyl)-1H-imidazole (550 mg, 2 mmol) and 2-bromo-5-chloropyridine (400 mg, 2.2 mmol) in degassed toluene (20 ml) under inert atmosphere. The reaction mixture was refluxed for 2 d. After evaporation of the solvent under reduced pressure, the crude was purified by flash chromatography (hexane/AcOEt, 70:30) giving 70 mg (15%) of 5-chloro-2-(1-(methoxymethyl)-1H-imidazol-4-yl)pyridine.
[0091] 1H NMR (400 MHz, CDCl3), δ (ppm):
9) 5-chloro-2-(thiazol-5-yl)pyridine
[0092]
[0093] Pd(PPh 3 )4 (110 mg, 0.1 mmol) was added portiowise to a stirred solution of 2-(trimethylsilyl)-5-(trimethylstannyl)thiazole (320 mg, 1 mol) and 2-bromo-5-chloropyridine (200 mg, 1.1 mmol) in degassed toluene (10 ml), under inert atmosphere. The reaction mixture was refluxed for 1 d. After evaporation of the solvent under reduced pressure, the crude was purified by flash chromatography (hexane/AcOEt 70:30%). Deprotection of the silyl group occurs during chromatography give 150 mg (80%) of 5-chloro-2-(thiazol-5-yl)pyridine.
[0094] 1H NMR (400 MHz, CDCl3), δ (ppm): 8.48 (1H, d); 8.32 (1 Hm s); 7.95 (1H, s); 7.72 (1H, d); 7.69 (1H, 1 H, s)
10) 5-bromo-2-(thiazol-2-yl)pyridine
[0095]
[0096] Pd(PPh 3 ) 4 (220 mg, 0.2 mmol) was added portionwise to a stirred solution of 2-(trimethylstannyl)thiazole (0.50 g, 2 mmol) and 2-Iodo-5-Bromopyridine (0.57 g, 2 mmol) in degassed toluene (20 ml) under inert atmosphere. The reaction mixture was refluxed for 14 h. After evaporation of the solvent under reduced pressure, the crude was purified by flash chromatography (hexane/AcOEt, 80:20) giving 400 mg (83%) of 5-bromo-2-(thiazol-2-yl)pyridine.
[0097] 1H NMR (400 MHz, CDCl3), δ (ppm):
11) 5-bromo-2-(thiazol-5-yl)pyridine (precursor r113)
[0098]
[0099] Pd(PPh 3 ) 4 (220 mg, 0.2 mmol) was added portionwise to a stirred solution of 2-(trimethylsilyl)-5-(trimethylstannyl)thiazole (640 mg, 2 mmol) and 2-Iodo-5-Bromopyridine (0.57 g, 2 mmol) in degassed toluene (20 ml), under inert atmosphere. The reaction was refluxed for 14 h and quenched with with saturated Na 2 CO 3 . After quenching with saturated Na 2 CO 3 solution, the mixture was extract with ether. The organic layers were dried with MgSO 4 and the solvent removed under reduced pressure. The crude was purified by flash chromatography (hexane/AcOEt, 70:30) giving 330 mg (70%) of 5-bromo-2-(thiazol-5-yl)pyridine.
[0100] 1 H NMR (400 MHz, CDCl3), δ (ppm): 8.84 (1H, s); 8.54 (1H, d); 8.32 (1H, s); 7.70 (1H, dd); 7.63 (1H, d);
12) 5-(2-bromophenyl)-2-(thiazol-2-yl)pyridine (r116)
[0101]
[0102] Pd(PPh 3 ) 4 (10 mg, 0.01 mmol) was added portiowise to a stirred solution of 2-bromophenylboronic acid (100 mg, 0.5 mmol) and 5-bromo-2-(thiazol-5-yl)pyridine (100 mg, 0.4 mmol) in dioxane (5 ml) under inert atmosphere. A solution of K 2 CO 3 (200 mg, 1.5 mmol) in water (2 ml) was then added and the reaction refluxed for 14 h. After quenching with saturated Na 2 CO 3 solution, the mixture was extract with ether. The organic layers were dried with MgSO 4 and the solvent removed under reduced pressure. The crude was purified by flash chromatography (hexane/AcOEt, 30:70) giving 60 mg (50%) of 5-(2-bromophenyl)-2-(thiazol-2-yl)pyridine.
[0103] 1 H NMR (400 MHz, CDCl3), δ (ppm): 8.68 (1H, d); 8.26 (1H, dd); 7.95 (1H, d); 7.89 (1H, dd); 7.72 (1H, dd); 7.48 (1H, d); 7.43 (1H, td); 7.37 (1H, dd); 7.29 (1H, td)
13) 2-(6-(thiazol-5-yl)pyridin-3-yl)pyridine (r117)
[0104]
[0105] 3-(trimethylstannyl)pyridine (0.24 g, 0.9 mmol) dissolved in anhydrous toluene (5 mL) was added dropwise to a solution of 5-(5-bromo pyridin-2-yl)thiazole (0.12 g, 0.5 mmol) in (10 mL) under Argon atmosphere; the reaction is stirred at reflux for 14 h. The solvent was then removed under vacuum and the crude purified by column chromatography (eluant: CH 2 Cl 2 /MeOH, 99:1) to give 0.06 g, 0.24 mmol of 2-(6-(thiazol-5-yl)pyridin-3-yl)pyridine (60% yield).
[0106] 1 H NMR (CDCl 3 400 MHz) δ (ppm):8.88 (s, 2H), 8.84 (d, 1H, J=2.3 Hz), 8.68 (d, 1H, J=4.8 Hz), 8.41 (s, 1H), 7.96 (dd, 1H, J1=8.1, J2=2.3 Hz), 7.92 (dt, 1H, J1=1.3, J2=7.9 Hz), 7.83 (d, 1H, J=8.1 Hz), 7.45 (dd, 1H, J1=8.1, J2=4.8 Hz).
14) 3-(3-Chloro-4-thiazol-5-yl-phenyl)-pyridine (r120)
[0107]
[0108] To a solution of 5-(4-Bromo-2-chloro-phenyl)-thiazok (3.4 g, 12 mmol) and 3-[1,3,2]Dioxaborinan-2-yl-pyridine (2.0 g, 12 mmol) in 15 mL of toluene in a Schlenk apparatus 5 mL of a saturated solution of Na 2 CO 3 in water were added. The mixture was degassed and [Pd(P(Ph 3 ) 4 ] (630 mg, 60 mmol) was added and the reaction stirred at 110 C for 12 h. The solvent is then evaported and the crude re-taken in CHCl 3 and filtered on celite and purified by column chromatography (eluant: 15:85, CHCl 3 /AcOEt) to give 1.40 g (42% yield) of 3-(3-Chloro-4-thiazol-5-yl-phenyl)-pyridine as a yellow solid.
[0109] 1 H NMR (CDCl 3 400 MHz), δ (ppm): 8.90 (s, 1H), 8.87 (d, 1H, J=2.0), 8.65 (dd, 1H, J=4.7, 2.0 Hz), 8.16 (s, 1H), 7.90 (m, 1H), 7.73 (d, 1H, J=1.6 Hz), 7.65 (d, 1H, J=8.2 Hz), 7.54 (dd, 1H, J=8.2, 2.0 Hz), 7.41 (m, 1H).
15) N-[5-(2-Chloro-4-pyridin-3-yl-phenyl)-thiazol-2-yl]-4-(4-methyl-piperazin-1-ylmethyl)-benzamide (r127)
[0110]
[0111] To a solution of 4-(4-Methyl-piperazin-1-ylmethyl)-benzoic acid (122 mg, 0.5 mmol) in DMF (15 mL) and DIEA (0.2 mL, 1.1 mmol) HBTU (200 mg, 0.5 mmol) e 5-(2-Chloro-4-pyridin-3-yl-phenyl)-thiazol-2-ylamine (150 mg, 0.5 mmol) were added. The reaction was stirred at RT for 12 h, then the solvent was removed under reduced pressure and the crude purified by column chromatography (eluant: 99:1, CHCl 3 /Et 3 N). Obtained 176 mg (70% yield) of N-[5-(2-Chloro-4-pyridin-3-yl-phenyl)-thiazol-2-yl]-4-(4-methyl-piperazin-1-ylmethyl)-benzamide.
[0112] 1 H NMR (DMSO, 400 MHz), δ (ppm): 8.86 (dd, 1H, J=2.4, 0.8 Hz), 8.65 (dd, 1H, J=4.8, 1.6 Hz), 7.99 (m, 2H), 7.89 (ddd, 1H, J=7.9, 2.4, 1.6 Hz), 7.71 (d, 1H, J=1.9 Hz), 7.61 (d, 1H, J=8.1 Hz), 7.56 (s, 1H), 7.53 (m, 2H), 7.52 (dd, 1H, J=8.0, 2.0 Hz), 7.41 (ddd, 1H, J=8.0, 4.9, 1.0 Hz), 3.6 (s, 2H), 2.50 (s largo, 4H), 2.46 (s largo, 4H), 2.28 (s, 3H)
16) 5-Bromo-furan-2-carboxylic acid[5-(2-chloro-4-pyridin-3-yl-phenyl)-thiazol-2-yl]-amide (r128)
[0113]
[0114] 5-(2-Chloro-4-pyridin-3-yl-phenyl)-thiazol-2-ylamine (150 mg, 0.5 mmol) and HTBU were added to a solution of 5-Bromo-furan-2-carboxylic acid (100 mg, 0.5 mmol) in DMF (15 mL) and DIEA (0.2 mL, 1.1 mmol). The reaction was stirred at RT for 12 h, the solvent was then removed under reduced pressure and the crude purified by column chromatography (eluant: 98:1:1, CHCl 3 /EtOH/Et 3 N) to give 98 mg (40% yield) of 5-Bromo-furan-2-carboxylic acid[5-(2-chloro-4-pyridin-3-yl-phenyl)-thiazol-2-yl]-amide.
[0115] 1 H NMR (DMSO, 400 MHz), δ (ppm): 9.90 (bs, 1H), 8.97 (d, 1H, J=2.4 Hz), 8.69 (dd, 1H, J=4.8, 1.7 Hz), 8.17 (dt, 1H, J=8.2, 2.2 Hz), 7.98 (m, 1H), 7.93 (s, 1H), 7.79 (s, 2H), 7.54 (m, 1H), 7.51 (dd, 1H, J=8.0, 4.8 Hz), 6.84 (d, 1H, J=3.6 Hz).
17) 5-bromo-N-(5-(6-(oxazol-2-yl)pyridin-3-yl)pyridin-2-yl)furan-2-carboxamide (r200)
[0116]
[0117] To a solution of 5-bromofuran-2-carbonyl chloride (18.0 g, 0.9 mmol) in dry DCM (10 ml) and freshly distilled Et 3 N (0.4 ml) 5-(6-(oxazol-2-yl)pyridin-3-yl)pyridin-2-amine (0.15 g, 0.6 mmol). The mixture is stirred at RT under Argon atmosphere for 1 h, evaporated and purified by by column chromatography (eluant: 60:35:5 CHCl3:EtOAc:Et3N). Obtained 0.04 g (17% yield) of 5-bromo-N-(5-(6-(oxazol-2-yl)pyridin-3-yl)pyridin-2-yl)furan-2-carboxamide.
[0118] 1 H NMR (CDCl 3 400 MHz) δ(ppm):8.96 (d, 1H, J=2.2 Hz), 8.62 (d, 1H, J=2.4 Hz), 8.49 (d, 1H, J=8.6 Hz), 8.26 (d, 1H, J=8.2 Hz), 8.04 (dd, 2H, J=2.3 Hz, J=8.2 Hz), 7.86 (s, 1H), 7.36 (s, 1H), 7.29 (d, 1H, J=3.6 Hz), 6.55 (d, 1H, J=3.6 Hz).
18) 4-(4-bromo-3-chlorophenyl)-2-methoxythiazole
[0119]
[0120] A solution of sodium methoxide in dry methanol under Argon atmosphere was cooled to 0° C. and 4-(4-bromo-3-chlorophenyl)thiazole (0.2 g, 0.6 mmol) in dry methanol (5 mL) was added dropwise. The reaction mixture is warmed to RT and refluxed for 4 h, then cooled, diluted with water (20 mL) and extracted with ether (3×20 mL). The organic phases are dried (MgSO 4 ) and evaporated to give 0.15 g (84% yield) of 4-(4-bromo-3-chlorophenyl)-2-methoxythiazole.
[0121] 1 H NMR (CDCl 3 400 MHz) δ(ppm):7.62 (d, 1H, J=1.9 Hz), 7.41 (dd, 1H, J=2.0 Hz, J=8.3 Hz), 7.34 (s, 1H), 7.31 (d, 1H, J=8.3 Hz), 4.11 (s, 3H).
[0122] General Procedure for Compounds r238, r235 r262
[0123] To a 0.1 M solution of boronic acid (1 eq) in Dioxane:H2O 5:1 the organic halide (1.2 eq) and K2CO3 (5 eq) are added. The solution is degassed, [PdP(Ph3)4] (5% mol) is added and reaction is heated to reflux and monitored by TLC. Upon completion, the solvent is evaporated and the crude re-taken in MeOH or Chloroform, filtered and purified by column chromatography.
19) 2-(4-bromo-2-chlorophenyl)furan
[0124]
[0125] Obtained by reaction of 4-bromo-2-chloro-1-iodobenzene with furan-2-yl-2-boronic acid. Yield after purification by column chromatography (eluant:hexane): 30%.
[0126] 1 H NMR (CDCl 3 400 MHz) δ (ppm):7.73 (d, 1H, J=8.6 Hz), 7.60 (d; 1H, J=2.0 Hz), 7.52 (dd, 1H, J=0.6 Hz, J=1.8 Hz), 7.44 (dd, 1H, J=2.0 Hz, J=8.5 Hz), 7.14 (dd, 1H, J=0.5 Hz, J=3.5 Hz), 6.53 (dd, 1H, J=1.8 Hz, J=3.4 Hz).
[0127] 13 C NMR (CDCl3 100 MHz) δ(ppm): 149.33, 142.37, 133.15, 132.02, 131.20, 130.14, 128.80, 120.70, 111.85, 111,33.
20) 5-(2-cloro-4-(piridin-3-il)fenil)-2-metossitiazolo (r262)
[0128]
[0129] Obtained by reaction of 4-(4-bromo-3-chlorophenyl)-2-methoxythiazole with pyridin-3-ylboronic acid. Yield after purification by column chromatography (eluant:hexane:ethyl acetate 6:4): 30%
[0130] 1 H NMR (CDCl 3 400 MHz) δ(ppm): 8.86 (s, 1H), 8.64 (d, 1H, J=4.2 Hz), 7.89 (dt, 1H, J=7.9 Hz, J=1.9 Hz), 7.69 (d, 1H, J=1.8 Hz), 7.58 (d, 1H, J=8.1 Hz), 7.50 (dd, 1H, J=1.8 Hz, J=8.1 Hz), 7.42 (m, 2H), 4.13 (s, 3H).
[0131] 13 C NMR (CDCl3 100 MHz) δ(ppm): 140.08, 136.53, 134.47, 134.26, 134.19, 131.32 (2C), 128.94, 125.61 (2C), 123.64, 58.17.
21) 3′-cloro-4′-(furan-2-il)bifenil-4-acido carbossilico (r238)
[0132]
[0133] Obtained by reaction of 2-(4-bromo-2-chlorophenyl)furan with 4-boronobenzoic acid. Yield after purification by column chromatography (eluant: CHCl3: methanol 95:5): 30%.
[0134] 1 H NMR (d6-DMSO 400 MHz) δ(ppm):8.01 (d, 2H, J=8.3 Hz), 7.93 (dd, 2H, J=3.2 Hz, J=5.1 Hz), 7.87 (s, 2H), 7.85 (s, 1H), 7.81 (dd, 1H, J=1.8 Hz, J=8.4 Hz), 7.20 (d, 1H, J=3.5 Hz), 6.68 (dd, 1H, J=1.8 Hz, J3.3 Hz).
[0135] 13 C NMR (d6-DMSO 100 MHz) δ(ppm): 143.66, 143.63, 130.00, 129.65, 128.84, 128.30, 128.02, 126.76, 126.00, 122.21, 111.53.
22) 5-(3-cloro-4-(tiazol-5-il)fenil)piridin-2-ammina (r235)
[0136]
[0137] Obtained by reaction of 4-(4-bromo-3-chlorophenyl)thiazole with 6-aminopyridin-3-ylboronic acid. Yield after purification by column chromatography (eluant: DCM: methanol 95:5): 42%.
[0138] 1 H NMR (CDCl 3 400 MHz) δ(ppm): 8.88 (d, 1H, J=0.6 Hz) 8.30 (dd, 1H, J=0.6 Hz, J=2.4 Hz), 8.14 (d, 1H, J=0.7 Hz), 7.73 (dd, 1H, J=2.5 Hz, J=8.7 Hz), 7.64 (d, 1H, J=1.8 Hz), 7.59 (d, 1H, J=8.1 Hz), 7.45 (dd, 1H, J=1.9 Hz, J=8.1 Hz), 6.68 (dd, 1H, J=0.7 Hz, J=8.6 Hz), 5.04 (s, 2H).
23) 5-(2,3-dichloro-4-methoxyphenyl)-2-(2-(methylthio)thiazol-5-yl)pyridine
[0139]
[0140] Pd(PPh 3 ) 4 (100 mg, 0.1 mmol) was added portiowise to a stirred solution of 2,3-dichloro-4-methoxyphenylboronic acid (220 mg, 1.0 mmol) and 5-bromo-2-(2-(methylthio)thiazol-5-yl)pyridine (350 mg, 1.0 mmol) in dioxane (5 ml) under inert atmosphere. A solution of K 2 CO 3 (1 g, 7.2 mmol) in water (10 ml) was then added and the reaction refluxed for 14 h. After quenching with saturated Na 2 CO 3 solution, the mixture was extract with ether. The organic layers were dried with MgSO 4 and the solvent removed under reduced pressure. The crude was purified by flash chromatography (hexane/AcOEt, 50:50) giving 110 mg (30%) of 5-(2,3-dichloro-4-methoxyphenyl)-2-(2-(methylthio)thiazol-5-yl)pyridine.
[0141] 1 H NMR (400 MHz, CDCl 3 ), δ (ppm): 8.57 (1H, d); 8.12 (1H, s); 7.77 (1H, dd); 7.66 (1H, d); 7.22 (1H, d); 6.97 (1H, d); 3.97 (3H, s); 2.75 (3H, s)
24) 5-(2,3-dichloro-4-methoxyphenyl)-2-(thiazol-5-yl)pyridine
[0142]
[0143] Pd(PPh 3 ) 4 (100 mg, 0.1 mmol) was added portionwise to a stirred solution of 2,3-dichloro-4-methoxyphenylboronic acid (220 mg, 1.0 mmol) and 5-bromo-2-(thiazol-5-yl)pyridine (240 mg, 1.0 mmol) in dioxane (5 ml) under inert atmosphere. A solution of K 2 CO 3 (1 g, 7.2 mmol) in water (10 ml) was then added, and the reaction was refluxed for 14 h. After quenching with saturated Na 2 CO 3 solution, the mixture was extract with ether. The organic layers were dried with MgSO 4 and the solvent removed under reduced pressure. The crude was purified by flash chromatography (hexane/AcOEt 50:50) giving 140 mg (30%) of 5-(2,3-dichloro-4-methoxyphenyl)-2-(2-(methylthio)thiazol-5-yl)pyridine.
[0144] 1 H NMR (400 MHz, CDCl 3 ), δ (ppm): 8.90 (1H, s); 8.63(1H, d); 8.45 (1H, s); 7.84 (1H dd); 7.79 (1H, d); 7.23 (1H, d); 6.99 (1H, d); 3.98 (3H, s)
25) 3-(6-(thiazol-2-yl)pyridin-3-yl)pyridine
[0145]
[0146] Pd(PPh 3 ) 4 (100 mg, 0.1 mmol) was added portiowise to a stirred solution of 5-bromo-2-(thiazol-2-yl)pyridine (480 mg, 2.0 mmol) in dry toluene (20 ml) under inert atmosphere, followed by addition of pyridin-3-yl-3-boronic acid (280 mg, 2.3 mmol) in EtOH (5 ml). A 2 N aqueous solution of Na 2 CO 3 (2.5 ml, 5 mmol) was then added and the reaction refluxed for 12 h. The solution was diluted with ether washed with saturated Na 2 CO 3 solution, and the organic layers dried with MgSO 4 . The solvent was removed under reduced pressure. The crude was purified by flash chromatography (hexane/AcOEt 90:10), giving 300 mg (60%) of 3-(6-(thiazol-2-yl)pyridin-3-yl)pyridine.
[0147] 1 H NMR (400 MHz, CDCl 3 ), δ (ppm): 8.91 (1H, d); 8.85 (1H, dd); 8.68 (1H, dd); 8.30 (1H, d); 8.01 (1H, dd); 7.96 (1H, dd); 7.93 (1H, dt); 7.49 (1H, d); 7.45 (1H, d)
26) ethyl 7-(diethylamino)heptanoate
[0148]
[0149] Diethylammine (0.43 ml, 4.2 mmol) and sodium iodide(0.14 g, 0.9 mmol) were added to a stirred solution of ethyl 7-bromoheptanoate (0.5 g, 2.1 mmol) in toluene (20 ml). The reaction mixture was refluxed for 36 h, cooled to room temperature, and then filtered. The organic layers were washed with saturated Na 2 CO 3 solution, dried over MgSO4 and concentrated in vacuo giving 0.34 g (70%) of ethyl 7-(diethylamino)heptanoate.
[0150] 1l H NMR ( 400 MHz, DMSOd 6 ), δ (ppm): 1.0 (6H, t), 1.25 (3H, t,), 1.2-1.3 (4H, m), 1.5-1.6 (2H, m), 1.6-1.7 (2H, m), 2.3 (2H, t,) 2.4 (2H, m), 2.55 (4H, q), 4.1 (2H,).
[0151] GC-MS: 229 (M −• ) 214, 200, 156.
27) 7-(diethylamino)heptanoic acid
[0152]
[0153] A 1 M aqueous solution of LiOH (4 ml) was added in 10 minutes to a stirred solution of Ethyl 7-bromoheptanoate (0.35 g, 1.5 mmol) in dioxane (15 ml). The reaction mixture was stirred at rt for 2 h, neutralized with diluted HCl and concentrated under reduced pressure until a white solid precipitates. The solid was then suspended to a solution of CHCl 3 /1% TEA, filtered and the organic layers was concentrated in vacuo giving 0.3 g (quantitative yield) of 7-(diethylamino)heptanoic acid.
[0154] 1 H NMR (400 MHz, DMSOd 6 ), δ (ppm): 0.9 (t, 3H, CH 3 ammina), 1.19-1.38 (m, 6H, CH 2 ), 1.45 (qui, 2H, CH 2 ), 2.1 (t, 2H, CH 2 COOH), 2.3 (t, 2H, CH 2 ), 2.4 (q, 4H; CH 2 ammina).
28) 7-(diethylamino)heptanoyl chloride
[0155]
[0156] Oxalil chloride (0.13 ml, 1.5 mmol) was added dropwise to a solution of 7-(diethylamino)heptanoicacid (0.3 g, 1.5 mmol) in dry THF under inert atmosphere and then two drops of dimethylformammide were added. The reaction mixture was refluxed for 15 minutes, cooled, concentrated in vacuo and used without further purification.
29) N-(5-(9H-fluoren-7-yl)thiazol-2-yl)-7-(diethylamino)heptanamide (r105)
[0157]
[0158] Procedure 1:
[0159] BOP (1 mmol, 0.44 g) and DIEA (3 mmol, 0.5 ml) were added to a stirred solution of 7-(diethylamino)heptanoicacid (1 mmol, 200 mg) in dry DCM (10 ml) under inert atmosphere. After 30 minutes was added the organic amine. The reaction was stirred at rt for additional 18 h and the solvent was removed under reduced pressure. The crude was purified by flash chromatography (CHCl 3 97%, NEt 3 2%, CH 3 OH 1%) giving 220 mg (50%) of N-(5-(9H-fluoren-7-ypthiazol-2-yl)-7-(diethylamino)heptanamide.
[0160] Procedure 2:
[0161] DCC (1.5 mmol, 0.3 g) and HBTU (3 mmol, 1.15 g) were added to a stirred solution of 7-(diethylamino)heptanoicacid (1 mmol, 200 mg) in dry DMF (10 ml) under inert atmosphere. After 5 minutes at rt, a solution of organic amine (1 mmol) in dry DMF (1 ml) was added. The reaction was stirred at RT for 18 h, and the solvent was removed under reduced pressure. The crude was purified by flash chromatography (CHCl 3 97%, NEt 3 2%, CH 3 OH 1%) giving 140 mg (30%) of N-(5-(9H-fluoren-7-yl)thiazol-2-yl)-7-(diethylamino)heptanamide.
[0162] 1 H NMR (400 MHz, CDCl 3 ), δ (ppm): δ (ppm): 1.03 (t, 6H), 1.15 (m, 4H), 1.36(m, 2H), 1.58(dqu, 2H), 2.22 (t, 2H), 2.34 (m, 2H), 2.53 (q, 4H), 3.95 (s, 2H), 7.19 (s, 1H), 7.32 (t, 1H), 7.39 (t, 1H), 7.56 (d, 1H), 7.83 (m, 3H), 8.01 (s, 1H).
30) 3-(methoxycarbonyl)propanoic acid
[0163]
[0164] BF3:Et 2 O (0.01 mmol) was added dropwise to a solution of dihydrofuran-2,5-dione (2 g, 0.02 mol) in MeOH (12 ml) under inert atmosphere. After 5 minutes at rt the mixture becomes clear, a saturated solution of NaHCO 3 was added, and the aqueous layers was washed with ether. The aqueous solutions was acidified with diluite HCl and extracted with ether. The ethereal phase was washed with brine, dried over MgSO 4 , and solvent was removed in vacuo giving 3-(methoxycarbonyl)propanoic acid 0.8 g (30%) as a white solid.
[0165] 1H NMR (400 MHz, CDCl3), δ (ppm):2.59-2.64 (m, 4H), 3.71(s, 3H).
31) 3-(5-(9H-fluoren-7-yl)thiazol-2-ylcarbamoyl)propanoate
[0166]
[0167] BOP (1.01 g, 2.3 mmol) and DIEA (1.2 ml, 6.8 mmol) were added to a stirred solution of 3-(methoxycarbonyl)propanoic acid (0.3 g, 2.3 mmol) in dry DCM (12 mL) under inert atmosphere. After 30 minutes 5-(9H-fluoren-7-yl)thiazol-2-amine (0.6 g, 2.3 mmol) was added. The reaction was stirred at rt for 18 h and the solvent was removed under reduced pressure. The crude was purified by flash chromatography (CHCl 3 /CH 3 OH 99:1) and crystallized in diethyl ether, giving 440 mg of 3-(5-(9H-fluoren-7-yl)thiazol-2-ylcarbamoyl)propanoate, 50% yield.) as a yellow solid.
[0168] 1H NMR (400 MHz, CDCl3), δ (ppm):2.60-2.77 (m, 4H), 3.59 (s, 3H), 3.96 (s, 2H), 7.30 (t, 1H), 7.37 (t, 1H), 7.58 (d, 1H), 7.63 (s, 1H), 7.89 (d, 1H), 7.93 (s, 2H), 8.09(s, 1H).
32) N-(5-(9H-fluoren-7-yl)thiazol-2-yl)-4-hydroxybutanamide (r108)
[0169]
[0170] LiCl (0.022 g, 0.52 mmol) was added to a stirred solution of 3-(5-(9H-fluoren-7-yl)thiazol-2-ylcarbamoyl)propanoate (0.1 g, 26 mmol) in 2:1 THF/EtOH (5 mL) at rt under inert atmosphere. After complete dissolution of the inorganic salt NaBH 4 (0.02 g, 0.52 mmol) was added portionwise. After 12 h the reaction mixture was quenched with diluted HCl and the solvent removed under pressure. The crude was purified by flash chromatography (CH 3 Cl/CH 3 OH 95:5) giving 30 mg (30%) of N-(5-(9H-fluoren-7-yl)thiazol-2-yl)-4-hydroxybutanamide.
[0171] 1 H NMR (400 MHz, CDCl 3 ), δ (ppm):1.73 (m, 2H), 2.48(m, 2H), 3.41(m, 2H), 3.96 (s, 2H), 7.30(t, 1H), 7.37 (t, 1H), 7.58 (d, 1H), 7.62 (s, 1H), 7.89(d, 1H), 7.92 (s, 2H), 8.09 (s, 1H).
33) N-[5-(9H-Fluoren-2-yl)-thiazol-2-yl]-3-(4-methyl-piperazin-1-yl)-propionamide
[0172]
[0173] Acryloyl chloride (0.026 ml, 0.32 mmol) was added dropwise to a stirred solution of 5-(9H-fluoren-7-yl)thiazol-2-amine (40 mg, 0.15 mmol) and Et 3 N (0.046 ml, 0.32 mmol) in dry DCM (5 ml) under inert atmosphere. After 20 minutes, N-methyl piperazine (0.0134 ml, 0.12 mmol) was added. The reaction was stirred at rt for 12, the solvent was removed reduce pressure, dissolved in EtOAc and washed with aqueous Na 2 CO 3 . The organic layers were dried with MgSO 4 and concentrated in vacuo. The crude was purified by flash chromatography (CH 2 Cl 2 /EtOH/Et 3 N 91:8:1), giving N-[5-(9H-Fluoren-2-yl)-thiazol-2-yl]-3-(4-methyl-piperazin-1-yl)-propionamide as a brown solid.
[0174] 1 H-NMR (CDCl 3 , 400 MHz), δ (ppm): 8.10 (1H, bs), 7.92 (2H, m), 7.90 (1H, d), 7.60 (1H, s) 7.40 (2H, m) 3.9 (2H, s), 2.90 (8H, m), 2.83 (2H, t), 2.60 (2H, CH 2 ), 2.20 (3H, s).
34) (4-Methyl-piperazin-1-yl)-acetic acid ethyl ester
[0175]
[0176] K 2 CO 3 (2.48 g, 18 mmol) and N-Methyl piperazine (2 mL, 18 mmol) were added to a solution of Bromo Ethyl Ester (2 mL, 18 mmol) in dry DMF (18 ml) under inert atmosphere. After 30 minutes at 50° C. the mixture was diluted with DCM, filtered and the organic layers distilled in vacuo giving (4-Methyl-piperazin-1-yl)-acetic acid ethyl ester as a brown oil.
[0177] 1 H-NMR (CDCl 3 , 400 MHz), δ (ppm): 4.18 (2H, q), 3.20 (2H, s), 2.60 (8H, m), 2.26 (3H, s), 1.26 (3H, t)
35) 2-(4-methylpiperazin-1-yl)acetic acid
[0178]
[0179] NaOH 3 N (4.8 mL, 14.4 mmol) was added to a stirred solution of (4-Methyl-piperazin-1-yl)-acetic acid ethyl ester (2.26 g, 12.13 mmol) in dioxane/water (60:40, 20 mL) After 4 h, the reaction was quenched with diluited HCl, diluted with DCM, filtered and the organic layers distilled in vacuo giving (4-Methyl-piperazin-1-yl)-acetic acid as a brown oil.
[0180] 1 H-NMR (DMSO, 400 MHz), δ (ppm): 4.0 (1H, bs), 3.02 (2H, s), 2.50 (8H, m), 2.16 (3H, s).
36) 2-(4-methylpiperazin-1-yl)acetyl chloride
[0181]
[0182] Oxalil chloride (0.3 ml, 3.47 mmol) was added dropwise to a stirred solution of (4-Methyl-piperazin-1-yl)-acetic acid (500 mg, 3.16 mmol) 15 ml of dry THF and placed under inert atmosphere. Two drops of dimethylformammide were added. The reaction mixture was refluxed for 1 h, and the solvent removed under reduced pressure giving 440 mg (80%) (4-Methyl-piperazin-1-yl)-acetyl chloride as a yellow solid.
[0183] 1 H-NMR (DMSO, 400 MHz), δ (ppm): 3.20 (2H, s), 2.78 (8H, m), 2.60 (3H, s).
37) N-(5-(9H-fluoren-7-yl)thiazol-2-yl)-2-(4-methylpiperazin-1-yl)acetamide (r106)
[0184]
[0185] DCC (0.31 g, 1.5 mmol) and HBTU (1.37 g, 3 mmol) were added to a stirred solution of (4-Methyl-piperazin-1-yl)-acetic acid (0.165 g, 1 mmol) in dry DMF (10 ml) under inert atmosphere was placed, and the mixture was stirred at RT for 5 minutes. The solution of 5-(9H-fluoren-7-yl)thiazol-2-amine (0.264 g, 1 mmol) in dry DMF (10 ml) was added dropwise. After 18 h at rt, the solvent was removed under reduced pressure. The crude was purified by flash chromatography (CHCl 3 /Et 3 N/MeOH 95:4:1) and then crystallized from ethyl ether giving 160 mg (40%) of N-(5-(9H-fluoren-7-yl)thiazol-2-yl)-2-(4-methylpiperazin-1-yl)acetamide.
[0186] 1 H NMR (400 MHz, DMSOd 6 ), δ (ppm): 2.13 (3H, s), 2.32(4H, bs), 2.5 (4H, bs), 3.28 (2H, s), 3.90 (2H, s), 7.31 (1H, t), 7.38 (t, 1H), 7.58 (d, 1H), 7.66 (s, 1H), 7.89 (d, 1H), 7.92 (s, 2H), 8.1 (s, 1H).
38) 5-bromofuran-2-carbonyl chloride
[0187]
[0188] Oxalil chloride (0.26 ml, 2.86 mmol) was added dropwise, to a stirred solution of 5-bromofuran-2-carboxylic acid (500 mg, 2.6 mmol) in dry THF(5 mL) under inert atmosphere. Two drops of dimethylformammide were added. The reaction mixture was refluxed for 15 minutes and the solvent removed under reduced pressure giving 0.48 g (90%) of 5-bromofuran-2-carbonyl chloride as a brown solid.
[0189] 1 H NMR (400 MHz, DMSOd 6 ), δ (ppm): 7,234 (1H, s); 6,795 (1H, s)
39) N-(5-(9H-fluoren-2-yl)thiazol-2-yl)-5-bromofuran-2-carboxamide (r88)
[0190]
[0191] DMF was added to a stirred suspension of 5-bromofuran-2-carboxylic chloride (0.280 g, 1.35 mmol) and 5-(9H-fluoren-7-yl)thiazol-2-amine (0.3 g, 1.14 mmol) in THF (10 ml), until complete dissolution of the reagents. Et 3 N (1 ml, 5.4 mmol) was then added. After 14 h at rt the solvent was removed under reduced pressure, the residue diluted with CHCl 3 and washed with brine. The organic layers were dried over MgSO 4 and concentrated under reduced pressure. The crude was purified by flash chromatography (CH 2 Cl 2 /EtOH/Et 3 N 93:6:1) giving 0.15 g (25%) of N-(5-(9H-fluoren-2-yl)thiazol-2-yl)-5-bromofuran-2-carboxamide.
[0192] 1 H NMR (400 MHz, DMSOd6), δ (ppm):3.98 (2H, s), 6.87 (1H, d), 7.31(1H, t), 7.38(1H, t), 7.58 (1H, d), 7.64 (1H, d), 7.69 (2H, s), 7.91(1H, d), 7.92-7.99(2H, m), 8.14 (1H, s).
40) 4-(4-methylpiperazin-1-carbonyl)-phenyl-boronic acid
[0193]
[0194] N-methyl-piperazine (0.22 ml, 1.98 mmol) and PyBrOP (0.93 g, 2 mmol) were added to a stirred solution of 4-carboxy phenyl boronic acid (0.33 g, 1.98 mmol) and DIEA (0.7 ml, 4 mmol) in dry DMF (7 ml) under inert atmosphere. After 14 h at rt the solvent was removed under reduced pressure and crude purified by flash chromatography (CH2Cl2/EtOH/Et3N 75:20:5) giving 0.19 g (40%) of 4-(4-methylpiperazin-1-carbonyl)-phenyl-boronic acid.
[0195] 1H NMR (400 MHz, CD3OD), δ (ppm): 7.85 (2H, d); 7.66 (2H, bd)
41) 5-[4-(4-Methyl-piperazine-1-carbonyl)-phenyl]-furan-2-carboxylic acid[5-(9H-fluoren-2-yl)-thiazol-2-yl]-amide (r104)
[0196]
[0197] 4-(4-methylpiperazin-1-carbonyl)-phenyl-boronic acid (0.170 g, 0.68 mmol) was added to a stirred solution of N-(5-(9H-fluoren-2-yl)thiazol-2-yl)-5-bromofuran-2-carboxamide (0.300 g, 0.68 mmol) in dioxane (50 mL) under inert atmosphere. A solution of K 2 CO 3 (0.3 g, 2.04 mmol) in H 2 O (10 ml) was then added and the mixture degassed. After addition of a catalytic amount of Pd(PPh 3 ) 2 (20 mg), the reaction was heated to 100° C. for 2 h, cooled to rt and stirred for additional 10 h. Solvents were removed under reduce pressure and the crude purified by flash chromatography (CH 2 Cl 2 /MeOH/EtN 3 79:20:1), giving 50 mg (13%) of 5-[4-(4-Methyl-piperazine-1-carbonyl)-phenyl]-furan-2-carboxylic acid[5-(9H-fluoren-2-yl)-thiazol-2-yl]-amide.
[0198] 1 H NMR (400 MHz, DMSOd 6 ), δ (ppm):2.20 (s, 3H), 2.26-2.45 (m, 8H), 3.99, (s, 2H), 7.27-7.34 (m, 2H), 7.39 (t, 1H), 7.51 (d, 2H), 7.60 (d, 1H), 7.66 (d, 1H), 7.74 (d, 1H), 7.87-8.05 (m, 4H), 8.12 (d, 2H), 8.19 (s, 1H).
42) N-(5-(9H-fluoren-7-yl)thiazol-2-yl)nicotinamide (r86)
[0199]
[0200] Et 3 N (2 ml, 15 mmol) was added to a stirred suspension of nicotinoyl chloride hydrochloride (0.270 g, 1.5 mmol) and 5-(9H-fluoren-7-yl)thiazol-2-amine (0.270 g, 1 mmol) in DCM (15 ml). After 2 d at rt, the solvents were removed under reduced pressure, diluted with DCM and washed with brine. The organic layers were dried with MgSO4 and concentrated in vacuo. The crude was purified by flash chromatography (CH 2 Cl 2 /MeOH/EtN 3 , 97:2:1) giving 36 mg (10%) of N-(5-(9H-fluoren-7-yl)thiazol-2-yl)nicotinamide.
[0201] 1H NMR (400 MHz, CDCl3), δ (ppm): 8.91 (1H, d); 8.69 (1H, s); 8.62 (1H, bs); 8.00 (1H, bs); 7.89-7.83 (3H, m); 7.60 (2H, m); 7.42 (2H, m); 7.24 (1H, s) 4.01 (2H, s).
43) N-(5-(9H-fluoren-7-yl)thiazol-2-yl)-2-iodobenzamide (r87)
[0202]
[0203] Until complete dissolution of the reagents DMF, was added to a stirred suspension of 2-iodobenzoyl chloride (0.390 g, 1.5 mmol) and 5-(9H-fluoren-7-yl)thiazol-2-amine (0.3 g, 1.14 mmol) in dry THF (10 ml) under inert atmosphere. Et 3 N (1.8 ml, 12 mmol) was then added. After 14 h at rt the solvents were removed under reduced pressure, and the residue was diluted with trichloromethane and washed with brine. The organic layers were dried with MgSO4 and concentrated under reduced pressure. The crude was purified by flash chromatography (CH 2 Cl 2 /MeOH/Et 3 N, 97:2:1) giving 110 mg of N-(5-(9H-fluoren-7-yl)thiazol-2-yl)-2-iodobenzamide.
[0204] 1 H NMR (400 MHz, CDCl 3 ), δ (ppm): 8.30 (1H, s), 8.10 (1H, s), 8.00-7.90 (2H, m), 7.82-7.77 (2H, m), 7.420-7.29 (3H, m), 7.24 (1H, s), 7.17 (1H, m), 7.025 (1H, s); 3.93 (2H, s).
44) 2-(methylthio)thiazole
[0205] A solution of n-BuLi (2.5 M, 2.1 ml, 5.2 mmol) in hexanes was added dropwise to a stirred solution of thiazole (0.36 ml, 5 mmol) in dry THF (20 ml) at −78° C. under inert atmosphere. After 1 h, 1,2-dimethyldisulfane (5.2 mmol) was added. The reaction mixture was stirred for additional 2 h, quenched with saturated Na 2 CO 3 , extracted with ether, and the organic layers dried with MgSO 4 . The crude was purified by distillation under reduce pressure giving 0.52 g (80%) of 2-(methylthio)thiazole.
[0206] 1 H NMR (400 MHz, CDCl 3 ), δ (ppm): 7.65 (1H, d); 7.20 (1H, d); 2.70 (3H, s);
45) 5-(trimethylstannyl)-2-(methylthio)thiazole
[0207] A solution of n-BuLi (2.5 M, 2.1 ml, 5.2 mmol) in hexanes was added dropwise to a stirred solution of 2-(methylthio)thiazole (0.52 g, 4 mmol) in dry THF (20 ml) at −78° C. under inert atmosphere. After 1 h Me 3 SnCl (5 mmol, 1 g) was added portionwise. After 14 h the reaction was quenched with saturated Na2CO3, extracted with ether and the organic layers were dried with MgSO4. The crude was purified by distillation under reduce pressure giving 0.90 g (70%) of 5-(trimethylstannyl)-2-(methylthio)thiazole.
[0208] 1 H NMR (400 MHz, CDCl 3 ), δ (ppm): 7.57 (1H, s); 2.69 (3H, s); 0.38 (3H, s)
46) 1-(9-benzenesulfonyl-9H-carbazol-2-yl)-ethanone 1
[0209]
[0210] 60% NaH in paraffin (21.2 mg, 0.53 mmol) was added to a stirred solution of 2-acetylcarbazole (100 mg, 0.48 mmol) in 3.5 mL of anhydrous THF at 0° C. After stirring at 0° C. for 20 min, benzenesulfonyl chloride (74 μL, 0.57 mmol) was added dropwise. The reaction mixture was stirred for 12 hours and then poured with 5% aqueous NaHCO 3 and extracted with EtOAc. The combined organic layers were dried (MgSO 4 ), and the solvent was removed under reduced pressure. The crude product was purified by recrystallization from EtOAc to furnish the desired compound in 80% (134 mg, 0.383 mmol) as a white solid; MS (ESI) m/z 350 [M+H + ]; 1 H NMR (CDCl 3 ; 300 MHz) δ 8.93 (s, 1H), 8.36 (d, 1H, J=8.5 Hz), 8.02-7.95 (m, 3H), 7.83 (d, 2H, J≈7.9 Hz), 7.57 (ddd, 1H, J=7.8 Hz, J=7.3 Hz, J=1.1 Hz), 7.48-7.32 (m, 4H), 2.75 (s, 3H); 13 C NMR (CDCl 3 ; 300 MHz) δ 197.5 (C), 139.5 (C), 138.0 (C), 137.6 (C), 136.0 (C), 134.0 (CH), 130.1 (C), 129.1 (2 CH), 128.8 (CH), 126.4 (2 CH), 125.3 (CH), 124.3 (CH), 124.0 (CH), 120.8 (CH), 119.9 (CH), 115.3 (CH), 115.1 (C), 26.9 (CH 3 ).
47) 4-(9-benzenesulfonyl-9H-carbazol-2-yl)-thiazol-2-ylamine 3
[0211]
[0212] To a suspension of CuBr 2 (1.28 g, 5.72 mmol) in EtOAc (13 mL) was added a solution of 2-acetyl-1-phenylsulfonyl-1H-carbazole (1) (1 g, 2.86 mmol) in EtOAc (13 mL) under argon at room temperature. The mixture was stirred under reflux for 90 min. 645 mg of CuBr 2 (2.88 mmol) were added in the mixture to allow complete conversion to the monobrominated derivative. After cooling, precipitates were removed by filtration and washed with ethyl acetate. Combined filtrates were washed with saturated aqueous NaHCO 3 solution and brine, dried over anhydrous MgSO 4 and evaporated to dryness in vacuo. The product 2 was used immediately without further purification.
[0213] To a stirred suspension of 2 (1.10 g, 2.57 mmol) in EtOH (15 mL) was added thiourea (195 mg, 76.12 mmol) and the mixture was heated at 70° C. for 2 h. After cooling to room temperature, the solvent was evaporated to dryness. The resulting solid was stirred in a mixture of EtOAc/saturated aqueous NaHCO 3 solution (2/1) until dissolution, and then extracted with EtOAc. The organic layer was washed with brine, dried over anhydrous MgSO 4 , filtrated and solvent was removed under reduced pressure. The crude product was purified by flash chromatography (EtOAc) to afford 3 in 69% yield (801 mg, 1.968 mmol) as a yellow solid; MS (ESI) m/z 408 [M+H + ]; 1 H NMR ((CD 3 ) 2 CO; 300 MHz) δ 8.92 (d, 1H, J=0.8 Hz), 8.33 (d, 1H, J=8.5 Hz), 8.05 (d, 1H, J=6.0 Hz), 8.03 (d, 1H, J=8.1 Hz), 7.94-7.89 (m, 3 H), 7.62-7.38 (m, 5H), 7.13 (s, 1H), 6.60 (bs, 2H); 13 C NMR (DMSO-d 6 ; 300 MHz) δ 168.4 (C), 149.6 (C), 138.2 (C), 137.8 (C), 136.6 (C), 134.8 (C), 134.7 (CH), 129.8 (2×CH), 127.6 (CH), 126.0 (2×CH), 125.8 (C), 124.7 (C), 124.5 (CH), 122.1 (CH), 120.7 (CH), 120.6 (CH), 114.6 (CH), 111.8 (CH), 102.7 (CH).
[0000]
[0214] Intermediate (2) was isolated as a white solid; MS (EI) m/z 427, 429 [M + ; 79 Br, 81 Br]; 1 H NMR (CDCl 3 ; 300 MHz) δ 8.96 (s, 1H), 8.38 (d, 1H, J=9.0 Hz), 8.02-7.95 (m, 3H), 7.86 (dd, 2H, J≈7.4 Hz), 7.57 (ddd, 1H, J=7.8 Hz, J=7.3 Hz, J=1.1 Hz), 7.48-7.32 (m, 4H), 4.59 (s, 2H); 13 C NMR (DMSO-d 6 ; 300 MHz) δ 191.1(C), 138.7 (C), 137.2 (C), 136.2 (C), 135.0 (CH), 133.0 (C), 130.1 (C), 129.8 (2×CH), 129.5 (CH), 126.3 (2×CH), 125.0 (CH), 124.8 (CH), 124.7 (C), 121.9 (CH), 121.0 (CH), 114.8 (CH), 114.7 (CH), 34.5 (CH 2 ).
48) General Procedure for the preparation of N-acyl substituted thiazole
[0215] To a 0.15 M stirred suspension of the (4-aminothiazol-2-yl)-1-phenylsulfonyl-1H-carbazole 3 in anhydrous CH 2 Cl 2 was added anhydrous pyridine (2 eq) and acyl chloride (1.5 eq) at room temperature under inert atmosphere. The mixture was stirred at room temperature until completion of the reaction (followed by T.L.C.). The resulting mixture was quenched with H 2 O and extracted three times with CH 2 Cl 2 . The resulting organic layers were washed with NH 4 Cl saturated aqueous solution and brine, dried over MgSO 4 , filtered and solvents were removed under reduced pressure.
49) N-[4-(9-Benzenesulfonyl-9H-carbazol-2-yl)-thiazol-2-yl]-acetamide 4
[0216]
[0217] The desired compound is obtained in 64% yield (70 mg from 100 mg of 3, 0.156 mmol) by flash chromatography on silica gel (CH 2 Cl 2 ) as a yellow solid; MS (ESI) m/z 448 [M+H + ]; 1 HNMR (CDCl 3 ; 300 MHz) δ 9.57 (bs, 1H), 8.83 (s, 1H), 8.32 (d, 1H, J=8.5 Hz), 7.93-7.88 (m, 3H), 7.81 (d, 2H, J≈7.9 Hz), 7.50 (ddd, 1H, J=8.2 Hz, J=7.9 Hz, J=1.1 Hz),7.44-7.39 (m, 2H), 7.31-7.27 (m, 3H), 2.02 (s, 3H); 13 C NMR (DMSO-d 6 ; 300 MHz) δ 168.8 (C); 158.8 (C), 148.4 (C), 138.2 (C), 137.8 (C), 136.5 (C), 134.8 (CH), 134.1 (C), 129.8 (2×CH), 127.8 (CH), 126.0 (2×CH), 125.6 (C), 125.2 (C), 124.5 (CH), 122.3 (CH), 121.0 (CH), 120.7 (CH), 114.6 (CH), 111.7 (CH), 108.9 (CH), 22.5 (CH 3 ).
50) N-[4-(9-Benzenesulfonyl-9H-carbazol-2-yl)-thiazol-2-yl]-benzamide 5
[0218]
[0219] The desired compound is obtained in 61% yield (76 mg from 100 mg of 3, 0.149 mmol) by flash chromatography on silica gel (CHCl 3 /Pet. Eth. 1/1) as a yellow solid; MS (ESI) m/z 510 [M+H + ], 1018 [2M+H + ]; 1 H NMR (CDCl 3 ; 300 MHz) δ 9.96 (bs, 1H), 8.91 (s, 1H), 8.32 (d, 1H, J=8.3 Hz), 8.03 (d, 2H, J≈7.7 Hz), 7.91-7.84 (m, 5H), 7.63-7.29 (m, 9H); 13 C NMR (CDCl 3 ; 300 MHz) δ 164.9 (C), 158.8 (C), 150.0 (C), 139.0 (C), 138.9 (C), 137.9 (C), 133.0 (CH), 133.8 (C), 133.0 (CH), 131.9 (C), 129.2 (2×CH), 129.0 (2×CH), 127.2 (3×CH), 126.6 (2×CH), 126.3 (CH), 126.2 (C), 124.2 (CH), 122.3 (CH), 120.3 (CH), 120.2 (CH), 115.2 (CH), 112.9 (CH), 108.8 (C).
51) Biphenyl-4-carboxylic acid[4-(9-Benzenesulfonyl-9H-carbazol-2-yl)-thiazol-2-yl]-amide 6
[0220]
[0221] The desired compound is obtained in 60% yield (174 mg from 200 mg of 3, 0.297 mmol) by flash chromatography on silica gel (CHCl 3 /toluene 1/1) as a yellow solid; MS (ESI) m/z 586 [M+H + ], 1170 [2M+H + ]; 1 H NMR (CDCl 3 ; 300 MHz) δ 9.89 (bs, 1H), 8.92 (s, 1H), 8.32 (d, 1H, J=8.3 Hz), 8.08 (d, 1H, J=8.5 Hz), 7.93-7.84 (m, 5H), 7.75 (d, 2H, J≈8.3 Hz), 7.64 (d, 2H, J≈7.0 Hz), 7.52-7.29 (m, 9H); 13 C NMR (CDCl 3 ; 300 MHz) δ 164.8 (C), 159.0 (C), 150.0 (C), 154.4 (C), 139.5 (C), 138.8 (C), 138.7 (C), 137.9 (C), 133.9 (CH), 133.8 (C), 130.4 (C), 129.2 (2×CH), 129.0 (2×CH), 128.3 (CH), 128.0 (2×CH), 127.5 (CH), 127.3 (2×CH), 127.2 (2×CH), 126.5 (2×CH), 126.1 (C), 126.0 (C), 124.1 (CH), 122.2 (CH), 120.2 (CH), 120.1 (CH), 115.1 (CH), 112,8 (CH), 108.8 (CH).
52) General Procedure for the Coupling Peptide
[0222] To a 2 M stirred mixture of the carboxylic acid in anhydrous DMF was added a 0.5 M solution of (4-aminothiazol-2-yl)-1-phenylsulfonyl-1H-carbazole 3 in anhydrous DMF, a 2 M solution of EDCI in dry DMF and 0.4 eq of DMAP, at room temperature under inert atmosphere. The reaction mixture was stirred at room temperature for 12 hours and DMF was evaporated in vacuo.
53) N-[4-(9-Benzenesulfonyl-9H-carbazol-2-yl)-thiazol-2-yl]-4-(4-methyl-piperazin-1-ylmethyl)-benzamide 7
[0223]
[0224] The desired compound is obtained in 24% yield (56 mg from 150 mg of 3, 0.090 mmol) by flash chromatography on silica gel (CH 2 Cl 2 /MeOH 95/5) as a white solid; MS (ESI) m/z 622 [M+H + ]; 1 HNMR (CDCl 3 ; 300 MHz) 9.86 (bs, 1H) 8.91 (s, 1H), 8.32 (d, 1H, J=8.3 Hz), 7.96-7.82 (m, 7H), 7.51-7.31 (m, 8H), 3.58 (s, 2H), 2.51 (br. m, 8H), 2.32 (s, 3H); 13 C NMR (DMSO-d 6 ; 300 MHz) δ 164.9 (C), 158.5 (C), 148.7 (C), 142.8 (C), 138.1 (C), 137.8 (C), 136.6 (C), 134.3 (CH), 133.9 (C), 130.6 (C), 129.4 (2×CH), 128.4 (2×CH), 127.9 (2×CH), 127.4 (CH), 125.7 (2×CH), 125.4 (C), 125.0 (C), 124.2 (CH), 122.2 (CH), 120.5 (CH), 120.3 (CH), 114.3 (CH), 111.6 (CH), 109.2 (CH), 60.8 (CH 2 ), 53.7 (2×CH 2 ), 51.2 (2×CH 2 ), 44.3 (CH 3 ).
54) 5-Bromo-furan-2-carboxylic acid[4-(9-benzenesulfonyl-9H-carbazol-2-yl)-thiazol-2-yl]-amide 8
[0225]
[0226] The desired compound is obtained in 20% yield (189 mg from 653 mg of 3, 0.328 mmol) by flash chromatography on silica gel (CH 2 Cl 2 ) as a yellow solid; MS (ESI) m/z 577, 579 [M+H + ; 79 Br, 81 Br]; 1 H NMR (CDCl 3 ; 300 MHz) δ 10.13 (bs, 1H), 8.89 (s, 1H) 8.31 (d, 1H, J=8.3 Hz), 7.90-7.80 (m, 5H), 7.48 (ddd, 1H, J=8.5 Hz, J=7.4 Hz, J=1.3 Hz), 7.44 (ddd, 1H, J=7.5 Hz, J=1.2 Hz, J=1.1 Hz), 7.41-7.24 (m, 5H), 6.49 (d, 1H, J=3.6 Hz); 13 C NMR (DMSO-d 6 ; 300 MHz) δ 158.1 (C), 155.0 (C), 149.0 (C), 147.5 (C), 138.3 (C), 137.9 (C), 136.5 (C), 134.8 (CH), 134.0 (C), 129.8 (2×CH), 127.9 (CH), 127.5 (C), 126.1 (2×CH), 125.7 (C), 125.4 (C), 124.6 (CH), 122.5 (CH), 121.0 (CH), 120.8 (CH), 118.9 (CH), 114.7 (CH), 114.5 (CH), 111.8 (CH), 109.8 (CH).
55) 5-[4-(Piperazine-1-carbonyl)-phenyl]-furan-2-carboxylic acid[4-(9-benzenesulfonyl-9H-carbazol-2-yl)-thiazol-2-yl]-amide 9
[0227]
[0228] The compound (8) (113 mg, 0.19 mmol), [1-(4-methyl)-piperazinyl carbonyl]boronic acid (56 mg, 0.22 mmol), Pd(PPh 3 ) 4 (34 mg, 0.03 mmol) and K 2 CO 3 (79 mg, 0.57 mmol) in 1,4 dioxane (8 mL) and H 2 O (2 mL) was degased with argon and then stirred at 100° C. for 15 hours. Solvents were removed under reduced pressure. The crude product was purified by flash chromatography on silica gel (CH 2 Cl 2 /MeOH 95/5) to afford 3 in 64% yield (90 mg, 0.128 mmol) as green foam; MS (ESI) m/z 702 [M+H + ]; 1 H NMR (CDCl 3 ; 300 MHz) δ 10.36 (bs, 1H), 8.84 (d,1H, J=0.8 Hz), 8.29 (d, 1H, J=8.3 Hz), 7.86 (d, 2H, J≈7.9 Hz), 7.82-7.78 (m, 4H), 7.76 (s, 1H), 7.52-7.27 (m, 9H), 6.80 (d, 1H, J=3.8 Hz), 3.82 (br. m, 2H), 3.49 (br. m, 2H), 2.50 (br. m, 2H), 2.39 (br. m, 2H), 2.33 (s, 3H); 13 C NMR ((CD 3 ) 2 CO; 300 MHz) δ 169.6 (C), 158.7 (C), 157.0 (C), 156.5 (C), 150.5 (C), 146.6 (C), 139.7 (C), 139.4 (C), 138.2 (C), 137.5 (C), 135.2 (CH), 132.8 (CH), 132.7 (CH), 132.7 (CH), 132.5 (CH), 131.1 (C), 130.3 (2×CH), 129.5 (CH), 129.3 (CH), 128.7 (2×CH), 128.4 (CH), 127.2 (2×CH), 127.1 (C), 126.7 (C), 125.5 (2×CH), 125.3 (CH), 123.2 (CH), 121.3 (CH), 121.2 (CH), 119.8 (CH), 115.8 (CH), 113.3 (CH), 109.8 (CH), 109.7 (CH), 46.1 (CH 3 ).
56) General procedure for the deprotection of N-sulfonyl with tetrabutylammonium fluoride
[0229] To a 1 M mixture of compound (3-9) in anhydrous THF was added 4 eq of TBAF (1.0 M solution in THF), under inert atmosphere. The mixture was refluxed until completion of the reaction (followed by T.L.C, 2-3 hours). Solvent was removed and the residue was dissolved in CH 2 Cl 2 . The organic layer was washed with water, brine, dried over anhydrous MgSO 4 , filtered and the solvent was removed under reduced pressure.
57) 4-(9H-Carbazol-2-yl)-thiazol-2-ylamine 10 (r156)
[0230]
[0231] The residue was purified by flash chromatography on silica gel (CHCl 3 /MeOH 95/5) and recrystallized from EtOH to furnish the desired compound as a white solid in 29% yield (8.4 mg, 0.032 mmol); MS (ESI) m/z 266 [M+H + ]; 1 H NMR ((CD 3 ) 2 CO; 300 MHz) δ 11.11 (bs, 1H), 8.84 (m, 3H), 8.47 (dd, 1H, J=8.1 Hz, J=1.7 Hz), 8.25 (d, 1H, J=8.1 Hz), 8.12 (ddd, 1H, J=7.8 Hz, J=7.1 Hz, J=0.6 Hz), 7.95 (ddd, 1H, J=7.8 Hz J=7.1 Hz, J=0.6 Hz), 7.73 (s, 1H), 7.18 (bs, 2H).
58) N-[4-(9H-Carbazol-2-yl)-thiazol-2-yl]acetamide 11
[0232]
[0233] The residue was recrystallized from EtOH to furnish the desired compound as a white solid in 33% yield (15 mg, 0.049 mmol); MS (ESI) m/z 308 [M+H + ]; 1 H NMR ((CD 3 ) 2 CO); 300 MHz) δ 11.04 (bs, 1H), 10.37 (bs, 1H), 8.15-8.10 (m, 3H), 7.76 (dd, 1H, J=1.5 Hz, J=8.3 Hz), 7.52 (d, 1H, J=8.1 Hz), 7.49 (s, 1H), 7.37 (ddd, 1H, J=7.7 Hz, J=7.0 Hz, J=0.9 Hz), 7.17 (ddd, 1H, J=7.7 Hz, J=7.0 Hz, J=0.9 Hz), 2.29 (s 3H); HRMS calcd for C 17 H 13 N 3 OS [M+H] + 308.0858 found 308.0857
59) N-[4-(9H-Carbazol-2-yl)-thiazol-2-yl]-benzamide 12 (r158)
[0234]
[0235] The residue was recrystallized from EtOH to furnish the desired compound as a white solid in 42% yield (17 mg, 0.046 mmol); MS (EST) m/z 370 [M+H + ]; 1 H NMR ((CD 3 ) 2 CO); 300 MHz) δ 11.48 (bs, 1H), 10.44 (bs, 1H), 8.23 (d, 2H, J≈7.0 Hz), 8.16-8.11 (m, 3H), 7.81 (dd, 1H, J=8.2 Hz, J=1.5 Hz), 7.62 (m, 4H), 7.51 (d, 1H, J=8.2 Hz), 7.39 (ddd, 1H, J=7.6 Hz, J=7.3 Hz, J=1.0 Hz), 7.18 (ddd, 1H, J=7.6 Hz, J=7.3 Hz, J=1.0 Hz); HRMS calcd for C 22 H 15 N 3 OS [M+H] + 370.1014 found 370.1013.
60) Biphenyl-4-carboxylic acid 4-(9H-carbazol-2-yl)-thiazol-2-yl]-amide 13 (r169)
[0236]
[0237] The residue was obtained by hot filtration from CHCl 3 to furnish the desired compound as a white solid in 10% yield (14 mg, 0.031 mmol); MS (ESI) m/z 446 [M+H +]; 1 H NMR (DMSO-d 6 ; 300 MHz) δ 12.87 (bs, 1H), 11.37 (bs, 1H), 8.26 (d, 2H, J≈8.4 Hz), 8.17-8.09 (m, 3H), 7.88 (d, 2H, J≈8.4 Hz), 7.81-7.75 (m, 4H), 7.55-7.36 (m, 5H), 7.17(t, 1H, J=7.3 Hz); HRMS calcd for C 28 H 19 N 3 OS [M+H] + 446.1327 found 446.1326.
61) N-[4-(9H-carbazol-2-yl)-thiazol-2-yl]-4-(4-methyl-piperazin-1-ylmethyl)-benzamide 14
[0238]
[0239] The residue was recrystallized from EtOH to furnish the desired compound as a white solid in 50% yield (20 mg, 0.041 mmol); MS (ESI) m/z 482 [M+H + ]; 1 H NMR (DMSO-d 6 ; 300 MHz) δ 12.73 (bs, 1H), 11.35 (bs, 1H), 8.16-8.08 (m, 5H), 7.77 (dd, 1H, J=8.1 Hz, J=1.3 Hz), 7.71 (s, 1H), 7.51-7.46 (m, 3H), 7.38 (td, 1H, J=0.9 Hz, J=7.3 Hz), 7.16 (td, 1H, J=0.9 Hz, J=7.3 Hz), 3.55 (s, 2H), 2.39 (br. m, 4H), 2.34 (br. m, 4H), 2.15 (s, 3H); HRMS calcd for C 28 H 27 N 5 OS [M+H] + 482.2015 found 482.2015.
62) 5-Bromo-furan-2-carboxylic acid[4-(9H-carbazol-2-yl)-thiazol-2-yl]-amide 15 (r170)
[0240]
[0241] The residue was recrystallized from EtOH to furnish the desired compound as a yellow solid in 66% yield (25 mg, 0.057 mmol); MS (ESI) m/z 438, 440 [M+H + ; 79 Br, 81 Br]; 1 H NMR (DMSO-d 6 ; 300 MHz) δ 12.83 (bs, 1H), 11.34 (bs, 1H), 8.16-8.10 (m, 2H), 8.05 (d, 1H, J=1.0 Hz), 7.77-7.73 (m, 3H), 7.50 (d, 1H, J=8.1 Hz), 7.38 (ddd, 1H, J=7.6 Hz, J=7.2 Hz, J=1.0 Hz), 7.16 (ddd, 1H, J=7.6 Hz, J=7.2 Hz, J=1.0 Hz), 6.91 (d, 1H, J=3.6 Hz).
63) 5-[4-(Piperazine-1-carbonyl)-phenyl]-furan-2-carboxylic acid[4-(9H-carbazol-2-yl)-thiazol-2-yl]-amide 16
[0242]
[0243] The residue was filtrated after trituration in MeOH to furnish the desired compound as a white solid in 39% yield (22 mg, 0.039 mmol); MS (ESI) m/z 562 [M+H + ]; 1 H NMR (DMSO-d 6 at 70° C.; 300 MHz) δ 13.06, (bs, 1H), 11.14 (bs, 1H), 8.15-8.08 (m, 5H), 7.77 (dd, 1H, J=8.1 Hz, J=1.5 Hz), 7.65-7.63 (m, 2H), 7.54-7.49 (m, 3H), 7.39 (ddd, 1H, J=7.5 Hz, J=5.7 Hz, J=1.1 Hz), 7.25 (d, 1H, J=3.6 Hz), 7.17 (ddd, 1H, J=7.54 Hz, J=5.7 Hz, J=1.1 Hz), 3.51 (br. m, 4H), 2.36 (br. m, 4H), 2.23 (s, 3H); HRMS calcd for C 32 H 27 N 5 O 3 S [M+H] + 562.1913 found 562.1911.
[0000]
No.
Compound
Formula
Synthesis
64)
r113
General synthesis strategies (page 8) starting from (11)
65)
r121
General synthesis strategies
66)
r122
General synthesis strategies
67)
r124
General synthesis strategies
68)
r201
General synthesis strategies as described for r200 (17) using 2 equivalent excess of 5-bromofuran-2-carbonyl chloride (38)
69)
R89
Synthesis similar to r104 (41) with a final step consisting in a keton reduction of carbonyl piperazine moiety.
70)
R233
General synthesis for 4-(9H-Carbazol-2-yl)-thiazol (NH2 of r156 exchanged with —OH)
[0244] 2. Alk Kinase Inhibitory Activity
[0245] Method: ELISA-Based In Vitro Kinase Assay
[0246] Recombinant ALK kinase was expressed in SP insect cells using the pBlueBacHis2C baculovirus vector system and purified using an anion exchange Fast Flow Q-sepharose column (Amersham-Pharmacia Biotech) followed by HiTrap™-nickel affinity column (Amersham-Pharmacia Biotech). Purified ALK protein was used to screen inhibitors in the ELISA-based kinase assay. A Nunc Immuno 96 well plate was incubated overnight at 37° C. with coating solution (125 μl/well) containing ALK peptide substrate (ARDIYRASFFRKGGCAMLPVK) at various concentrations in PBS. Wells were then washed with 200 μl of wash buffer (PBS-Tween 0.05%) and left to dry for at least 2 hours at 37° C. The kinase reaction was performed in the presence of 50 mM Tris pH 7.5, 5 mM MnCl 2 , 5 mM MgCl 2 , 0.3 mM ATP and purified rALK in a total volume of 100 μl/well at 30° C. for 15 minutes. For inhibitor testing the reaction mix was preincubated with the inhibitor or solvent control for 10 mins at room temperature before transferring to the ELISA plate. After the reaction wells were washed 5 times with 200 μl of wash buffer. Phosphorylated peptide was detected using 100 μl/well of a mouse monoclonal anti-phosphotyrosine antibody (clone 4G10 UpstateBiotech Ltd) diluted 1:2000 in PBS+4% BSA. After 30 minutes incubation at room temperature the antibody was removed and wells were washed as described above. 100 μl of a secondary antibody (anti-mouse IgG, Horseradish Peroxidase linked whole antibody, Amersham Pharmacia Biotech) diluted 1:1000 in PBS+4% BSA was added to each well and the plate was incubated again for 30 minutes at room temperature before washing as above. The plate was developed using 100 μl/well TMB Substrate Solution (Endogen) and the reaction was stopped by adding an equal volume of H 2 SO 4 0.36 M. Finally, the absorbance was read at 450 nm using an Ultrospec® 300 spectrophotometer (Amersham-Pharmacia Biotech). The concentration of the test solution showing 50% inhibition as compared with the control was expressed as IC 50 .
[0247] Results from ELISA Kinase Assay
[0000]
TABLE 1
IC 50 values on ALK
compound
Identifier
IC 50 (μM)
Formula
r19
MFCD00045579
1.2
r35
MFCD01765083
7.7 ± 0.2
r36
MFCD01765086
27
r37
MFCD01765092
1.5 ± 0.3
r68
MFCD01765084
3.1 ± 0.34
r69
MFCD01765087
9.3 ± 2.9
r70
MFCD01765088
5.5 ± 2.3
r75
MFCD01934429
8.8 ± 0.85
r78
MFCD01934431
103
r79
MFCD00113424
24 ± 1.5
r80
MFCD00113296
48
r81
MFCD00205741
46.5
r43
MFCD01764268
27.3
r48
MFCD00206686
1.6 ± 0.15
r49
MFCD01312821
1.5 ± 0.17
r66
MFCD02050262
3.6 ± 0.5
r67
MFCD00366058
4.7 ± 0.7
r67
MFCD00366058
4.7 ± 0.7
r83
MFCD00110238
11.7
r85
MFCD00096941
16 ± 4.8
r84
MFCD00806357
11 ± 1.3
Example 1 Compound No.
r114
(1)
0.75 ± 0.13
r218
(2)
1.3 ± 0.5
r236
(4)
1.3 ± 0.4
r237
(6)
31 ± 5.7
r239
(7)
20 ± 2.3
r113
(64)
57 ± 5
r116
(12)
27 ± 1.6
r117
(13)
58 ± 5.8
r120
(14)
12 ± 1.2
r121
(65)
42 ± 3.3
r122
(66)
37 ± 2.7
r124
(67)
11 ± 0.72
r127
(15)
4.6
r128
(16)
6.7
r200
(17)
4.8 ± 0.7
r201
(68)
17 ± 1.5
r235
(22)
21 ± 2.5
r238
(21)
9.6 ± 1.1
r262
(20)
3.7 ± 0.5
r86
(42)
6.7 ± 0.5
r87
(43)
4.3 ± 0.3
r88
(39)
1.4 ± 0.1
r89
(69)
1.3 ± 0.2
r104
(41)
2.9 ± 0.2
r105
(29)
8.2 ± 0.3
r106
(37)
9.5 ± 0.4
r108
(32)
7.0 ± 0.3
r156
(57)
82 ± 9
r158
(59)
10 ± 0.73
r169
(60)
17 ± 1.4
r170
(62)
14 ± 1.6
r233
(70)
2.1 ± 0.7
[0248] 3. Inhibition of the Proliferation of NPM/ALK Transformed Cells
[0249] Method: Tritiated Thymidine Uptake Cell Proliferation Assay
[0250] BaF3 cells, transformed with the oncogenic fusion protein NPM/ALK, were seeded in U-bottomed 96-well plates at 10 000 cells/well in a volume of 100 μL in supplemented medium. Serial dilutions of inhibitors were added to the appropriate wells and volumes adjusted to 200 μL. Controls were treated with the equivalent volume of vehicle, DMSO, alone. Plates were incubated at 37° C. for 72 h. 3 [H-]-thymidine (1 μCi/well) was added for the last 16 h of incubation. Cells were harvested on to glass filters and 3 [H]-thymidine incorporation was measured using a scintillation counter (1430 MicroBeta, Wallac, Turku, Finland). The 50% inhibitory concentration (IC 50 ) was defined as the concentration of inhibitor that gave a 50% decrease in 3 [H]-thymidine uptake compared with controls.
[0251] Results for Proliferation Assay
[0000]
TABLE 2
IC 50 values on the proliferation of BaF3 cells transformed with
NPM/ALK
compound
Identifier
IC 50 (μM)
r78
MFCD01934431
7.6
r79
MFCD00113424
33
r80
MFCD00113296
31
r49
MFCD01312821
12
r66
MFCD02050262
4.8
Compound
IC 50 (μM)
r89
36
r104
7
r105
2.3
r106
1.9
[0252] 4. Abl T315I Mutant Kinase Inhibitory Activity
[0253] Method: ELISA-Based In Vitro Kinase Assay
[0254] Recombinant Abl T315I protein was expressed in Sf9 cells using the pBlueBacHis2C baculovirus expression vector. Abl T315I was purified using an anion exchange Fast Flow Q-sepharose column (Amersham-Pharmacia Biotech) followed by HiTrap™-nickel affinity column (Amersham-Pharmacia Biotech). Purified Abl T3151 was used in the ELISA-based kinase assay to screen inhibitors as described above. The kinase reaction was performed in the presence of 50 mM Tris pH 7.5, 1 mM MnCl 2 , 5 mM MgCl 2 , 0.3 mM ATP, peptide substrate (ARDIYRASFFRKGGCAMLPVK) and purified Abl T315I. The concentration of the test solution showing 50% inhibition as compared with the control was expressed as IC 50 .
[0000]
TABLE 3
IC 50 values on Abl T315I
Compound
IC 50 (μM)
r87
6.43 ± 0.43
r88
1.45 ± 0.35
r104
7.0 ± 1.4
r114
2.1
compound
Identifier
IC 50 (μM)
r37
MFCD01765092
3.3 ± 0.81
REFERENCES
[0000]
1. Rabbitss, T. H. Nature, 1994, 372, 143.
2. Ben-Neriah, Y., Daley, G. Q., Mes-Masson, A. M., Witte, O. N. & Baltimore, D. Science. 1986, 233, 212.
3. Gambacorti-Passerini, C. B., Gunby, R. H., Piazza, R., Galietta, A., Rostagno, R. & Scapozza, L. Lancet Oncol. 2003, 4, 75-85.
4. Morris, S. W; Kirstein, M. N.; Valentine, M. B.; Dittmer, K. G.; Shapiro, D. N.; Saltman, D. L.; Look; A. T. Science, 1994, 263,1281-1284.
5. Shah, N. P., Tran, C., Lee, F. Y., Chen, P., Norris, D. & Sawyers, C. L. Science 2004 305, 399-401.
6. Puttini, M.; Coluccia, A. M.; Boschelli, F.; Cleris, L.; Marchesi, E.; Donella-Deana, A.; Ahmed, S.; Redaelli, S.; Piazza, R.; Magistroni, V.; Andreoni, F.; Scapozza, L.; Formelli, F.; Gambacorti-Passerini, C. Cancer Res. 2006, 66, 11314-11322.
7. Weisberg, E., Manley, P. W., Breitenstein, W., Bruggen, J., Cowan-Jacob, S. W., Ray, A., Huntly, B., Fabbro, D., Fendrich, G., Hall-Meyers, E., Kung, A. L., et al. Cancer Cell. 2005 7, 129-141.
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Inhibitors of the oncogenic tyrosine kinase ALK and of the Bcr-Abl mutant T315I Bcr-Abl, pharmaceutical compositions containing the same and their use for the treatment of hyper-proliferative diseases.
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FIELD OF THE INVENTION
This invention generally relates to the field of scuba equipment and more specifically to a buoyancy compensator having an attached backpack. During use, the buoyancy compensator and backpack conform about a diver's body.
BACKGROUND OF THE INVENTION
The buoyancy compensator is a vest-shaped device worn about a diver's upper torso to assist in maintaining a diver's buoyancy at a neutral point under water. Within the buoyancy compensator there is an inflatable air bladder. By inflating and deflating the air bladder, the buoyancy of the buoyancy compensator and therefore the diver may be adjusted.
A backpack, on which is mounted one or more pressurized air tanks, is frequently attached to the buoyancy compensator. The backpack rests against the back of the diver, and belting on the buoyancy compensator secures the buoyancy compensator and backpack about the diver's upper torso. It is important for the diver's comfort that the buoyancy compensator and backpack are securely attached to each other and that they both act to conform about the diver's upper torso.
One style of buoyancy compensator is generally formed by an inner and outer lining of polyurethane coated nylon cloth. Each lining has a gas impermeable polyurethane inner layer and a nylon outer backing layer. The two linings are oriented so that the polyurethane inner layers are opposite each other and the nylon backing layers face outward. The inner polyurethane layers are integrally bonded together about the inner and outer peripheral edges of the linings to form a gas tight seal and thereby the inflatable air bladder. The bonding of the polyurethane layers is generally accomplished with RF welding. The backpack is attached to the backside of the buoyancy compensator by means of stitching, belts, fasteners, or the like. An important assembly consideration of conventional buoyancy compensators is that at the attachment point, one or both of the cloth linings may be cut or punctured. To prevent leakage from the air bladders at the attachment point, the polyurethane layers of cloth linings are bonded together to establish an air tight seal which encircles the attachment point.
One of the drawbacks of the prior art buoyancy compensators is the method of attaching the backpack to the compensator. The attachment of the backpack to the compensator by stitching, belting, or fastening, followed by sealing about the attachment point adds costly steps to the construction of the compensator.
An additional drawback of conventional buoyancy compensators is the discomfort the attached backpack may cause the diver. The backpack is generally made of a rigid polymer, and the part of the backpack which interfaces with a diver's back is generally planar. When the compensator and backpack are securely fastened to the diver, the planar backplate contacts and presses against the generally curved back of the diver, which may cause discomfort.
A further drawback is that when the air bladder within the buoyancy compensator is inflated, the generated pressure generally causes ballooning of the linings. This ballooning is undesirable as it may squeeze the diver and restrict the diver's movements. The ballooning may be lessened by restraining the distance the linings can move apart from each other. One present arrangement for restraining the linings is to bond opposing portions of the two linings to each other or to attach a series of vertical internal restraints to the linings. The restraints are attached to the linings by bonding the restraints to the inner layers of the linings at directly opposing locations. The restraints typically are aligned to each other and placed in that portion of the compensator which extends about the sides of the diver's torso. However, when the compensator is inflated and the frontal portions of the buoyancy compensator are secured about a diver's torso, these types of internal restraints cause the linings to form a planar configuration or flatten out. This flattening out of the vest, particularly in that portion of the vest extending about the sides of the diver, causes so-called "diver squeeze" which is undesirable.
It is therefore an object of the present invention to provide a buoyancy compensator vest and attached backpack which conforms about a diver's torso. A related object is to provide a backpack having a baseplate which conforms to the back of a diver.
It is also an object of the present invention to provide a buoyancy compensator vest and backpack in which the backpack is attached to the compensator vest at the attachment point and is sealed in a single step.
It is an additional object of the present invention to provide a buoyancy compensator having linings which curve about the sides of a diver when the air bladder is inflated.
SUMMARY OF THE INVENTION
Accordingly, a buoyancy compensator assembly for a diver is provided with a vest having an inner gas impermeable layer adapted to face a wearer, and a congruently-shaped, opposing gas impermeable outer layer. The peripheral edges of the inner and outer layers are sealingly bonded to each other. The vest has an opening through the inner and outer layers in a back portion of the vest. A backpack is provided for removably retaining a longitudinally extending breathing gas tank, and has a baseplate generally disposed within the opening. The baseplate includes a peripheral edge extending into the vest. The edge is disposed between, and sealingly bonded to the inner and outer layers of the vest, so that the layers form an inflatable chamber to be selectedly inflated to adjust the buoyancy of the diver. Thus, an important feature of the present invention is that the backpack is secured to the vest, and the inner and outer layers of the vest are sealed to each other in a single step.
Another feature of the present invention is a restraining sheet located between, and alternately attached to, the inner layer and outer layer to form aligned bands. The sheet forces the inner layer to curve inward to fit about the sides of the diver when the chamber is inflated.
Yet another feature of the present invention is that the backpack is constructed so that when the breathing gas tank is strapped onto the backpack, the baseplate curves to fit about the back of the diver.
BRIEF DESCRIPTIONS OF THE DRAWINGS
FIG. 1 is a rear perspective view of a diver wearing the buoyancy compensator of the invention;
FIG. 2 is a rear exploded perspective view of the buoyancy compensator of FIG. 1;
FIG. 3 is a frontal elevational view of the buoyancy compensator of FIG. 2 in an opened position and with parts shown broken away for clarity;
FIG. 4 is a sectional view taken along the line 4--4 of FIG. 3 and in the direction indicated generally;
FIG. 4a is an expanded sectional view of an alternate attachment between the buoyancy compensator and backpack;
FIG. 5 is a sectional view taken along the line 5--5 of FIG. 3 and in the direction indicated generally showing the buoyancy compensator deflated; and
FIG. 6 is the view of FIG. 5 with the buoyancy compensator inflated.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to FIG. 1, a buoyancy compensator embodying the present invention is indicated generally at 10. The buoyancy compensator 10 includes a vest 12 and attached backpack 14. The backpack 14 supports at least one tank 16 of compressed air or other breathing gas on which is mounted a regulator 18.
Referring to FIGS. 2, 3 and 5, the vest 12 is formed of an inner lining 20 and a congruently shaped outer lining 22. The inner and outer linings 20, 22 preferably are composed of a material having a nylon cloth outer layer 20a and 22a and a gas impermeable polyurethane inner layer 20b and 22b. The inner and outer linings 20, 22 are attached to each other about their peripheral edges 24 to establish an air tight seal. This attachment is accomplished by integrally bonding the opposing inner layers 20b, 22b to each other by electric or RF welding as is well known in the art. The bonding may also be accomplished with adhesives or other suitable means.
Referring to FIG. 3, the vest 12 includes a back portion 26 which extends about the back of the diver; left and right frontal portions 30, 28 (as worn by the diver); and left and right side portions 32, 34 which correspond to, and extend about the sides of a diver's upper torso. The left front and side portions 30, 32 and right front and side portions 28, 34, form openings 38 and 36, respectively, for the diver's arms.
Referring to FIG. 2, the backpack 14 is preferably composed of a generally stiff yet resilient material such as polyurethane or the like. The backpack 14 includes a vertically extending base plate 40. A lower portion 40a of the base plate 40 has a plurality of laterally spaced, vertically oriented slots 42, 44, 46, 48 through which passes a cummerbund belt 50 to secure the backpack 14 about the diver's waist. The belt 50 may pass through the slots 42, 44, 46, 48 so that it passes from inside the vest 12 through slot 42 to the outside and returns to the inside through slot 44. The belt 50 then passes from the inside through slot 46 to the outside and returns to the inside through slot 48. The left and right ends 50a and 50b of the cummerbund 50 are secured about the waist by an attachment mechanism such as a VELCRO® brand, hook and loop fastener arrangement.
Rigidly and integrally connected to, and extending longitudinally along sides 54 of a middle portion 40b of the base plate 40 is a pair of thinned, outwardly protruding and generally vertically extending supports 56 and 58. The tops or rearwardly facing edges 56a, 58a of the supports 56, 58 contact the tank 16 along the sides of the frontal portion 16a of the tank (best seen in FIG. 1). Laterally extending between the supports 56, 58 are upper and lower ribs 60, 62.
Returning to FIG. 4, between the supports 56 and 58 and between the ribs 60 and 62, (best seen in FIG. 2), the baseplate 40 has a pair of slots 64, 66. A tank securement band 68 circumscribes the tank 16, and extends from the tank through the slot 64 to the inside of the vest 12 and returns outward to the tank through the slot 66. The band 68 is clamped about the tank by an overcenter latch 70 (best seen in FIG. 1) or other suitable means. The overcenter latch 70 also provides an adjustment portion 72 to vary the length of the band 68 as is well known in the art. Each of the tops 56a, 58a of the supports 56, 58, respectively, have notches 74 formed to allow for the passage of the band 68 around the tank 16 without a pinching of the band by the supports.
The upper and lower ribs 60 and 62 have concave curved outer edges 60a, 62a opposite the tank 16. When there is no tension in the band 68 and the backpack is in a relaxed position, as shown in solid lines in FIG. 4, the base plate 40 has a generally planar inner surface 76. Also, when the backpack is in a relaxed position, the upper and lower ribs 60 & 62 and supports 56, 58 are configured so that as the front portion 16a of the tank 16 contacts the supports, there is a clearance C between the outer edges 60a and the tank. Tightening the band 68 during securement of the tank 16 draws the tank toward the baseplate 40 and the clearance C diminishes. The tightening also causes the tank 16 to push against each of the supports 56, 58 with lateral and forward directed forces F1 while the band 68 is applying a force F2 on the central area of the baseplate, which is directed outward toward the tank 16. The laterally offset forces F1 and F2 cause the inner surface 76 to bend and form a convex curve, in the lateral direction, as shown in phantom lines in FIG. 4. This convex shape conforms the inner surface 76 of the backpack 14 more closely to the back of the diver than previous configurations.
The upper & lower ribs 60 and 62, and baseplate 40, being composed of a resilient material, cause the baseplate 40 and supports 56, 58 of the backpack 14 to exert an outward springlike or biasing force against the tank 16. The biasing force is translated into a tensile force in the band 68. This spring-like force is important because the band 68 is typically made of a woven material such as nylon webbing which has a tendency to slightly lengthen or slacken when the band becomes wet, which typically occurs when the diver goes into the water. When the band 68 slackens, the biasing force of the backpack 14 displaces the tank 16 away from the baseplate 40 which absorbs the slack and prevents the band from loosening so that the tank remains firmly secured to the backpack 14.
The baseplate 40 also includes a set of longitudinal bracing ribs 78 which extend through the upper & lower ribs 60 and 62 between slots 64 and 66. The bracing ribs 78 strengthen the central area between the slots 64 and 66 to prevent any breakage or bending of the baseplate due to the force F2 applied on the baseplate 40 by the band 68.
Referring now to FIGS. 2 and 4, an upper portion 40c of the baseplate 40 may have a set of five laterally aligned slots 80, 82, 84, 86 and 88. Through the middle slot 84 extends a loop of an elastic webbing 90 having ends which, in the preferred embodiment, are attached to a back padding 92. The back padding 92 is congruently shaped with the baseplate 40 and fits flush against the inner surface 76 (partially shown in FIG. 4) and between the baseplate 40 and the diver. A bar slide 94, through which the elastic webbing 90 extends, is sized so that when the slide is flush against the baseplate 40, the slide prevents the loop from going through the middle slot 84, but the slide can travel through the slot 84 when turned on its side so that the back padding 92 may be replaced. The back padding 92 may also be secured against the inner surface 76 by threading the cummerbund belt 50 through the padding as the belt extends from slot 44 to slot 46 of the baseplate 40.
A tank locator strap 96 has an outer loop which circumscribes the upper portion of the tank 16 to locate the buoyancy compensator in a preferred position on the tank. One end of the strap 96 may pass through the slots 80, 82 so that it passes from the outside through slot 80 to the inside and then returns through slot 82 to the outside where the end is then threaded through the bar slide 94. Similarly the other end of the strap 96 passes from the outside through slot 88 to the inside and then returns through slot 86 where the end is threaded through the bar slide 94. By adjusting the length of the strap 96 with the bar slide 94, the strap 96 securably locates the tank 16 upon the backpack 14.
Referring now to FIGS. 2-4, to connect the backpack 14 to the vest 12, the baseplate 40 is integrally and rigidly attached to a peripheral thinned edge 98 which is preferably composed of polyurethane. The central portion of the back portion 26 of the vest 12 is provided with an opening 100 which extends through the inner and outer linings 20, 22 and is sized to fit about the edge 98 so that the edge is sandwiched between the inner and outer linings 20, 22 of the vest 12 in a zone bordering the opening 100. Returning to FIG. 4, because the edge 98 is of the same general polyurethane composition as the inner layers 20b, 22b of the inner and outer linings 20, 22, respectively, the edge 98 is attached to the linings by integrally bonding the edge to the inner polyurethane layers 20b, 22b, to establish an air-tight seal. The bonding is preferably accomplished by RF or electric welding or other suitable means. The backpack 14 is thus attached to the vest 12 and the air tight seal is established about the attachment point in a single step which reduces manufacturing expenses.
If desired, a secondary seal 101 may be formed between the inner and outer linings 20, 22 to circumscribe the edge 98 of the backpack 14. The secondary seal 101 is formed by bonding the inner polyurethane layers 20b, 22b of the inner and outer linings 20, 22 to each other. The bonding can be performed at the same time as the bonding between the edge 98 and the linings 20, 22.
Referring to FIG. 4A, in an alternate embodiment, only the outer lining 22 has the opening 100, and the inner surface 76 of the baseplate 40 contacts the inner lining 20. To form air-tight seals, the edge 98 is integrally bonded to the inner layer 20b of the inner lining 20 to attach the backpack to the vest, and the inner and outer linings 20, 22 are integrally bonded to each other immediately adjacent the edge 98 to form an air-tight seal. The bonds between the edge 98 and inner layer 20b and between the inner and outer linings 20, 22 may be performed in a single process.
Referring now to FIG. 5, with the bonding of the inner lining 20 to the outer lining 22 about their peripheral edges 24 and the bonding between the edge 98 (FIG. 4) and the inner and outer lining about the opening, an air-tight bladder 102 is formed. The bladder 102 defines an air tight chamber 103. The present buoyancy compensator 12 is not limited to vests having two-layer inner and outer linings but may also include vests having outer linings and separate inner linings which form the air bladder, whereby the edge 98 would be integrally bonded to the air bladder and the outer lining may be attached to the backpack by appropriate attachment means.
Referring to FIG. 1, to provide air to the bladder 102, the buoyancy compensator 10 includes a power inflator assembly 104 in communication with the chamber 103. The inflator assembly 104 can be of the type known in the prior art, and is connected by hose 106 to the regulator 18 attached to the tank 16.
Referring now to FIGS. 3 and 5, when the bladder 102 is inflated, a left and right restraining system generally designated 110 and 112 cause the left and right side portions 32 and 34 to form inwardly curving arcs which conform about the sides of the diver. Referring to FIG. 5, the right restraining system 112 includes a sheet 114 of material having outer layers 116 of polyurethane sandwiching an inner layer of nylon cloth 118. The sheet 114 is configured so that the upper and lower peripheral edges of the sheet form a gap between the sheet 114 and the upper and lower peripheral edges 24 of the vest 12 to permit free air flow around the sheet and, therefore, throughout the chamber 103.
The sheet 114 is attached to the vest 12 to form an odd number of at least three vertically aligned attachment bands or ribs 122. The outer attachment bands 122a of the sheet 114 are attached to the outer lining 22 and the intermediate attachment bands 122b alternate between the inner lining 20 and the outer lining 22 to form a corrugated appearance when viewed from above. For example, in the preferred embodiment there are five attachment bands 122 formed between the sheet 114 and inner and outer linings 20, 22. The outer attachment bands 122a are bonded to the outer lining 22. The intermediate bands 122b adjacent the outer bands 122a are attached to the inner lining 20 and the intermediate band 122b in the center is attached to the outer lining 22.
Referring now to FIG. 6, when the air bladder 102 is inflated, the sheet 114 restrains the distance the inner lining 20 and outer lining 22 may move apart from each other. In addition, the alternating attachment of the sheet 114 to the inner lining 20 and outer lining 22 causes the portion of the air bladder 102 that is restrained by the restraining system 112 to form an inwardly curved and flexible lateral cross-section that conforms about the sides of the diver's torso, minimizing diver squeeze.
The sheet 114 is attached to the inner and outer layer to form the ribs 122 preferably by bonding the polyurethane outer layers 116 to the polyurethane inner layers 20b and 22b of the inner and outer linings 20, 22 by RF welding or other suitable means.
The left restraining system 110 is constructed in a similar manner as the right restraining system 112 described above with a sheet 114 alternately attached to the inner and outer linings 20, 22, so that when the air bladder 102 is inflated, the restrained portion of the bladder curves to conform about the left side of the diver.
A specific embodiment of the novel buoyancy compensator having an attached backpack according to the present invention has been described for the purposes of illustrating the manner in which the invention may be made and used. It should be understood that implementation of other variations and modifications of the invention in its various aspects will be apparent to those skilled in the art, and that the invention is not limited by the specific embodiment described. It is therefore contemplated to cover by the present invention any and all modifications, variations, or equivalents that fall within the true spirit and scope of the basic underlying principles disclosed and claimed herein.
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A buoyancy compensator assembly for a diver is provided with a vest having an inner gas impermeable layer adapted to face a wearer and a congruently shaped opposing gas impermeable outer layer. The peripheral edges of the inner and outer layers are sealingly bonded to each other. The vest has an opening through a back portion of the vest. A backpack for removably retaining a longitudinally extending breathing gas tank has a baseplate generally disposed within the opening. Attached to the periphery of the baseplate is an edge. The edge is disposed between and integrally bonded to the inner and outer layers whereby the layers form a chamber to be selectively inflated to adjust the buoyancy of the diver. A restraining sheet is located between and alternately attached to the inner layer and outer layer to form aligned bands. The sheet forces the inner layer to curve inward about the sides of the diver when the chamber is inflated. The backpack is constructed so that when the breathing gas tank is strapped onto the backpack the baseplate curves to fit about the back of the diver.
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BACKGROUND OF THE INVENTION
1. The Field of the Invention
The present invention relates to a satellite signal receiver, and in particular, to a power controller for a satellite signal receiver used for devices, such as mobile terminals or mobile phones, that have a satellite signal reception unit.
2. Related Art
One conventional satellite signal receiver is known by Japanese Patent Laid-open Publication No. 8-304526, of which configuration is illustrated by FIG. 1 .
The satellite signal receiver shown in FIG. 1 includes a positional information generator 1 , operational command receiver 2 , power supply 3 , and power switching unit 4 that turns on or off power of the positional information generator 1 .
The positional information generator 1 is equipped with an receiving antenna 5 for receiving electric waves that has been transmitted from satellites, satellite receiver 6 , positional data output circuit 7 , and transmitting antenna 8 . The satellite receiver 6 demodulates a signal of the received electric waves to computes a current position of this apparatus. The operational command receiver 2 includes a receiving antenna 9 for receiving in wireless an operational command that has been received from the manager, and a reception circuit 10 via the receiving antenna 9 .
When the receiver is in operation, only the power of the operational command receiver 2 is turned on to wait for receiving an operational command from the manager. When the manager transmits an operational command, the operational command receiver 2 receives the operational command and activates the power switching unit 4 so that it turns on. This unit 4 operates to supply the power from a power supply 3 to each element of the positional information generator 1 , so that each element is energized. The satellite receiver 6 demodulates each satellite signal supplied from the antenna 5 in such a manner that a current position of this receiver is computed based on the signals from a plurality of satellites. The computed positional data are the subject to demodulation in the positional data output circuit 7 , before being sent to the manager via the transmission antenna 8 .
After the positional information generator 1 generates positional data, the power switching unit 4 will be kept to be on for a certain time, intermittently, or until receiving a command for stopping the operation. During the period of the on-state of the power switching unit 4 , the generator 4 generates positional data.
According to this satellite signal receiver, if there is no need for demands for positional information, powering a main part of the apparatus is stopped, while the power is prepared whenever it is necessary. Hence consumption of useless power is suppressed.
However, the foregoing satellite signal receiver is configured so that an external command controls the turn on/off of power of the satellite receiver 6 . Therefore, even when this receiving apparatus is located such that it is impossible for this apparatus to receive satellite electric waves or it is extremely difficult for this apparatus to perform such reception, thereby positioning being impossible, the external command causes the satellite receiver to be activated. This results in that the power is consumed uselessly.
SUMMARY OF THE INVENTION
An object of the present invention is to provide, with due consideration to the drawback of such a conventional satellite signal receiver, a power supply controller for a satellite signal receiver, which is able to control operational conditions of a satellite receiver depending on positioning conditions.
In order to accomplish the above object, the present invention provides satellite signal receiver comprising: a satellite signal reception unit for calculating a current position of the satellite signal receiver using an electric wave from a satellite, in response to a positioning request; a timer for clocking an elapsed time in calculating the current position of the satellite signal receiver; and power-on/off controlling means for controlling an on/off state of power supplied to both the satellite signal reception unit and the timer on the basis of information including the positioning request, the elapsed time clocked by the timer, and a condition under which the satellite signal reception unit receives the signal from the satellite.
Preferably, the power-on/off controlling means includes: switch means for switching on or off the power supplied to both the satellite signal reception unit and the timer; and control means for controlling turn on/off operations of the switch means based on the information. It is also preferred that the information about the condition is information about the number of ephemerides. In this case, preferably, the control means includes first control means for turning on the switch means in response to the positioning request, setting means for adjustably setting a period of active time counted from a first time instant at which the switch means turns on to a second time instant at which the satellite signal reception unit calculates the current position, and second control means for turning off the switch means when the elapsed time reaches the period of active time. Byway of example, the setting means is configured so that larger the less the number of ephemerides, the larger the period of active time.
Still preferably, the information about the condition is information about an elapsed time from the last calculation of the current position.
As a further configuration according to the present invention, there is provided a satellite signal receiver comprising: a satellite signal reception unit for intermittently calculating a current position of the satellite signal receiver at adjustable intermittent intervals by using an electric wave from a satellite; a timer for clocking an elapsed time every time when the current position of the satellite signal receiver is calculated; and power-on/off controlling means for intermittently controlling an on/off state of power supplied to the satellite signal reception unit on the basis of information including the elapsed time clocked by the timer every time when the current position of the satellite signal receiver is calculated.
According to the above constructions, the power supplied to both the satellite signal reception unit and the timer, or to the satellite signal reception unit is turned on in response to a positioning request issued or at intermittent intervals. During such supply of the power, the power can be turned on/off to control a period of time for supplying the power or intermittent intervals for supplying the power, according to information held by the satellite signal reception unit or its receiving condition. Thus, in cases the satellite signal receiver is placed at situations in which the positioning is impossible, the time for supplying of the power is shortened to avoid useless consumption of the power.
BRIEF DESCRIPTION OF THE DRAWINGS
In the accompanying drawings:
FIG. 1 is a block diagram showing the configuration of a conventional satellite signal receiver;
FIG. 2 is a block diagram showing the configuration of a satellite signal receiver employed in a first to fifth embodiments of the present invention;
FIG. 3 is a flowchart depicting control of power in the satellite signal receiver according to the first embodiment;
FIG. 4 is a flowchart depicting control of power in the satellite signal receiver according to the second embodiment;
FIG. 5 is a flowchart depicting control of power in the satellite signal receiver according to the third embodiment;
FIG. 6 is a flowchart depicting control of power in the satellite signal receiver according to the fourth embodiment;
FIG. 7 is a flowchart depicting specification of a period of active time necessary for power control conducted in the satellite signal receiver according to the fifth embodiment;
FIG. 8 is a block diagram showing the configuration of a satellite signal receiver employed in a sixth and seventh embodiments of the present invention;
FIG. 9 is a flowchart depicting control of power in the satellite signal receiver according to the sixth embodiment; and
FIG. 10 is a flowchart depicting control of power in the satellite signal receiver according to the seventh embodiment.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Embodiments of the present invention will now be described in conjunction with the appended drawings.
First Embodiment
FIG. 2 is a block diagram showing the configuration of a satellite signal receiver in accordance a first embodiment of the present invention. Incidentally, a satellite signal receiver used in a second to fifth embodiments, which will be described later, also adopt the identical configuration to that shown in FIG. 2 .
As shown in FIG. 2, the satellite signal receiver is equipped with an antenna 5 , satellite signal reception unit 6 , timer 11 , communication unit 13 , power supply 3 , power switching unit 4 , and control unit 12 .
Among these constituents, the antenna 5 is placed to receive an electric wave from a satellite. The satellite signal reception unit 6 has a memory device 14 to store various types of information and a clock device 15 to clock a positioning time instant, and performs signal demodulation processing on the received electric wave to calculate a current position of this satellite signal receiver.
The communication unit 13 conducts communication with a certain external system in such a manner that it not only receives a positioning request from the external system but also transmit to the external system date of a calculated current position. The power switching unit 4 turns on/off power supplied from the power supply 3 to both the satellite signal reception unit 6 and the timer 11 . The control unit 12 controls the operation of each unit. A time instant to turn on/off the power switching unit 4 is controlled by the control unit 12 based on information involving an elapsed time measured by the timer 11 .
The operation of the satellite signal receiver in accordance with the first embodiment of the present invention will now be described in conjunction with FIGS. 2 and 3. FIG. 3 is a flowchart showing power control conducted in the satellite signal receiver. The control unit 12 executes the processing shown in FIG. 3 .
When the control unit 12 receives a request for positioning from an external system through the communication unit 13 (step 100 ), the control unit 12 turns on the power switching unit 4 to activate both the satellite signal reception unit 6 and the timer 11 (step 101 ).
By the way, the positioning of the satellite signal receiver is not always possible, and it mostly depends on circumstances to receive the electric waves from satellites. Thus, a period of activity time (a period to time-out) counted from the turn-on of the power switching means 4 to the calculation of a current position of this satellite signal receiver (positioning), specifically, the output of positional information from the satellite signal reception unit 6 , is specified in advance. A period of time to the expected next positioning usually varies depending on the number of ephemerides, which is stored by the memory device 14 of the satellite signal reception unit 6 under continuous supply of power from the power supply 3 .
Therefore, the control unit 12 acquires information in relation to the number of ephemerides stored by the memory device 14 (Step 102 ), then determines if there is any difference between the number of ephemerides and a given threshold of number (step 103 ). Depending on these determined results, the control unit 12 performs a process to change the period of activity time from a time instant at which the power supply switch unit 4 is turned on to a time instant when the control unit 12 acquires positioning information.
In the example of FIG. 3, the period of activity time is specified as T 01 #short when the number of ephemerides is equal or larger to or than its given threshold (step 104 ). In contrast, the period of activity time is specified as T 01 #long (>T 01 #short) when the number of ephemerides is smaller than the threshold (step 105 ). Alternatively, this determination may involve three or more stages with two or more pieces of thresholds.
Subsequently, the control unit 12 compares a period of elapsed time measured by the timer 11 with the period of activity time (step 106 ). When the measured period of elapsed time becomes equal or larger to or than the period of activity time with no calculation of a current position of this satellite signal receiver made by the satellite signal reception unit 6 , the control unit 12 regards the positioning as being impossible. In this case, the control unit 12 turns off the power switching unit 4 (step 107 ), then notifies the not-shown external system of an unsuccessful positioning through the communication unit 13 (step 108 ).
In contrast, in cases where the period of elapsed time measured by the timer 11 is smaller than that of the period of activity time, the control unit 12 tries to acquire positioning information from the satellite signal reception unit 6 (step 109 ). Then the control unit 12 begins a process to determine whether the positioning has been finished or not (step 110 ). When the positioning has been finished, the control unit 12 sends an “off” commands to the power switching unit 4 (step 111 ), and outputs the positioning information to the not-shown external system via the communication unit 13 (step 112 ). If the positioning has not been finished yet, the control unit 12 returns to the process at step 106 to repeat the foregoing processing.
As explained above, in the satellite signal receiver according to the first embodiment of the present invention, the period of activity time is adjusted depending on information about the number of ephemerides stored by the memory device of the satellite signal reception unit. Thus the period of activity time can be approached or made to agree to or with a remaining period of time to the next positioning to be expected as closer as possible. It is therefore possible to shorten a period of time to power the satellite signal reception unit under a condition the positioning cannot be conducted, thus reducing useless consumption of the power.
Second Embodiment
Referring to FIGS. 2 and 4, a second embodiment of the present invention will now be described.
A satellite signal receiver according to the second embodiment differs only in that the control unit 12 and the satellite signal reception unit 6 are constructed to perform a further series of processing different from that in the first embodiment. The remaining configuration and operations of this satellite signal receiver are identical to those in the first embodiment, so the differences with respect to the processing and operations are mainly described.
FIG. 4 is a flowchart showing power control for the satellite signal receiver according to the second embodiment, which is executed by both of the control unit 12 and the satellite signal reception unit 6 .
When receiving a request for positioning issued outside through the communication unit 13 (step 200 ), the control unit 12 turns on the power switching unit 4 in order to activate both of the satellite signal reception unit 6 and the timer 11 (step 201 ).
By the way, a period of elapsed time counted from a time instant when the clock device 15 counted a positioning time at the last positioning conducted by the satellite signal reception unit 6 has also influence on a period of time to the next positioning to be expected. Considering this fact, in the satellite signal reception unit 6 of the present embodiment, a time instant clocked by the clock device 15 at a certain positioning is memorized by the memory device 14 .
Therefore, based on the current time instant clocked by the incorporated clock device 15 to which the power supply 3 supplies power anytime and the last positioning time instant memorized by the memory device 14 , the satellite signal reception unit 6 calculates a period of elapsed time from the last poisoning time instant (step 202 ). The calculated period of elapsed time is sent to the control unit 12 .
Responsively to reception thereof, the control unit 12 will move to processing to adjust the period of activity time counted from a time instant when the power is turned on to a time instant when position information is obtained (step 203 ). Specifically, it is determined whether or not the calculated period of elapsed time from the last positioning is equal or larger to or than a given threshold set for the period.
In the example of FIG. 4, the period of activity time is specified as T 02 #long when the period of elapsed time is equal or larger to or than its given threshold (step 204 ). In contrast, the period of activity time is specified as T 02 #short (<T 02 #long) when the period of elapsed time is smaller than the threshold (step 205 ). Alternatively, this determination may involve three or more stages with two or more pieces of thresholds.
Subsequently the control unit 12 determines whether or not the period of elapsed time measured by the timer 11 is equal or larger to or than the period of activity time (step 206 ). If the period of elapsed time measured by the timer 11 is equal or larger to or than the period of activity time with no calculation of a current position of this satellite signal receiver, the control unit 12 regards the positioning as being impossible. In this case, the control unit 12 turns off the power switching unit 4 (step 207 ), then notifies the not-shown external system of an unsuccessful positioning through the communication unit 13 (step 208 ).
In contrast, in cases where the period of elapsed time measured by the timer 11 is smaller than that of the period of activity time, the control unit 12 tries to acquire positioning information from the satellite signal reception unit 6 (step 209 ). Then the control unit 12 begins a process to determine whether the positioning has been finished or not (step 210 ). When the positioning has been finished, the control unit 12 sends an “off” commands to the power switching unit 4 (step 211 ), and outputs the positioning information to the not-shown external system via the communication unit 13 (step 212 ). If the positioning has not been finished yet, the control unit 12 returns to the process at step 206 to repeat the foregoing processing.
As explained above, in the satellite signal receiver according to the second embodiment of the present invention, the period of activity time is adjusted depending on a period of time elapsing from the last positioning. Thus the period of activity time can be approached or made to agree to or with a remaining period of time to the next positioning to be expected as closer as possible, thereby a period of time to power the satellite signal reception unit being shortened. Useless consumption of the power can be suppressed.
Third Embodiment
Referring to FIGS. 2 and 5, a third embodiment of the present invention will now be described.
A satellite signal receiver according to the third embodiment differs only in that the control unit 12 and the satellite signal reception unit 6 are constructed to perform further processing different from that in the first embodiment. The remaining configuration and operations of this satellite signal receiver are identical to those in the first embodiment, so the differences with respect to the processing and operations are mainly described.
FIG. 5 is a flowchart showing power control for the satellite signal receiver according to the third embodiment, which is executed by both of the control unit 12 and the satellite signal reception unit 6 .
When receiving a request for positioning issued outside through the communication unit 13 (step 300 ), the control unit 12 turns on the power switching unit 4 in order to activate both of the satellite signal reception unit 6 and the timer 11 (step 301 ).
The calculation of a current position (i.e., positioning) requires that the signals from a given number of satellites necessary for the positioning be detected. In consideration of this, in this embodiment, a period of activity time for signal detection is specified (step 302 ). Such period of signal-deception activity time is counted from at a time instant when the power switching unit 4 is turned on to a time instant when the signals from the given number of satellites necessary for the positioning are detected.
Then it is determined whether or not a period of elapsed time measured by the timer 11 is equal or larger to or than the period of signal-deception activity time (step 303 ). IF the determination is YES at step 303 (the signals from the given number of satellites necessary for the positioning have not been detected), the control unit 12 turns off the power switching unit 4 (step 304 ), then notifies the not-shown external system of an unsuccessful positioning through the communication unit 13 (step 305 ).
By contrast, if the determination is NO at step 303 (the signals from the given number of satellites necessary for the positioning have been detected within the period of signal-detection activity time), it is then determined whether or not the number of received satellite signals is equal or larger to or than a necessary number (step 306 ). In cases the number of received satellite signals is equal or larger to or than the necessary number, a period of positioning activity time, which is counted from the turn-on of the power to positioning, is specified (step 307 ). However, if the number of received satellite signals is lower than the necessary number, the processing is returned to step 303 .
Subsequently the control unit 12 determines whether or not the period of elapsed time measured by the timer 11 is equal or larger to or than the period of positioning activity time (step 308 ). If the period of elapsed time measured by the timer 11 is equal or larger to or than the period of positioning activity time, the control unit 12 regards the positioning as being impossible. In this case, in the same manner as above, the control unit 12 turns off the power switching unit 4 (step 304 ), then notifies the not-shown external system of an unsuccessful positioning through the communication unit 13 (step 305 ).
In contrast, in cases where the period of elapsed time measured by the timer 11 is smaller than that of the period of positioning activity time, the control unit 12 tries to acquire positioning information from the satellite signal reception unit 6 (step 309 ). Then the control unit 12 begins a process to determine whether the positioning has been finished or not (step 310 ). When the positioning has been finished, the control unit 12 sends an “off” commands to the power switching unit 4 (step 311 ), and outputs the positioning information to the not-shown external system via the communication unit 13 (step 312 ). If the positioning has not been finished yet, the control unit 12 returns to the process at step 308 to repeat the foregoing processing.
As explained above, in the satellite signal receiver according to the third embodiment of the present invention, the period of positioning activity time is specified to regulate an interval from the turn-on of the power to the detection of all the signals necessary for the positioning. This makes it possible to decide a condition in which the positioning is impossible. Useless consumption of the power can be suppressed.
Fourth Embodiment
Referring to FIGS. 2 and 6, a fourth embodiment of the present invention will now be described.
A satellite signal receiver according to the fourth embodiment differs only in that the control unit 12 and the satellite signal reception unit 6 are constructed to perform further processing different from that in the first embodiment. The remaining configuration and operations of this satellite signal receiver are identical to those in the first embodiment, so the differences with respect to the processing and operations are mainly described.
FIG. 6 is a flowchart showing power control for the satellite signal receiver according to the fourth embodiment, which is executed by both of the control unit 12 and the satellite signal reception unit 6 . The processing shown in FIG. 6 is only different in step 407 from that shown in FIG. 5 .
In other words, in FIG. 6, when the number of received satellite signals is equal or larger to or than the necessary number for positioning, the control unit 12 clears the count of the timer 11 (step 407 ), then specifies a period of activity time starting from the detection of the signals to the next positioning (step 408 ).
As explained above, the satellite signal receiver according to the fourth embodiment of the present invention adopts a period of activity time starting from the detection of all satellite signals necessary in number for positioning to the positioning, during which time the power is turned on. Thus the period of activity time can be approached or made to agree to or with a remaining period of time to the next positioning to be expected as closer as possible, thereby a period of time to power the satellite signal reception unit being shortened. Useless consumption of the power can be suppressed.
Fifth Embodiment
Referring to FIGS. 2 and 7, a fifth embodiment of the present invention will now be described.
A satellite signal receiver according to the fifth embodiment differs only in that the control unit 12 and the satellite signal reception unit 6 are constructed to perform further processing different from that in the first embodiment. The remaining configuration and operations of this satellite signal receiver are identical to those in the first embodiment, so the differences with respect to the processing and operations are mainly described.
FIG. 7 is a flowchart showing power control for the satellite signal receiver according to the fifth embodiment, which is executed by both of the control unit 12 and the satellite signal reception unit 6 . The processing shown in FIG. 7 corresponds to the processing expressed by steps 406 to 408 , which is a specification process of the period of activity time that starts from the signal detection to positioning. The remaining part of the processing, though not shown in FIG. 7, is identical to that shown in FIG. 6 .
As shown in FIG. 7, from the satellite signal reception unit 6 , the control unit 12 obtains information about the numbers of satellites of which ephemeredes are memorized (step 501 ), then obtains information about the numbers of satellites from which signals are acquired (step 502 ). Then determined is if or not only satellites from which the signals have been received and ephemerides have been acquired are enough for calculation of positioning (step 503 ). If the determination is YES, a shorter period of activity time 1 is specified, because it will be no longer necessary to acquire data to the ephemeris (step 504 ). But the determination is NO, that is, the present satellites of which signals have been detected and of which ephemerides have been acquired are still short of satellites, a longer period of activity time 2 (>the period of activity time 1 ) is specified, for more ephemerides should be acquired (step 505 ).
In this way, the satellite signal receiver of this fifth embodiment is configured to adjust a period of activity time starting from the signal detection of all satellites necessary in number for positioning to the positioning, depending on whether or not the positioning requires acquisition of more ephemerides. Hence, the period of activity time can be close or made agree to or with a remaining period of time to the next positioning to be expected. Accordingly, the power is avoided from being consumed uselessly.
Sixth Embodiment
Referring to FIGS. 8 and 9, a sixth embodiment of the present invention will now be described.
FIG. 8 shows the configuration of a satellite signal receiver according to the sixth embodiment. Compared to the constituents shown in FIG. 2, a positioning-failure counter 16 of which count shows the number of failures in positioning is added to be connect to the control unit 12 and a power supply line from the power supply 3 to the timer 11 is added. The control unit 12 is configured to perform a different type of processing shown in FIG. 9 . The remaining constituents and processing are the same or identical as or to those in the first embodiment, so only such different elements will now be described mainly.
FIG. 9 outlines power control conducted by the satellite signal receiver in the sixth embodiment.
In the present embodiment, the satellite signal reception unit 6 is made to operate in an intermittent manner, so that the timer always receives power from the power supply 3 through the added power supply line.
Thus, the timer 11 is subject to the determination whether or not a period of elapsed time measure by the timer 11 is equal or lager to or than a predetermined intermittent reception interval (step 607 ). When the determination is YES, that is, a period of elapsed time measure by the timer 11 is equal or lager to or than the intermittent reception interval, the control unit 12 turns on the power switching unit 4 to activate the satellite signal reception unit 6 as well as clear a count of the timer 11 (step 601 ).
Then it is determined if the period of elapse time measure by the timer 11 is equal or larger to or than a period of activity time (step 602 ). If the determination is YES at step 602 , the control unit 12 regards the positioning as being impossible. In this case, the control unit 12 turns off the power switching unit 4 (step 603 ), then notifies the not-shown external system of an unsuccessful positioning through the communication unit 13 (step 604 ). The control unit 12 then increments a count of the positioning-failure counter 16 (the count is increased by one) (step 605 ).
By contrast, if the determination is NO at step 602 (the period of elapsed time measure by the timer 11 is less than the period of activity time), the control unit 12 tries to read positional information from the satellite signal reception unit 6 (step 608 ).
Then the control unit 12 begins a process to determine whether the positioning has been finished or not (step 609 ). When the positioning has been finished, the control unit 12 sends an “off” commands to the power switching unit 4 (step 610 ), and outputs the positioning information to the not-shown external system via the communication unit 13 (step 611 ). In this case, a count of the positioning-failure counter 16 is set to zero (cleared; step 612 ). If the positioning has not been finished yet, the control unit 12 returns to the process at step 602 to repeat the foregoing processing.
After the positioning-failure counter 16 has been set at step 605 or step 612 , the intermittent reception interval is adjusted depending on counts of the positioning-failure counter 16 (step 606 ). For instance, the internal is set to 10 minutes when a positioning-failure counter's count is 2 or more, while it is set to 5 minutes when a positioning-failure counter's count is less than 2. As an alternative example, the period of activity time may be changed according to counts of the positioning-failure counter 16 .
After adjustably setting the intermittent reception signal, the control unit 12 determines, like the above, whether or not the period of elapsed time measured by the timer 11 is equal to or over the intermittent reception interval that has been adjusted above (step 607 ). This determination is repeated if NO is kept at step 607 .
If the determination is YES, that is, the period of elapsed time measured by the timer 11 reaches the intermittent reception interval, the processing is moved to step 601 to repeat the foregoing process. Namely, the power switching unit 4 is turned on to activate the satellite signal reception unit 6 as well as clear the count of the timer 11 . As stated above, the satellite signal receiver of this sixth embodiment performs the power control similar to the first embodiment under intermittent operations of the satellite signal reception unit 6 . In this receiver, when the positioning cannot be conducted in series, the intermittent operation interval is widened. As a result, it is therefore possible to shorten a period of time to power the satellite signal reception unit under a condition the positioning cannot be conducted, thus reducing useless consumption of the power.
Seventh Embodiment
Referring to FIGS. 8 and 10, a seventh embodiment of the present invention will now be described.
FIG. 10 outlines power control conducted by the satellite signal receiver in the seventh embodiment. The processing in FIG. 10 is almost the same as that shown in FIG. 9 except that step 705 is added after step 704 corresponding to step 604 in FIG. 9 .
Specifically, after notifying the not-shown external system of an unsuccessful positioning through the communication unit 13 (step 704 ), the control means 11 determines whether or not the number of satellites of which signals have been received is zero (step 705 ). If the determination is YES, that is, none of signals have been received from any satellites, the positioning-failure counter 16 is incremented (step 706 ). In contrast, at least one signal has been received from any satellite (YES at step 705 ), the positioning-failure counter 16 is cleared to zero in its count (step 713 ).
As a result, in the satellite signal receiver according to the seventh embodiment, the power control identical to that explained in the first embodiment is performed with the satellite signal reception unit operating intermittently. In this intermittent satellite signal reception, there is a possibility that any satellite signal cannot be received over a plurality of successive intermittent receptions. Such occasions occur when, for example, the receiver is located at particular places, such as being among city's buildings, which make the reception of electric waves impossible or fairly difficult. In such a case, a period of time to supply the power is shortened through the processing at step 705 , thus saving the power consumption.
For the sake of completeness, it should be mentioned that the various embodiments explained so far are not definitive lists of possible embodiments. The expert will appreciates that it is possible to combine the various construction details or to supplement or modify them by measures known form the prior art without departing from the basic inventive principle.
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A satellite signal receiver includes a satellite signal reception unit, timer, and power-on/off controlling element. The satellite signal reception unit calculates a current position of the satellite signal receiver using an electric wave from a satellite, in response to a positioning request. The timer is used to clock an elapsed time in calculating the current position of this receiver. The power-on/off controlling element controls an on/off state of power supplied to both the satellite signal reception unit and the timer on the basis of information including the positioning request, the elapsed time clocked by the timer, and a reception condition of the satellite signal reception unit. Accordingly, a period of time for supplying the power is automatically turned on/off to be shortened in cases the positioning is impossible, thus the power being saved.
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BACKGROUND OF THE INVENTION
The present invention relates to a spot-type disc brake of the type including a brake carrier including a mounting section extending substantially in parallel to a brake disc and two brake carrier arms which project beyond the rim of the brake disc. The disc brake also includes a brake housing axially displaceable on the brake carrier and accommodates actuating means. The housing straddles the rim of the brake disc and two brake shoes, with the brake shoes being supported and guided on the brake carrier.
A stop-type disc brake of this type is disclosed in the German patent DE 28 04 808 B2. In present spot-type disc brakes, the brake shoes, in the end zones thereof, are provided with radially extending bridges which are formed to support and guide the brake shoes and to uniformly transfer the forces developed during deceleration in the circumferential direction to the two brake carrier arms. In these disc brakes the two brake shoes have identically configurated back plates. While these brakes offer a satisfactory solution to the problem of providing for uniform force distribution such that the brake carrier arms may be correspondingly dimensioned, the manufacture of these brakes involves substantial effort and is relatively expensive.
SUMMARY OF THE INVENTION
It is, therefore, the object of the present invention, to improve the conventional spot-type disc brake in that manufacturing efforts and costs are reduced.
This object is achieved according to the invention which provides for finished guide elements to be mounted on the brake housing such that additional processing operations on the brake housing, such as broaching and the like, can be eliminated. According to the invention, the guide elements for this purpose are in the form of guide pins.
According to an advantageous feature of this invention, the guide elements are disposed on the side of the brake housing opposite the actuating means. The brake shoe on which the guide element is mounted includes at least one substantially radially extending bridge forming at least one abutment face for the guide element. Advantageously, an abutment face extending in substantially radial direction is provided on the bridge and, in side-by-side relationship therewith, an abutment face extending in substantially tangential direction is provided for the guide element.
According to another highly advantageous feature of the invention, the brake shoe associated with the actuating means is provided with a back plate which is shorter in length than the back plate of the other brake shoe and does not require bridges extending crosswise for the support and the force transfer. The elimination of such support bridges is possible without affecting force transfer because according to the invention the brake pad, in the area of the mounting section, is disposed in a guide shaft. Accordingly, manufacturing costs in the area supporting the inner brake shoe are thereby reduced.
According to another important feature, the brake shoe associated with the actuating means includes abutment faces extending in substantially radial direction to which are associated abutment faces correspondingly disposed on the brake carrier. This brake shoe also includes substantially tangentially extending bearing faces to which are associated correspondingly extending bearing faces disposed on the brake carrier. The bearing faces on the brake carrier are disposed in the plane of the piston of the actuating means, with the contact faces of the brake shoe associated with the actuating means being minimized and thereby insensitive to corrosion.
The brake shoe associated with the brake applying means, advantageously, can be provided with a spring capable of being supported on the brake housing, with the spring, preferably, being configurated as a stem spring having two windings of which one is disposed on one side of the back plate of the brake shoe and of which the other is located on the other side of the back plate of the brake shoe, with recesses, being provided in the back plate. Specifically, a spring of the type shown and described in German Patent DE-OS 32 20 632.1 may be used.
Advantageously, a bolt guide is provided on the side of the housing associated to the actuating means to form the guide for the brake housing. The bolt guide includes two guide bolts having a guide sleeve and a threaded bolt passed therebetween for fixation to the brake carrier.
Provided between the guide bolts and the corresponding bores in the brake housing are flexible damping sleeves including a rubber material exhibiting anti-friction properties so as to avoid the use of floating insets as is employed with conventional brakes. To preclude ingress of dirt into the interior of the damping sleeve, the same is provided with radially inwardly projecting sealing lips especially located at the two ends. The sealing lips are so configurated as to maintain the sealing function during any radial displacement of the guide bolt, which is achieved by sealing lip shaping and prestressing. Preferrably, the sealing lips include conical flanks and, in a non-loaded condition, are of a small inside diameter.
According to another advantageous feature, the outer brake shoe includes an abutting and a bearing face, respectively, for receiving a guide member on the brake caliper. The abutting or bearing faces are provided in the area of a brake shoe bridge which extends substantially in a radial direction.
The inner brake shoe associated with the actuating means, is of shorter length than an outer brake shoe. The outer shoe is provided with the bridge which extends in both the transverse and in the radial direction, circumferentially effective forces are transferred to the two brake carrier arms through the bridge.
BRIEF DESCRIPTION OF THE DRAWING
The invention will be better understood after reading the following Detailed Description Of The Preferred Embodiment in conjunction with the drawing in which:
FIG. 1 is a plan view of a spot-type disc brake according to the invention;
FIG. 2 is a front partial cross-sectional view of the disc brake of FIG. 1, as viewed from the outside; and
FIG. 3 is a cross-sectional view of a damping sleeve.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Shown in the drawing is a floating caliper spot-type disc brake for automotive vehicles, including a brake carrier 1 having a mounting section 1a to be stationarily affixed to a steering knuckle of an automotive vehicle. Brake shoes 3, 4 are axially displaceably guided and held on the brake carrier on either side of a brake disc (not shown) and a brake caliper 5 externally straddles the rim of the brake disc and the brake shoes 3, 4 in U-shaped manner. The brake carrier 1, in circumferential and tangential directions, respectively, relative to the brake disc includes spaced-apart brake carrier arms 6, 7 straddling the rim of the brake disc and grooves 8, 9, 10, 11 on either side of the brake disc. The delimiting surfaces of the grooves 8, 9 and 10, 11, respectively, disposed in a brake carrier arm 6 and 7, respectively, are each disposed in common planes extending in parallel to the axis of rotation of the brake disc.
The wall surface 12 facing the brake center, in the circumferential direction, is slightly off-set, with only the axially outer section 12a being a machined surface. The same structure applies to the other wall surface 13 and 13a, wherein section 13a is a machined surface. The wall surfaces of grooves 8, 9, 10 and 11 opposite the wall surfaces 12, 13 are designated by numerals 14, 15, 16, 17. Wall surfaces 14, 15, 16, 17 terminate within the outer circumference of the brake disc to abut bearing surfaces 23, 24, 25, 26 which are located in a common plane extending in the tangential or circumferential direction and which coincide with the surface center of gravity of the brake piston 30. These bearing 23, 24, 25, 26 surfaces are all machined surfaces.
The carrier plates of the brake shoes 3, 4 are mounted on the bearing faces 23, 24, 25, and 26. The carrier plate of the outer brake shoe 3 includes ends 19, 21 which extend down to the wall faces 12, 13 to support itself, and the front sides 34, 35 thereof, are disposed externally of the outer circumference of the brake disc. Provided at the ends of the brake shoe 3 are radially inwardly directed lugs 19', 21' the front surfaces of which face one another and are in abutment with the wall faces 15, 17, with the clearance between the wall faces 15, 17 and the front faces of the lugs being equal to or smaller than the clearance between the front sides 34, 35 and the wall surfaces 12, 13. This structure assures that the frictional forces acting on the brake shoes during application of the brake either are transferred solely to the front brake carrier arm or to both carrier arms, but in no case to solely the rear brake carrier arm.
The carrier plate of the inner brake shoe 4 in the end areas thereof includes two bearing surfaces mounted on the correspondingly machined supporting faces 23, 24 of the brake carrier. Abutment faces of the carrier plate extending vertically thereto are supported on correspondingly machined abutment faces provided in the area of the mounting section of the brake carrier, one of which is designated by numeral 35.
The brake housing 5 is connected in a manner axially displaceable to the brake carrier by means of bolt guides 27 disposed on the side of the brake carrier 1 facing away from the brake disc. Between the bolt guides 27, the brake housing 5 is provided with a hydraulic brake applying cylinder 28 to which pressure fluid is supplied through a connecting bore 29. Piston 30 of the actuating cylinder 28 through the front face thereof is directly in abutment with the brake shoe 4. A rubber protective cap 31 protects the sliding surface of the piston 30 against damage or ingress of dirt.
The brake housing 5, on the side of the brake disc opposite the actuating cylinder 28 includes two lugs extending circumferentially, wherein axially extending pins 61, 62 are fixed. Pins 61, 62 are press fitted into corresponding bores. The pins extend toward the brake disc and are mounted on the bearing surfaces formed by the carrier plate of the outer brake shoe 3, one of which, in FIG. 2, is designated by numeral 63. Bearing faces 63 substantially extend in the circumferential direction. Abutment faces substantially extend at right angles thereto, one of which, in FIG. 2, is designated by numeral 64.
Both the abutment faces 64 and the bearing faces 63, in the area of a transverse-extending bridge 65, are formed on the carrier plate of the brake shoe 3. Pins 61, 62 are mounted against the respective bearing faces 63 and abutment faces 64 thereby providing a guide. The portion of brake housing 5 disposed between the abutment faces 64, forms a support resulting in a reduction of flexing stress at the carrier plate of the brake carrier. The ends of the brake shoe 3, are, therefore, exposed to only minor flexible deformation.
Disposed on the side of the housing opposite the actuating cylinder 28 is a wire spring 32 forming circumferentially extending arms that are supported on the bottom side of the brake carrier arms 6, 7, and free ends which engage apertures in the brake housing 5 for fixing the spring. The brake housing 5 is thereby loaded over the brake carrier through the carrier plate of the brake shoe 3. Stated differently, the spring forces the brake housing 5 and, hence, the pins 61, 62 against the bearing faces 63 of the carrier plate of the brake shoe 3, with the brake shoe being forced against the bearing surfaces 24, 26 formed on the brake carrier arms 6, 7.
The inner brake shoe 4 includes a centrally located pad-free section 70. Provided on the front and on the rear side of that section 70, are recesses 71, 72 in which are disposed windings 73, 74 of a stem spring 75. The free stems 76, 77 of the stem spring 75 are supported on the inner side of the brake housing 5 which, in that area, forms a shoulder 78. The brake shoe 4 is forced by the stem spring 75 against the bearing surfaces 23, 25 on the brake carrier arms 6, 7.
Two bolt guides 27 are provided for guiding the brake housing on the side proximate the actuating means. Bolt guides 27 each include a threaded bolt 80 guided through a guide sleeve 81 and threaded into the brake carrier. The head 82 of the threaded bolt 80 forces the guide sleeve 81 against a surface of the brake carrier. Seated between the guide sleeve 81 and a bore 82 in the brake housing 5 is a flexible damping element 83 shown in detail in FIG. 3. The flexible damping member 83 includes a substantially cylindrical base body 84 provided on the inner side thereof with radially inwardly protruding sealing lips 85, 86. Provided between the sealing lips 85, 86 respectively disposed at the end of a sealing area, are further protruding lips 87 which, protrude radially inwardly a lesser degree than the sealing lips 85, 86. The sealing lips 85, 86 include conical flanks 88, 89 facing one another. Faces 90, 91 of the sealing lips 85, 86 facing away from one another, are of an accurate configuration. Formed on the outer circumference of the damping sleeve 83 is a groove 92 to insert the damping member into the bore 82 of brake housing 5 and maintain same therein. Additional lips may be provided on an extension 93 joining the cylindrical base body of the damping member, with a sleeve 94 being provided in the end region in the form of embodiment as shown in FIG. 3. The damping sleeve 94 is made of a rubber material having anti-friction properties. Ingress of dirt into the interior of the damping sleeve is reliably precluded by means of the sealing lips 85, 86, with the sealing lips 85, 86 being so designed that the sealing function during a radial displacement of the guide bolt, is maintained. The seal is achieved by appropriate shaping and prestressing of the lip. For that purpose, the sealing lips 85, 86, specifically, are of a small inside diameter in the non-loaded condition and include the afore-mentioned conically extending flanks.
Operation of the spot-type disc brake will now be explained in greater detail with reference to FIG. 2. Basic to the description of operation is the assumption that the brake disc rotates in the counter-clockwise direction as indicated by arrow 43. The line of action 45 of the resultant frictional forces extends through point 44 coinciding with the piston center. If the clearance arising during manufacture between the wall face 15 and the neighboring front face of the brake shoe 3 is smaller than the clearance between the wall face 17 and the front side 35, the brake shoe, in the indicated direction of rotation of the brake disc, will first be supported on the wall surface 12a. As the line of action of the resulting frictional forces extends approximately at the level of the supporting surface 24, no substantial torque will occur on the brake shoe 3. The end 19 will be held through frictional engagement with the wall surface 12 in its at rest position on the supporting surface 26. If the brake shoe 3, with a greater clearance between its front faces and the wall face 17, or after a flexible deformation of the brake carrier arm 6, with the front side 35 thereof is supported on the wall face 12a, due to the position of the abutment face radially externally of the line of action 45 achieved by recesses 37 in the abutment faces 34, 35, a torque occurs on the brake shoe 3 tending to force the end 19 of the brake shoe 3 against the supporting face 26. As a result of the mirror-inverted configuration of the brake shoe 3, this will also apply, in analogy, to the reverse direction of rotation. The inner brake shoe 4 with the brakes applied, will be forced with the radially extending abutment face against the corresponding abutment face 35 of the brake carrier arm 7.
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A spot-type disc brake is disclosed including a brake carrier including a mounting section extending substantially in parallel to a brake disc, and two brake carrier arms protruding beyond the rim of the brake disc. A brake housing is disposed in axially displaceable manner on the brake carrier and accommodates an actuating means. The brake housing straddles the rim of the brake disc and two brake shoes wherein the brake shoes are supported and guided on the brake carrier. To permit a simple and low-cost manufacture, at least one guide member is fixed to the brake housing which for guiding the brake housing is mounted on guide sections of one of the brake shoes.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a method, apparatus, and medicine for clogging blood vessels of an eye fundus.
2. Description of the Prior Art
There is known a method for clogging blood vessels of an eye fundus. There is also known a photocoagulator used as an apparatus for clogging blood vessels of an eye fundus. In the photocoagulator, an infrared fluorescent agent, called indocyaninegreen, is injected into a subject. When the infrared fluorescent agent circulates through the blood vessels of the eye fundus of the subject, infrared rays of light for excitation are projected onto the eye fundus and, as a result, the infrared fluorescent agent is excited to emit fluorescence. While a region emitting the fluorescence is being observed, a diseased part, such as neovascular vessels of a choroid, in the depth of the eye fundus is specified. After that, a near-infrared semiconductor laser beam is projected onto the diseased part so as to coagulate and treat the diseased part.
In this conventional method and apparatus, however, injury to normal tissues is unavoidable during the treatment because of photocoasulation. Therefore, it is expected to develop a fundus treating method by which a diseased part only is treated to the utmost without injury to normal tissues, and develop an apparatus and a medicine used for the treatment.
SUMMARY OF THE INVENTION
The present invention was made in view of the foregoing. It is therefore an object of the present invention to provide a fundus vessel clogging method by which only a diseased part of an eye fundus is treated to the utmost without injuring normal tissues, an apparatus used for clogging the blood vessels, and a medicine to clog them.
In order to achieve the object, a fundus vessel clogging method according to an aspect of the present invention includes the steps of furnishing a subject with a photosensitive substance which remains in a diseased part in the depth of the eye fundus where an infrared fluorescent agent remains and which undergoes a photochemical change in the diseased part by the use of a laser beam with a specific wavelength as well as furnishing the subject with the infrared fluorescent agent, specifying the diseased part in accordance with emission of infrared fluorescence, and projecting the laser beam with the specific wavelength onto the diseased part so that the photosensitive substance will produce a photochemical change, thereby clogging blood vessels of the diseased part in the depth of the eye fundus.
In order to achieve the object, a fundus vessel clogging apparatus according to an aspect of the present invention includes an illuminating optical system for illuminating an eye fundus of a subject, who has been furnished with an infrared fluorescent agent, with infrared rays of light so as to excite the infrared fluorescent agent and emit infrared fluorescence, a photographic optical system for observing and photographing the eye fundus, and a projecting optical system for projecting a laser beam with a specific wavelength onto the subject who has been furnished with a photosensitive substance which undergoes a photochemical change by means of the laser beam. In the apparatus, the laser beam is projected onto the photosensitive substance and thereby blood vessels of the diseased part in the depth of the eye fundus are selectively clogged while a region emitting the infrared fluorescence is being observed.
In order to achieve the object, a medicine according to an aspect of the present invention includes a mixture containing an infrared fluorescent agent and a photosensitive substance of the following general formula (CHEMICAL FORMULA 3): ##STR1##
In order to achieve the object, a medicine according to another aspect of the present invention includes a mixture containing an infrared fluorescent agent and a photosensitive substance of the following general formula (CHEMICAL FORMULA 4): ##STR2##
A fundus vessel clogging apparatus according to another aspect of the present invention is characterized in that a diseased part in the depth of an eye fundus is specified by infrared fluorescence, and a laser beam with a specific wavelength is projected onto a photosensitive substance which accumulates in the diseased part and undergoes a photochemical change by means of the laser beam for the purpose of treatment for the diseased part.
It is preferable to project an aiming laser beam which serves to distinguish a part where the laser beam is projected from a part where the infrared fluorescence emits in such a way as to superimpose the aiming laser beam upon the laser beam. More preferably, the aiming laser beam is intermittently projected.
According to the present invention, the infrared fluorescent agent and the photosensitive substance remain in the diseased part. In this situation, the remaining of the photosensitive substance in the diseased part is larger than that of the infrared fluorescent agent therein. Therefore, the diseased part is observed and specified by the infrared fluorescent agent, and thereafter a laser beam with a wavelength by which the photosensitive substance produces a photochemical change is projected. Thereby, since only the photosensitive substance produces a photochemical change, an influence on normal tissues is avoided as much as possible, and accordingly the diseased part only can be treated. In this case, if a mixture containing an infrared fluorescent agent and a photosensitive substance is used as a medicine, intravenous injection into the subject can be given at a time.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic drawing showing optical systems of a fundus blood vessel clogging apparatus according to a first embodiment of the present invention.
FIG. 2 is a schematic sectional view showing the tissue structure of an eye fundus according to the present invention.
FIG. 3 is a schematic drawing showing optical systems of a fundus blood vessel clogging apparatus according to a second embodiment of the present invention.
FIG. 4 is a plan view showing a pattern plate of FIG. 3.
DETAILED DESCRIPTION OF THE EMBODIMENTS
FIG. 1 shows an embodiment of a method for clogging blood vessels of an eye fundus and an apparatus, which is applied to a fundus camera, for clogging the blood vessels. In FIG. 1, reference numeral 1 designates an illuminating optical system of the fundus camera, and reference numeral 2 designates a photographic optical system thereof. The illuminating optical system 1 includes a halogen lamp 3 and a xenon tube 4. The halogen lamp 3 is conjugate to the xenon tube 4 with respect to a condenser lens 5. The illumination light of the halogen lamp 3 and that of the xenon tube 4 are condensed by a condenser lens 6 and then are guided to a reflecting mirror 8 through an annular diaphragm 7. A laser diode may be used instead of the halogen lamp 3.
The illumination light reflected by the reflecting mirror 8 passes through a relay lens 9, is then reflected by a perforated mirror 10, is guided to the eye fundus R of a subject through an objective lens 11, and illuminates the eye fundus R. The light beam from the eye fundus R passes through the objective lens 11 and is then guided to a focusing lens 13 through a hole 12 of the perforated mirror 10. A quick return mirror 14 is disposed behind the focusing lens 13. When a photograph is taken with a film (i.e., when a still image is recorded), the quick return mirror 14 is removed from the optical path of the photographic optical system 2. An image of the fundus is formed on a film 15 by the focusing lens 13. On the other hand, during observation, the light beam from the fundus R is reflected by the quick return mirror 14, and the fundus image is formed on a CCD 16. A signal output of the CCD 16 is converted into an image signal by an image processing circuit (not shown), and the fundus image is formed on a TV monitor (not shown). A surgeon performs an operation, mentioned later, while observing the TV monitor. In the case of visible fluorescence, a fundus image may be observed by the use of a finder optical system 16' which is made up of a quick return mirror 14' and an eyepiece 15'. When the finder optical system 16' is not used, the quick return mirror 14' is placed out of the optical path of light reflected by the quick return mirror 14.
In accordance with a photographic mode, an exciter filter 17 for visible fluorescence and an exciter filter 18 for infrared fluorescence are inserted into the optical path between the annular diaphragm 7 and the condenser lens 6. Correspondingly to the insertion of the exciter filter 17 for visible fluorescence and the exciter filter 18 for infrared fluorescence into the optical path of the illuminating optical system 1, a barrier filter 19 for visible fluorescence and a barrier filter 20 for infrared fluorescence are inserted into the optical path between the perforated mirror 10 and the focusing lens 13 of the photographic optical system 2. When the exciter filter 17 for visible fluorescence is inserted into the optical path of the illuminating optical system 1, green illumination light is guided to the fundus R, and the fundus R is illuminated with the green illumination light. On the other hand, when the exciter filter 11 for infrared fluorescence is inserted into the optical path of the illuminating optical system 1, red and infrared illumination light is guided to the fundus R, and the fundus R is illuminated therewith. In a color photographic mode except the fluorescence photographic mode, the exciter filters 17, 18 are placed out of the optical path of the illuminating optical system 1, and the barrier filters 19, 20 are placed out of the optical path of the photographic optical system 2.
In the optical path of the illuminating optical system 1, there is disposed a reflecting optical member 22 which serves as a constituent part of a laser projection optical system 21 used for photocoagulation between the reflecting mirror B and the relay lens 9. In this embodiment, a half mirror is used as the reflecting optical member 22. The laser projection optical system 21 includes a laser light source 23. Herein, a source for emitting a laser beam having a wavelength range of visible light (wavelength of 664 nm) is used as the laser light source 23. A selective diaphragm 24 is disposed in front of the laser light source 23. The selective diaphragm 24 is conjugate to the fundus R with respect to the objective lens 11. When a blood vessel clogging treatment is conducted, a shutter 25 is inserted between the CCD 16 and the quick return mirror 14 in accordance with the power of a laser beam. The shutter 25 has a function of preventing the CCD 16 from being burned by the reflection of a laser beam having a high power. Likewise, a shutter 25' is inserted into the finder optical system 16'. The laser projection optical system 21 includes a laser light source 27 used for aiming. The laser light source 23 is conjugate to the laser light source 27 with respect to a half mirror 28. Relay lenses 29, 30 are disposed between the half mirror 28 and the reflecting optical member 22.
The selective diaphragm 24 consists of diaphragms 31, 32 which differ in aperture diameter from each other. Either of the selective diaphragms 31, 32 is inserted between the relay lens 29 and the relay lens 30. When a treatment for clogging blood vessels of a diseased part is conducted, a laser spot is formed on the fundus R in accordance with the diameter of an aperture of the selective diaphragm 24. A laser beam emitted by the laser light source 27 is designed to have a wavelength range within which the laser beam can pass through the barrier filter 20. In this embodiment, the wavelength of the laser light source 27 is of a green range.
Since color photography and visible fluorescence photography are not directly relevant to the present invention, an explanation thereof is omitted. Thus, infrared fluorescence photography will be explained.
When the infrared fluorescence photography is carried out, an infrared fluorescent agent, called indocyaninegreen, of the following chemical formula (CHEMICAL FORMULA 5) is injected into the veins of the subject or is taken by the subject in advance. ##STR3##
The infrared fluorescent agent circulates through the fundus and is then illuminated with excitation light having a specific wavelength which has passed through the exciter filter 18 for infrared fluorescence. Thereby, infrared fluorescence is emitted. If the fundus R has a diseased part K1, such as neovascular vessels, as shown in FIG. 2, the infrared fluorescent agent remains in the diseased part K1. Thereby, the amount of fluorescence from the diseased part K1 becomes larger than that of fluorescence from around the diseased part K1. Therefore, the diseased part K1 shining brightly on a TV monitor can be located. Conventionally, an infrared laser beam has been projected, taking careful aim, onto the diseased Part K1, and thereby the diseased part K1 has been coagulated. However, disadvantageously, this conventional photocoagulation method brings about an injury to normal tissues therearound. In the present invention, therefore, a photosensitive substance of the following constitutional formula (CHEMICAL FORMULA 6) is injected into the veins of the subject or is taken by the subject. ##STR4##
This photosensitive substance is a tetrapyrrole derivative. Mono-L-aspartiru chlorin/e6/4 sodium salt (Abbreviated Npe6), one of the tetrapyrrole derivatives, is accumulated together with the infrared fluorescent agent in the endothelium of blood vessels of the diseased part K1 such as neovascular vessels. Active oxygen is then generated by the projection of a laser beam having the wavelength of 664 nm thereonto, and thereby the blood vessels of the diseased part K1 are clogged.
The following formula (CHEMICAL FORMULA 7) is a stereoisomer of CHEMICAL FORMULA 6. It is preferable to use a chemical compound of this formula instead of CHEMICAL FORMULA 6. ##STR5##
The photosensitive substances are mixed with the infrared fluorescent agent, and advantageously a mixture containing them is given to the subject by intravenous injection at a time.
As described above, the laser light source 23 emits a laser beam having the wavelength of 664 nm in order to cause the photosensitive substance to generate a photochemical change. When the diseased part K1 is treated, a laser spot is formed on the fundus R in accordance with the diameter of an aperture of the selective diaphragm 24. The laser power of the laser light source 23 can be regulated by a power regulator (not shown). It is desirable that the laser light source 23 is capable of making the laser oscillation with the projection intensity of 20 to 500 mW/cm 2 and with the full power of at least 500 mW.
In the laser projection optical system 21, a laser beam is projected by aiming at a marker which is a region of infrared fluorescence shining brightly in the fundus R. Thereby, the photosensitive substance is caused to generate a photochemical change. Consequently, neovascular vessels can be clogged without injuring normal tissues to the utmost.
FIG. 3 shows a second embodiment of a fundus camera to which the present invention is applied. The fundus camera of the second embodiment is constructed such that a pattern plate 33 is disposed between the laser light source 27 for aiming and the half mirror 28, and the relay to the eye fundus R is made through relay lenses 34, 35. As shown in FIG. 4, for example, a star-shaped aiming pattern is projected onto the pattern plate 33. Thereby, a distinction can be easily drawn between a part where the laser beam is projected and a part where infrared fluorescence is emitted. In order to distinguish the two parts more easily, a construction may be employed in which the laser light source 27 for aiming is intermittently driven to flicker the aiming pattern.
According to the present invention, the method for clogging blood vessels of an eye fundus and the apparatus and medicine used for clogging the blood vessels have the advantage that only the blood vessels of a diseased part are clogged for a surgical treatment almost without injury to normal tissues.
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An apparatus for clogging blood vessels of an eye fundus includes an illuminating optical system (1) for illuminating an eye fundus of a subject, who has been given an injection of an infrared fluorescent agent, with infrared rays of light and exciting the infrared fluorescent agent so as to generate infrared fluorescence, a photographic optical system (2) for observing and photographing the eye fundus, and a projecting optical system (21) for projecting a laser beam of light having a specific wavelength onto the subject who has been also given an injection of a photosensitive substance which undergoes a photochemical change by the laser beam. In the apparatus, while a region which emits infrared fluorescence is being observed, the laser beam is projected onto the photosensitive substance so as to clog blood vessels of a diseased part in the depth of the eye fundus.
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CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This present application is a continuation patent application of International Application No. PCT/SE02/00260 filed 21 Feb. 2002 which was published in English pursuant to Article 21(2) of the Patent Cooperation Treaty, and which claims priority to Swedish Application No. 0100585-9 filed 21 Feb. 2001. Both applications are expressly incorporated herein by reference in their entireties.
BACKGROUND OF INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to an apparatus for damping resonance in a conduit for transporting exhaust gases from an internal combustion engine.
[0004] 2. Background
[0005] In most cases, a silencer system consists of one or more chamber(s) with intermediate conduits. The sound pressure inside the conduit will vary with the position along the conduit. Pipe resonance can sometimes occur in an exhaust system and stems from ignition pulses from the engine being reflected between the mouth of the exhaust pipe and a preceding part of the exhaust system, frequently that part being the chamber in the silencer closest to the end pipe. In most cases, this only happens at a specific engine speed, where the wavelength of the ignition frequency coincides with the length between the two adjacent reflecting pipe ends.
[0006] In cases when resonance has occurred in the pipe, the differences in sound pressure will be particularly great between different positions. A high sound pressure then builds up in the end pipe, and sound escapes into the surrounding environment via the mouth to a greater extent than would otherwise have been the case. Known solutions to this problem usually involve the insertion of additional silencer units, which results in higher costs and can also lead to an increase in the pressure drop.
SUMMARY OF INVENTION
[0007] One object of the invention is therefore to produce an apparatus which solves the above-described problem(s), and without appreciably raising manufacturing costs.
[0008] To this end, an apparatus configured according to the teachings of the presently disclosed invention includes a conduit that is provided with at least one perforation located at a distance from the outer end of the conduit. By virtue of this design of the apparatus, an effective reduction in the resonance level is brought about in a simple manner without impacting costs of manufacture in any significant way.
BRIEF DESCRIPTION OF DRAWINGS
[0009] The invention will be described in greater detail below with reference to illustrative embodiments shown in the accompanying drawings, in which:
[0010] [0010]FIG. 1 shows a diagrammatic plan view of a portion of a conduit designed according to a first variant of the invention;
[0011] [0011]FIG. 2 is a longitudinal section through a portion of a conduit designed according to a second variant of the invention;
[0012] [0012]FIG. 3 is a longitudinal section through a portion of a conduit designed according to a third variant of the invention;
[0013] FIGS. 4 - 5 show modifications of the variant of the invention shown in FIG. 2; and
[0014] FIGS. 6 - 7 show a part of the plate wall of the conduit in a section and a plan view, respectively, illustrating examples of different perforations.
DETAILED DESCRIPTION
[0015] The invention relates to an apparatus that can be applied to exhaust systems and silencer systems in various types of internal combustion engine arrangements, for example engines which function according to the Otto, Diesel or Wankel principles. The engine can be located in a vehicle, for example a passenger car, a truck, a work vehicle, a marine vessel or other type of craft. The invention can also be applied to fixed engine installations, such as engine-driven power plants and the like. The apparatus can then be located in different positions along the pipe portions which form part of the exhaust and silencer systems of the engine. Such a pipe portion can form, for example, the end pipe which transports exhaust gases from a silencer out into the surrounding environment.
[0016] [0016]FIG. 1 shows a pipe portion 10 , curved essentially at a right angle, with an outlet end 11 and an inlet end 12 , the wall 13 of which has a perforation 14 on the inside of the curve. The perforation connects the inner volume of the pipe to the surrounding environment. When the pipe portion is mounted in an exhaust system, for example as an end pipe, and a pulsating exhaust gas flow passes through the pipe portion, resonance may occur. Some of the sound pressure in this resonance can escape to the surrounding environment via the perforation 14 . This means that the size of the resonance is reduced. In this way, the escaping sound, both from the mouth of the outlet and 11 and through the perforation 14 , will occur at a significantly lower sound pressure level than would have exited the end 11 . Overall, a smaller magnitude sound will be emitted to the surrounding environment from the exhaust system.
[0017] Exhaust emissions through the perforation 14 can be avoided, because the hole is located in a part of the flow passage where the static pressure is comparatively lower than in other parts of the passage.
[0018] [0018]FIG. 2 shows on a larger scale an alternative embodiment of the invention in which a number of perforations 14 are made in the pipe wall 13 of a pipe section 10 having a portion 10 a with a slightly reduced flow area. In this connection, the flow rate will increase within this portion with a commensurate reduction in static pressure in the pipe as a consequence. As a result, surrounding air can be sucked into the pipe through the perforations without exhaust gases escaping.
[0019] [0019]FIG. 3 illustrates a further variant of the invention, where an indentation 15 has been made in the pipe wall 13 in such a manner that a reduction in the flow area has been brought about in this part. Downstream of the indentation 15 , the pipe wall forms a step 16 essentially at right angles out to the normal cross section. A perforation 14 is located on the downstream side of this step. An exhaust gas flow through the pipe section in FIG. 3 will increase its flow rate at the indentation 15 . The reduced pressure will draw air in from the surrounding environment of the pipe via the perforation 14 .
[0020] Another way of avoiding leakage of exhaust gases via a perforation can be to introduce a partly sound-permeable material which will serve as flow resistance. This material can be applied on the outside of the pipe, inside the pipe or in the perforations themselves. The material can consist of steel, another metal, glass fiber, textile material, ceramic and so forth. The material can, for example, have a structure in the form of a mesk, net, unstructured or structured fabric, and also porous medium.
[0021] [0021]FIG. 4 shows a modification of the invention where a conduit designed according to FIG. 2 has been provided with an outer sleeve 17 which covers the perforations and is provided with a large number of small perforations 18 . The purpose of the outer sleeve 17 is essentially to “conceal” the perforations 14 . The outer sleeve 17 also provides a certain damping of sound leakage via the perforations 14 . This leakage can be damped further by virtue of a space 19 between the conduit 10 and the outer sleeve being filled with a suitable damping material, for example mineral wool.
[0022] [0022]FIG. 5 shows another modification of the invention where a conduit designed according to FIG. 2 has been provided with an internal cuff made of sound-permeable non-woven fabric.
[0023] As is evident from FIGS. 6 and 7, the perforations 14 can be made in a number of different ways. The invention comprises a hole which is usually made in a geometrical shape, for example round, square, V-shaped, slot-shaped or any other shape.
[0024] The invention is not to be regarded as being limited to the illustrative embodiments described above, but a number of other variants and modifications are possible within the scope of the following patent claims. For example, the apparatus according to the invention can comprise a combination of a number of pipe portions 10 arranged in series or in parallel.
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Method and apparatus for damping resonance in a conduit ( 10 ) utilized for transporting exhaust gases from an internal combustion engine. The resonance is damped by virtue of the conduit ( 10 ) being provided with at least one perforation ( 14 ) located at a distance from the outlet end ( 11 ) of the conduit.
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FIELD OF THE INVENTION
[0001] The present invention belongs to the technical field of lithium-ion secondary batteries and in particular relates to a lithium-ion secondary battery and a formula for the gel electrolyte thereof.
BACKGROUND OF THE INVENTION
[0002] As a very important part of a lithium-ion secondary battery, liquid electrolyte typically consists of lithium salt, an organic solvent and an additive. However, being a flowing liquid, the organic solvent has a potential leakage hazard. Besides, the general use of carbonic ester and carboxylic ester as the organic solvent of a liquid electrolyte leads to a poor high-temperature performance of a battery; moreover, the inherent inflammability of the organic solvent makes the battery potentially explosive.
[0003] A great amount of research has been made on polymer electrolyte. As a substitute for liquid electrolyte, polymer electrolyte, with distinct advantages including no liquid leakage, excellent high-temperature performance, high cell hardness and high safety, can meet new industrial requirements on Lithium-ion secondary battery.
[0004] The common gel polymer electrolyte used in polymer electrolyte is generally prepared using an in-situ thermal polymerization method in the following way: mix a micromolecular monomer, a liquid electrolyte and an initiator uniformly, inject the mixture into a cell, heat the cell to form a gel so that the micromolecular monomers are cross-linked into a polymer substrate of a network structure under the initiation of the initiator, and trap the liquid electrolyte in the polymer substrate.
[0005] However, the gel polymer electrolyte prepared using this method has the following disadvantages: the average molecular weight of the formed polymer substrate is low for the sake of the chain transfer and the chain termination reaction caused by the existence of an solvent during the polymerization process of micromolecular monomers, resulting in a poor bonding between a separator and an electrode material for the low cohesive strength of the generated polymer substrate and a low mechanical strength of a cell which leads to a great swelling of a cell during a cycle process, moreover, residual micromolecules also affect the electrochemical performance of the cell.
[0006] Thus, it is indeed necessary to provide a gel electrolyte formula in which a monomer having a relatively large average molecular weight is introduced to prepare a gel electrolyte having a high cohesive strength and to enable a battery containing the electrolyte to meet basic electrochemical performances with superb mechanical strength, excellent cycle performance and a relatively high safety.
SUMMARY OF THE INVENTION
[0007] One of the purposes of the present invention is to address the disadvantages of the prior art with a gel electrolyte formula in which a monomer having a relatively large average molecular weight is introduced to prepare a gel electrolyte of a high cohesive strength.
[0008] To achieve the purpose above, the present invention adopts the following technical scheme:
[0009] a gel electrolyte formula comprises 90-99.4% by weight of a liquid electrolyte, 0.5-3% by weight of a monomer, 0.25‰-0.6% by weight of a cross-linking agent and 0.1-1.5% by weight of an initiator,
[0010] wherein the monomer is modified polyvinyl alcohol and the derivates thereof, the average molecular weight of which is 5×10 4 g/mol to 15×10 4 g/mol.
[0011] With respect to the prior art, the present invention forms a gel electrolyte by using a modified polyvinyl alcohol having a relatively high average molecular weight and the derivates thereof, which are polymerized under the initiation of an initiator to form a network polymer substrate of a high cohesive strength which is further cross-linked under the cross-linking effect of a cross-linking agent into a three-dimensional network skeleton of a high mechanical strength to trap a liquid electrolyte in the skeleton, as the monomer in the gel electrolyte. As the formed skeleton has a high mechanical strength, a cell containing the gel electrolyte also has a relatively high mechanical strength and is therefore less swelled during a cycle process.
[0012] The modified polyvinyl alcohol and the derivates thereof containing a certain hydroxyl, when cross-linked into a network polymer substrate under the initiation of the initiator, form intramolecular hydrogen bonds or extramolecular hydrogen bonds to further increase the cohesive strength of the polymer substrate. Further, with a certain adhesion, the modified polyvinyl alcohol and the derivates thereof are capable of enhancing the interface binding force between the gel electrolyte and the surface of the cathode, the surface of the anode or the separator to inhibit the swelling of the battery during a cycle process. Apparently, the average molecular weight of the modified polyvinyl alcohol and the derivates thereof cannot be too large, otherwise, the solubility and the polymerization activity of the modified polyvinyl alcohol and the derivates thereof are undesirable, on the other hand, the average molecular weight of the modified polyvinyl alcohol and the derivates thereof cannot be too small, otherwise, the chain transfer and the chain termination reaction caused by the existence of the solvent makes it difficult to form a polymer substrate having a relatively high cohesive strength, moreover, residual micromolecules also affect the electrochemical performance of the cell.
[0013] If the amount of the added initiator is too small, then the polymerization reaction is incomplete, resulting in an undesirable mechanical performance of the battery, on the other hand, if the amount of the added initial is too large, then the cost is increased, and the electrical performance of the battery is influenced, for example, the capacity of the battery is lowered.
[0014] If the amount of the added cross-linking agent is too small, then the cross-linking reaction is incomplete, resulting in an undesirable mechanical performance of the battery, on the other hand, if the amount of the added cross-linking agent is too large, then the cost is increased.
[0015] As an improvement of the gel electrolyte formula disclosed herein, the weight percent of each of the aforementioned components is as follows:
[0016] liquid electrolyte: 93%-98%;
[0017] monomer: 1%-2%;
[0018] cross-linking agent: 0.75%0-0.4%; and
[0019] initiator: 0.2%-1%. This formula is a preferable one.
[0020] As an improvement of the gel electrolyte formula disclosed herein, the average molecular weight of the modified polyvinyl alcohol and the derivates thereof is preferably 8×10 4 g/mol to 12×10 4 g/mol.
[0021] As an improvement of the gel electrolyte formula disclosed herein, the derivates include at least one of polyvinly acetal, polyvinyl butyral and polyvinyl formal, which are prepared through the aldolization reaction of polyvinyl alcohol with acetaldehyde, butyraldehyde and formaldehyde and have a high-stability high-strength six-membered cyclic acetal structure, thus, a polymer substrate polymerized by the derivates has a high cohesive strength.
[0022] As an improvement of the gel electrolyte formula disclosed herein, the modified polyvinyl alcohol and the derivates thereof refer to polyvinyl alcohol modified by a double-bonded silane coupling agent and the derivates thereof.
[0023] As an improvement of the gel electrolyte formula disclosed herein, the modified polyvinyl alcohol and the derivates thereof are prepared in the following way: prepare a mixed solvent with water and ethanol in a mass ratio of (1-9):(9-1), heat the mixed solvent while stirring the mixed solvent, add polyvinyl alcohol or a derivate thereof which accounts for 5-30% by mass of the mixed solvent, slowly add a certain mass of a silane coupling agent until no oily polymer is separated out of the mixed solvent after polyvinyl alcohol or the derivate thereof is completely dissolved, and then filter, clean and purify the oily polymer to obtain a pure silane-modified polyvinyl alcohol or a derivate thereof.
[0024] The silane coupling agent is capable of apparently enhancing the interface binding force between the gel electrolyte and the surface of the cathode, the surface of the anode or the separator to inhibit the swelling of the battery during a cycle process. A dehydration-condensation reaction may occur between the hydrolyzed silane coupling agent and polyvinyl alcohol and the derivates thereof to obtain a double-bonded modified polyvinyl alcohol and the derivates thereof.
[0025] As an improvement of the gel electrolyte formula disclosed herein, the silane coupling agent includes at least one of γ-(methacryloxy)propyltrimethoxylsilane, vinyltriisopropoxysilane, vinyldibutoxymethylsilane and ethoxydimethylvinylsilane.
[0026] As an improvement of the gel electrolyte formula disclosed herein, the cross-linking agent includes at least one of diallycarbonate, trimethylolpropane triacrylate, polyoxyethylene diacrylate, dipentaerythritol pentaacrylate, N,N′-methylenebisacrylamide, N,N-dimethylacrylamide, diacetone acrylamide, divinyl benzene and crotonic acid, each of which contains two or more double bonds and has an excellent cross-linking effect.
[0027] As an improvement of the gel electrolyte formula disclosed herein, the initiator is at least one of azodiisobutyronitrile (AIBN), 2,2′-azobisisoheptonitrile, 2,2′-azobis-(2-methylbutyronitrile), 1,1-azobis(cyclohexane-1-carbonitrile, benzoylperoxide (BPO), hydrogen peroxide, dodecamoyl peroxide, isobutyryl peroxide and cumene peroxide.
[0028] The liquid electrolyte includes lithium salt, a non-aqueous organic solvent and an additive.
[0029] The lithium salt, the molar concentration of which is 0.85 mol/L to 1.3 mol/L, is selected from at least one of LiPF 6 , LiBF 4 , LiAsF 6 , LiCIO 4 , LiBOB (Lithium bis(oxalate)borate), LiDFOB (lithium difluoroborate), LiCF 3 SO 3 , LiC 4 F 9 SO 3 , Li(CF 3 SO 2 ) 2 N and Li(C 2 F 5 SO 2 ) 2 N.
[0030] The non-aqueous organic solvent includes at least one of carbonic ester, carboxylic ester, an etheric compound and an aromatic compound.
[0031] The carbonic ester includes a cyclic carbonate and a chain carbonate in a mass ratio of 3:1 to 1:10.
[0032] The cyclic carbonate is at least one of ethylene carbonate, propylene carbonate and 2,3-butylene carbonate, and the chain carbonate is at least one of dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, dipropyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, methyl butyl carbonate and butylene carbonate.
[0033] The carboxylic ester includes an unsubstituted carboxylic ester and a halogenated carboxylic ester. The unsubstituted carboxylic ester is selected from at least one of methyl formate, ethyl formate, n-propyl formate, isopropyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, γ-butyrolactone, γ-valerolactone and caprolactone, and the halogenated carboxylic ester is selected from at least one of methyl fluoroformate, ethyl fluoroformate, methyl monofluoroacetate, methyl difluoroacetate, ethyl monofluoroacetate, ethyl difluoroacetate, ethyl trifluoroacetate, propyl flurorformate, 3-fluoropropionate, 3,3-methyl difluoropropionate, 3,3,3-methyl trifluoropropionate, 3-ethyl fluoropropionate, 3,3-ethyl difluoropropionate and 3,3,3-ethyl trifluoropropionate.
[0034] The etheric compound includes an unsubstituted etheric compound and a halogenated etheric compound, wherein the unsubstituted etheric compound is one or more of butyl oxide, dimethoxymethane, dimethoxyethane, diethoxymethane, diethoxyethane, tetrahydrofuran and di methyltetrahydrofuran, and the halogenated etheric compound is selected from monofluorodimethoxymethane, monofluorodimethoxyethane, monofluorodiethoxymethane and monofluorodiethoxyethane.
[0035] The aromatic compound is selected from methylbenzene, fluorobenzene, o-Fluorotoluene, trifluorotoluene, 4-fluorotoluene, p-fluoromethoxybenzene, o-fluoromethoxybenzene, o-bifluoromethoxybenzene, 1-fluoro-4-tert-butyl benzene and fluorobiphenyl.
[0036] The additive includes at least one of vinylene carbonate, vinyl ethylene carbonate, fluoroethylene carbonate and 1,3-propane suhone. The total weight of the additive is 1 wt %-10 wt % of the total mass of the liquid electrolyte.
[0037] The other purpose of the present invention is to provide a lithium-ion secondary battery comprising an electrolyte, a cathode, an anode and a separator spaced between the cathode and the anode, wherein the electrolyte is a gel electrolyte formed by initiating the formula disclosed herein with heat or light. Preferably, the formula is initialized with heat at a temperature of 45-85 degrees centigrade.
[0038] With respect to the prior art, by using a modified polyvinyl alcohol and the derivates thereof having a relatively large average molecular weight in the gel electrolyte of a lithium-ion secondary battery, the present invention meets basic electrochemical performances with superior mechanical strength, excellent cycle performance and high safety.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0039] The present invention and the beneficial effects thereof are further described below in detail with reference to specific embodiments which are not to be construed as limiting the present invention.
Embodiment 1
[0040] The gel electrolyte formula provided in the embodiment consists of 97.4% by weight of a liquid electrolyte, 1.7% by weight of a monomer, 0.3% by weight of a cross-linking agent and 0.6% by weight of an initiator,
[0041] wherein the monomer, which is polyvinyl alcohol having an average molecular weight of 9×10 4 g/mol, is modified using γ-(methacryloxy)propyltrimethoxysilane, the cross-linking agent is trimethylolpropane triacrylate, the initiator is benzoyl peroxide, and the liquid electrolyte composed of EC:PC:DEC:LiPF 6 :VC in a ratio of 25:35:25:12.5:2.5 is recorded as C1.
[0042] To prepare the gel electrolyte, polyvinyl alcohol having an average molecular weight of 9×10 4 g/mol and a saponification degree of 75% is selected first, then water and ethanol are prepared into a mixture in a mass ratio of 1:9, the mixture is heated while being stirred, then the polyvinyl alcohol, which accounts for 10% by mass of the mixture of water and ethanol, is added and completely dissolved in the mixture, the obtained solution is heated while being stirred, a certain mass of γ-(methacryloxy)propyltrimethoxysilane is added slowly until no generated oily polymer is separated out from the mixture of water and ethanol, the polymer is filtered, cleaned and purified to obtain powder of a pure macromolecular polyvinyl alcohol monomer L1 modified by γ-(methacryloxy)propyltrimethoxysilane.
[0043] Raw materials are prepared with the liquid electrolyte C1, the macromolecular monomer L1 and trimethylolpropane triacrylate in a mass ratio of 97.4:1.7:0.3. 97.4 g liquid electrolyte C1 is heated at 50 degrees centigrade, then 1.7 g macromolecular monomer L1 is added until a completely clean and transparent solution is formed, the solution is cooled to room temperature, sequentially, 0.3 g trimethylolpropane triacrylate is added and stirred uniformly, then 0.6 g initiator BPO is added, the solution is continuously stirred until a clear solution is formed, the clear solution is placed still for further use, then a gel electrolyte precursor is obtained.
[0044] An anode sheet and a cathode sheet are prepared using the ordinary method, and then a separator is arranged between the cathode sheet and the anode sheet according to the ordinary battery winding procedure to prepare a cell, then the cell is baked to be injected with the electrolyte.
[0045] The gel electrolyte precursor is injected into the baked cell, the cell is placed still for 24 h after being sealed and then cold-pressed to guarantee that the whole film is completely infiltrated by the electrolyte, sequentially, the cell is baked for 5 h at 70 degrees centigrade at a pressure of 1 Mpa so that the initiator can initiate the polymerization reaction of the monomer to form a uniform gel, then a formation processing, a shaping processing and a degassing processing are conducted for the gel to obtain a shaped battery which is numbered S1.
Embodiment 2
[0046] The gel electrolyte formula provided in the embodiment consists of 96% by weight of a liquid electrolyte, 2.9% by weight of a monomer, 0.1% by weight of a cross-linking agent and 1% by weight of an initiator,
[0047] wherein the monomer, which is polyvinyl butyral having an average molecular weight of 10×10 4 g/mol, is modified by vinyltriisopropoxysilane, the cross-linking agent is polyoxyethylene diacrylate, the initiator is azodiisobutyronitrile, and the liquid electrolyte composed of EC:PC:DMC:LiBF 4 :fluoroethylene carbonate in a ratio of 25:35:25:12.5:2.5 is recorded as C2.
[0048] To prepare the gel electrolyte, the polyvinyl butyral having an average molecular weight of 10×10 4 g/mol is selected first, then water and ethanol are prepared into a mixture in a mass ratio of 2:8, the mixture is heated while being stirred, then the polyvinyl butyral, which accounts for 20% by mass of the mixture of water and ethanol, is added and completely dissolved in the mixture, the obtained solution is heated while being stirred, a certain mass of vinyltriisopropoxysilane is added slowly until no generated oily polymer is separated out from the mixture of water and ethanol, the polymer is filtered, cleaned and purified to obtain powder of a pure macromolecular polyvinyl butyral monomer L2 modified by vinyltriisopropoxysilane.
[0049] Raw materials are prepared with the liquid electrolyte C2, the macromolecular monomer L2 and polyoxyethylene diacrylate in a mass ratio of 96:2.9:0.1. 96 g liquid electrolyte C2 is heated at 50 degrees centigrade, then 2.9 g macromolecular monomer L2 is added until a completely clean and transparent solution is formed, the solution is cooled to room temperature, sequentially, 0.1 g polyoxyethylene diacrylate is added and stirred uniformly, 1 g initiator azodiisobutyronitrile is added, the solution is continuously stirred until a clear solution is formed, the clear solution is placed still for further use, then a gel electrolyte precursor is obtained.
[0050] An anode sheet and a cathode sheet are prepared using the normal method, and then a separator is arranged between the cathode sheet and the anode sheet according to the ordinary battery lamination procedure to prepare a cell, then the cell is baked to be injected with the electrolyte.
[0051] The gel electrolyte precursor is injected into the baked cell, the cell is placed still for 24 h after being sealed and then cold-pressed to guarantee that the whole film is completely infiltrated by the electrolyte, sequentially, the cell is baked for 5 h at 80 degrees centigrade at a pressure of 0.5 Mpa so that the initiator can initiate the polymerization reaction of the monomer to form a uniform gel, then a formation processing, a shaping processing and a degassing processing are conducted for the gel to obtain a shaped battery which is numbered S2.
Embodiment 3
[0052] The gel electrolyte formula provided in the embodiment consists of 99% by weight of a liquid electrolyte, 0.7% by weight of a monomer, 0.5%0 by weight of a cross-linking agent and 0.25% by weight of an initiator,
[0053] wherein the monomer, which is polyvinyl acetal having an average molecular weight of 7×10 4 g/mol, is modified by vinyldibutoxymethylsilane, the cross-linking agent is dipentaerythritol pentaacrylate, the initiator is 2,2′-azobis-(2-methylbutyronitrile), and the liquid electrolyte composed of EC:PC:DMC:LiBF 4 :PS in a ratio of 25:35:25:12.5:2.5 is recorded as C3.
[0054] To prepare the gel electrolyte, the polyvinyl acetal having an average molecular weight of 7×10 4 g/mol is selected first, then water and ethanol are prepared into a mixture in a mass ratio of 3:7, the mixture is heated while being stirred, then the polyvinyl acetal, which accounts for 15% by mass of the mixture of water and ethanol, is added and completely dissolved in the mixture, a certain mass of vinyldibutoxymethylsilane is added slowly until no generated oily polymer is separated out from the mixture of water and ethanol, the polymer is filtered, cleaned and purified to obtain powder of a pure macromolecular polyvinyl acetal monomer L3 modified by vinyldibutoxymethylsilane.
[0055] Raw materials are prepared with the liquid electrolyte C3, the macromolecular monomer L3 and dipentaerythritol pentaacrylate in a mass ratio of 99:0.7:0.05. 99 g liquid electrolyte C3 is heated at 50 degrees centigrade, then 0.7 g macromolecular monomer L3 is added until a completely clean and transparent solution is formed, the solution is cooled to room temperature, sequentially, 0.05 g dipentaerythritol pentaacrylate is added and stirred uniformly, 0.25 g initiator 2,2′azobis-(2-methylbutyronitrile) is added, the solution is continuously stirred until a clear solution is formed, the clear solution is placed still for further use, then a gel electrolyte precursor is obtained.
[0056] An anode sheet and a cathode sheet are prepared using the normal method, and then a separator is arranged between the cathode sheet and the anode sheet according to the ordinary battery lamination procedure to prepare a cell, then the cell is baked to be injected with the electrolyte.
[0057] The gel electrolyte precursor is injected into the baked cell, the cell is placed still for 24 h after being sealed and then cold-pressed to guarantee that the whole film is completely infiltrated by the electrolyte, sequentially, the cell is baked for 5 h at 50 degrees centigrade at a pressure of 1.2 Mpa so that the initiator can initiate the polymerization reaction of the monomer to form a uniform gel, then a formation processing, a shaping processing and a degassing processing are conducted for the gel to obtain a shaped battery which is numbered S3.
Embodiment 4
[0058] The gel electrolyte formula provided in the embodiment consists of 95.3% by weight of a liquid electrolyte, 3% by weight of a monomer, 0.2% by weight of a cross-linking agent and 1.5% by weight of an initiator,
[0059] wherein the monomer, which is polyvinyl formal having an average molecular weight of 15×10 4 g/mol, is modified by ethoxydimethylvinylsilane, the cross-linking agent is N,N′-methylenebisacrylamide, the initiator is 2,2′-azobisisoheptonitrile, and the liquid electrolyte composed of EC:PC:DMC:LiBF 4 :FEC in a ratio of 25:35:25:12.5:2.5 is recorded as C4.
[0060] To prepare the gel electrolyte, the polyvinyl formal having an average molecular weight of 15×10 4 g/mol is selected first, then water and ethanol are prepared into a mixture in a mass ratio of 4:6, the mixture is heated while being stirred, then the polyvinyl formal, which accounts for 5% by mass of the mixture of water and ethanol, is added and completely dissolved in the mixture, a certain mass of ethoxydimethylvinylsilane is added slowly until no generated oily polymer is separated out from the mixture of water and ethanol, the polymer is filtered, cleaned and purified to obtain powder of a pure macromolecular polyvinyl formal monomer L4 modified by ethoxydimethylvinylsilane.
[0061] Raw materials are prepared with the liquid electrolyte C4, the macromolecular monomer L4 and N,N′-methylenebisacrylamide in a mass ratio of 95.3:3:0.2. 95.3 g liquid electrolyte C4 is heated at 50 degrees centigrade, then 3 g macromolecular monomer L4 is added until a completely clean and transparent solution is formed, the solution is cooled to room temperature, sequentially, 0.2 g N,N′-methylenebisacrylamide is added and stirred uniformly, 1.5 g initiator 2,2′-azobisisoheptonitrile is added, then the solution is continuously stirred until a clear solution is formed, the clear solution is placed still for further use, then a gel electrolyte precursor is obtained.
[0062] An anode sheet and a cathode sheet are prepared using the normal method, and then a separator is arranged between the cathode sheet and the anode sheet according to the ordinary battery lamination procedure to prepare a cell, then the cell is baked to be injected with the electrolyte.
[0063] The gel electrolyte precursor is injected into the baked cell, the cell is placed still for 24 h after being sealed and then cold-pressed to guarantee that the whole film is completely infiltrated by the electrolyte, sequentially, the cell is baked for 5 h at 60 degrees centigrade at a pressure of 0.1 Mpa so that the initiator can initiate the polymerization reaction of the monomer to form a uniform gel, then a formation processing, a shaping processing and a degassing processing are conducted for the gel to obtain a shaped battery which is numbered S4.
Embodiment 5
[0064] The gel electrolyte formula provided in the embodiment consists of 98% by weight of a liquid electrolyte, 1% by weight of a monomer, 0.6% by weight of a cross-linking agent and 0.4% by weight of an initiator,
[0065] wherein the monomer, which is polyvinyl butyral having an average molecular weight of 15×10 4 g/mol, is modified by ethoxydimethylvinylsilane and vinyltriisopropoxysilane, the cross-linking agent is the mixture of N,N-dimethylacrylamide and diacetone acrylamide (in a mass ratio of 1:2), the initiator is dodecamoyl peroxide, the liquid electrolyte composed of EC:PC:DMC:LiPF 6 :FEC in a ratio of 25:35:25:12.5:2.5 is recorded as C5.
[0066] To prepare the gel electrolyte, the polyvinyl butyral having an average molecular weight of 15×10 4 g/mol is selected first, then water and ethanol are prepared into a mixture in a mass ratio of 5:5, the mixture is heated while being stirred, then the polyvinyl butyral, which accounts for 20% by mass of the mixture of water and ethanol, is added and completely dissolved in the mixture, a certain mass of the mixture of ethoxydimethylvinylsilane and vinyltriisopropoxysilane (in a mass ratio of 1:1) is added slowly until no generated oily polymer is separated out from the mixture of water and ethanol, the polymer is filtered, cleaned and purified to obtain powder of a pure macromolecular polyvinyl butyral monomer L5 modified by silane.
[0067] Raw materials are prepared with the liquid electrolyte C4, the macromolecular monomer L4 and the mixture of N,N-dimethylacrylamide and diacetone acrylamide in a mass ratio of 98:1:0.6. 98 g liquid electrolyte C5 is heated at 50 degrees centigrade, then 1 g macromolecular monomer L5 is added until a completely clean and transparent solution is formed, the solution is cooled to room temperature, sequentially, 0.2 g N,N-dimethylacrylamide and 0.4 g diacetone acrylamide are added and stirred uniformly, 0.4 g initiator dodecamoyl peroxide is added, the solution is continuously stirred until a clear solution is formed, and the clear solution is placed still for further use, then a gel electrolyte precursor is obtained.
[0068] An anode sheet and a cathode sheet are prepared using the normal method, and then a separator is arranged between the cathode sheet and the anode sheet according to the ordinary battery lamination procedure to prepare a cell, then the cell is baked to be injected with the electrolyte.
[0069] The gel electrolyte precursor is injected into the baked cell, the cell is placed still for 24 h after being sealed and then cold-pressed to guarantee that the whole film is completely infiltrated by the electrolyte, sequentially, the cell is baked for 5 h at 85 degrees centigrade at a pressure of 0.7 Mpa so that the initiator can initiate the polymerization reaction of the monomer to form a uniform gel, then a formation processing, a shaping processing and a degassing processing are conducted for the gel to obtain a shaped battery which is numbered S5.
Embodiment 6
[0070] The gel electrolyte formula provided in the embodiment consists of 96.7 by weight of a liquid electrolyte, 2.25% by weight of a monomer, 0.3% by weight of a cross-linking agent and 0.75% by weight of an initiator,
[0071] wherein the monomer, which is polyvinyl formal having an average molecular weight of 8×10 4 g/mol, is modified by ethoxydimethylvinylsilane, the cross-linking agent is divinyl benzene, the initiator is the mixture of cumene peroxide and isobutyryl peroxide (in a mass ratio of 1:4), and the liquid electrolyte composed of EC:γ-BL:DEC:LiBF 4 :VC in a ratio of 25:35:25:12.5:2.5 is recorded as C6.
[0072] To prepare the gel electrolyte, the polyvinyl formal having an average molecular weight of 8×10 4 g/mol is selected first, then water and ethanol are prepared into a mixture in a mass ratio of 9:1, the mixture is heated while being stirred, then the polyvinyl formal, which accounts for 25% by mass of the mixture of water and ethanol, is added and completely dissolved in the mixture, a certain mass of ethoxydimethylvinylsilane is added slowly until no generated oily polymer is separated out from the mixture of water and ethanol, the polymer is filtered, cleaned and purified to obtain powder of a pure macromolecular polyvinyl formal monomer L6 modified by ethoxydimethylvinylsilane.
[0073] Raw materials are prepared with the liquid electrolyte C6, the macromolecular monomer L6 and divinyl benzene in a mass ratio of 95:2.2:0.3. 96.7 g liquid electrolyte C6 is heated at 50 degrees centigrade, then 2.25 g macromolecular monomer L6 is added until a completely clean and transparent solution is formed, the solution is cooled to room temperature, sequentially, 0.3 g divinyl benzene is added and stirred uniformly, 0.15 g cumene peroxide and 0.6 g isobutyryl peroxide are added, the solution is continuously stirred until a clear solution is formed, and the clear solution is placed still for further use, then a gel electrolyte precursor is obtained.
[0074] An anode sheet and a cathode sheet are prepared using the normal method, and then a separator is arranged between the cathode sheet and the anode sheet according to the ordinary battery lamination procedure to prepare a cell, then the cell is baked to be injected with the electrolyte.
[0075] The gel electrolyte precursor is injected into the baked cell, the cell is placed still for 24 h after being sealed and then cold-pressed to guarantee that the whole film is completely infiltrated by the electrolyte, sequentially, the cell is baked for 5 h at 45 degrees centigrade at a pressure of 1 Mpa so that the initiator can initiate the polymerization reaction of the monomer to form a uniform gel, then a formation processing, a shaping processing and a degassing processing are conducted for the gel to obtain a shaped battery which is numbered S6.
[0076] Comparative Sample 1
[0077] Comparative example 1 is merely different from embodiment 1 in that the monomer is glycidyl methacrylate and the finally obtained battery is numbered B1, and the other content of the comparative example is the same as that of embodiment 1 and is therefore not described repeatedly here.
[0078] The following performance tests are conducted for the batteries S1-S6 and B1.
[0079] Impact test: take 10 batteries from each of the battery groups S1-S6 and B1, fully charge the batteries and fix the batteries on a nail fixture, then conduct an impact test for the batteries by reference to the UL1642 test standard, the result is shown in the following Table T1.
[0080] Nail test: fully charge batteries S1-56 and B1, fix the batteries on a nail fixture, make the nail fixture penetrate the center of the batteries at a speed of 10 mm/s using an iron nail having a diameter of 2.5 mm, then count up the number of burning batteries, meanwhile, monitor the temperature rise curve of the nail penetration position and record the maximum value Tmax in the temperature rise curve, the result is shown in the following Table 1.
[0081] Cycle performance test: place the batteries still for 5 min, charge the batteries at a constant current rate of 0.5 C until the voltage is 4.2V, continue to charge the batteries with a constant voltage until the rate is reduced to 0.05C, place the batteries still for 5 min, discharge the batteries with a constant current rate of 0.5 C until the voltage is 3.0V to obtain an initial discharge capacity D0 (mAh), place the batteries still 3 min, charge the batteries at constant current rate of 0.5 C until the voltage is 4.2V, record the thickness of the barriers as T1, place the batteries still for 3 min, discharge the batteries at a rate of 0.5 C until the voltage is 3.0V, record the discharge capacity as D1, repeat this process for 500 times to obtain a final discharge capacity D500 (mAh), calculate the capacity retention ratio of the batteries after 500 times of cycle by dividing D500 by D1, record the thickness of the fully charged batteries as T500 and calculate the thickness swelling rate of the batteries after 500 times of cycle according to a formula: (T500/T1)−1), the result is shown in the following table T1.
[0000]
TABLE 1
Result of performance tests on batteries S1-S6 and B1
The
Thickness
number of
Initial
Capacity
swelling rate
the
discharge
retention ratio
after 500
batteries
Tmax
Battery
D0
after 500
times of
passing
(° C.) in
No.
(mAh)
times of cycle
cycle
impact test
nail test
B1
1620
0.8126
9.2%
3
118
S1
1650
0.8621
6.9%
6
106
S2
1666
0.8813
6.0%
10
86
S3
1671
0.9103
4.6%
10
91
S4
1681
0.9078
5.3%
8
94
S5
1675
0.9113
5.8%
8
97
S6
1695
0.9221
6.7%
7
100
[0082] It can be seen from Table 1 that compared with battery B1, batteries S1-S6 are higher in capacity retention ratio and lower in thickness swelling rate, are more likely to pass the impact test and less increased in temperature in the nail test as the batteries S1-S6 are improved in capacity performance, cycle performance and safety for the use of a monomer having a relatively molecular weight in the present invention which endows the formed gel electrolyte with a relatively high cohesive strength and endows the batteries with an excellent mechanical strength as well as basic electrochemical performance.
[0083] Proper variations and modifications can be devised by those skilled in the art on the aforementioned embodiments according to the disclosure and teaching of the present invention. Thus, the present invention is not limited to the specific embodiments disclosed and described above, and the modifications and variations devised should fall into the protection scope of the appending claims. In addition, the terms, as used herein, are merely illustrative of, but are not to be construed as limiting the present invention.
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The present invention belongs to the technical field of lithium-ion secondary batteries and in particularly relates to a lithium-ion secondary battery and the gel electrolyte formula thereof. The gel electrolyte formula comprises 90-99.4% by weight of a liquid electrolyte, 0.5-3% by weight of a monomer, 0.25-0.6% by weight of a cross-linking agent and 0.1-1.5% by weight of an initiator, wherein the monomer is modified polyvinyl alcohol and the derivates thereof, the average molecular weight of which is 5×10 4 to 15×10 4 g/mol. With respect to the prior art, by using modified polyvinyl alcohol and the derivates thereof having a relatively large average molecular weight as the monomer in a gel electrolyte, the present invention forms a polymer substrate having a relatively high mechanical strength so that a cell containing the gel electrolyte is high in mechanical strength and is therefore less swelled in a cycle process.
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BACKGROUND OF THE INVENTION
The present invention relates to a push-button switch device, and in particular a push-button switch device suitable for equipment incorporating a large number of push-button switches such as pendant switches.
FIG. 19 depicts the electric circuit of a 2-step type push-button switch for controlling an inverter used generally for a pendant switch. The push-button switch device 100 consists of a switch unit 101 and an output unit connected to an AC source at respective R and S terminals. The switch unit 101 is provided with two push-button switches PBa, PBb. The push-button switch PBa is provided with a 1st-stage switch 103 and a 2nd-stage switch 104 while the push-button switch PBb has a 1st-stage switch 105 and a 2nd-stage switch 106. FIG. 19 shows an example in which the 2nd-stage switches of the both push-button switches transmit a one same signal and are connected to one same transmitting line al.
With this arrangement, the 3 kinds of signals transmitted by the switch unit 101 are connected with the output unit 102 by transmitting lines a1, a2, a3 respectively, and the output unit 102 works with the signals from the switch unit 107 through detecting members 107, 108, 109 each formed by a photocoupler, for example, provided for the respective transmitting lines, so as to transmit operating signals. Namely, the 3 transmitting lines a1, a2, a3 are required to transmit 3 different kinds of signals. For that reason, equipment incorporating a large number of push-button devices in one operating unit such as a pendant switch for operating a crane, hoist, etc., for example, requires wires of a number at least 3 times larger than the number of push-button switch devices plus one common line.
In that case, there is no problem if the number of push-button switch devices incorporated in the pendant switch, etc. is small. In recent times, however, inverter control is being increasingly used in place of the electromagnetic contactor and the specifications of pendant switch are becoming more an more complicated with incorporation of a buzzer switch or switching between linked operation and single operation, etc. Therefore, there is a general tendency for multi-point construction of the pendant switch and multi-stage construction of individual switches. This leads to an increase in the number of cable wires, an increase in the outer dimensions of the pendant switch and an increase in the weight of the cable itself. As a result, the wire bundle becomes rigid and makes the operation of pendant switch difficult in some cases.
SUMMARY OF THE INVENTION
The object of the present invention is to reduce the size of the switch unit and the reduce the number of wires by adopting a double transmission system in which a plural number of signals are transmitted through one cable to simplify the circuit.
To achieve the above object, the present invention is composed of a switch unit having a pair of push-button switches and diodes and an output circuit for detecting an electric current sent from the switch unit, in which selective closing of the push-button switches in the switch unit results in transmitting a plural number of signals, those plural number of signals being transmitted to the output unit through a common transmitting line, and in which the output unit is provided with discriminating means for discriminating such signals and transmitting prescribed operating signals according to the signal current.
With such arrangement, the push-button switch device of the present invention can reduce the number of the signal lines conducted between the switch unit and the output unit. Therefore, if the switch unit is incorporated in a pendant switch, for example, it is possible to reduce the weight of the conductors themselves and increase the operability and the reliability of the pendant switch at the same time. Moreover, it becomes possible to use the same cable as the signal line of an AC commercial voltage circuit without using any special shielded wire, etc. as the signal line.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a general circuit diagram of the first example of the push-button switch device of the present invention.
FIG. 2 is an explanatory chart of a signal current of the first example.
FIG. 3 is a general circuit diagram of the second example of the push-button switch device of the present invention.
FIG. 4 is an explanatory chart of a signal current of the second example.
FIG. 5 is an explanatory chart of a signal current waveform.
FIG. 6 is a circuit diagram of the output unit of the second example.
FIG. 7 is a general circuit diagram of the third example of the push-button switch device of the present invention.
FIG. 8 is an explanatory chart of a signal current of the third example.
FIG. 9 is a circuit diagram of the output unit of the third example.
FIG. 10 is a general circuit diagram of the fourth example of the push-button switch device of the present invention.
FIG. 11 is an explanatory chart of a signal current of the fourth example.
FIG. 12 is a circuit diagram of the output unit of the fourth example.
FIG. 13 is a general circuit diagram of the fifth example of the push-button switch device of the present invent ion.
FIG. 14 is an explanatory chart of a signal current of the fifth example.
FIG. 15 is a perspective view of the push-button switch of the fifth example.
FIG. 16 is a general circuit diagram of the sixth example of the push-button switch device of the present invention.
FIG. 17 is an explanatory chart of a signal current of the sixth example.
FIG. 18 is a circuit diagram of the output unit of the sixth example.
FIG. 19 is a circuit diagram of switch signals for inverter control using a conventional 2-stage push-button switch device.
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be explained hereafter based on an illustrated examples. It is noted that like parts are designated by like reference numeral and letters throughout the accompanying drawings.
FIG. 1 and FIG. 2 indicate the first example. This push-button switch device 1 consists of a switch unit 2 and an output unit 3. The switch unit 2 is composed of a pair of push-button switches PB1, PB2 and diodes D1, D2 (hereinafter simply referred to as PB for push-button switches and D for diodes when they are called by a general name in the respective examples). The push-button switch PB1 and the diode D1 are connected in series, with the diode D1 in a forward direction, while the push-button switch PB2 and the diode D2 are connected in series, with the diode D2 in a reverse direction, and these two circuits are connected in parallel. The two circuits are connected to the output unit 3 through a common transmitting line S1.
The output unit 3 is provided with discriminating means PC1, PC2 (hereinafter simply referred to as PC when they are called by a general name). FIG. 1 shows an example of using photocouplers as such discriminating means and a phototransistor for output, but it is also possible to use a cds cell, MOS relay, etc. instead. One discriminating means PC1 works with a normal half-wave rectification signal i.e. closing of push-button switch PB1 and the other discriminating means PC2 works with a half-wave rectification signal in a reverse direction i.e. closing of push-button switch PB2, to apply operating signals to an interface IF, for example, of the next process.
FIG. 2 indicates the current flowing through the transmitting line S1 with the closing of the respective push-button switches and the output of the discriminating means in the output unit. Namely, upon closing of the push-button switch PB1, only a pulsating current of positive half-wave rectification is output and upon, closing of the other push-button switch PB2, only a pulsating current of negative half-wave rectification is output, and upon simultaneous closing of both push-button switches, full-wave alternating current is output. The respective discriminating means PC1, PC2 of the output unit 3 transmit output signals in response to such outputs as mentioned earlier. However, both discriminating means PC1, PC2 transmit output signals simultaneously in response to an alternating current. Namely, the switch circuit is arranged in such a way that the 4 signals produced with the closing of the respective push-button switches PB1, PB2 are transmitted to the output line 3 through one transmitting line S1.
Next, FIG. 3 to FIG. 6 indicate the second example. The push-button switch device of this example shows an a switch unit using a 2-stage type push-button switch in which the switch unit 11 of the push-button switch device 10 consists of a first push-button switch PB3, a second push-button switch PB4 and a diode D1. The first-stage switch 13 of the first push-button switch PB3 and the first-stage switch 15 of the second push-button switch PB4 are provided in series to the common diode D1 and closing of the other second-stage switches 14, 16 outputs an alternating signal respectively.
The first-stage switch 13 and the second-stage switch 14 of said first push-button switch PB3 and the first-stage switch 15 and the second-stage switch 15 of the second push-button switch PB4 are connected respectively to a common transmitting line S3.
Reference in the IL drawings, indicates an interlock provided to prevent simultaneous closing of the two push-button switches.
FIG. 4 shows outputs produced upon closing of the push-button switches. In the drawing, the columns 1, 2 of the push-button switches PB3, PB4 indicate the ON state of the first-stage switch and the second-stage switch respectively. The output waveform of those switches appears as shown in FIG. 5, W0 indicating 0 output, W1 the pulsation of positive half-wave rectification and W2 the alternating current of full wave, while W3 indicates the pulsation of negative half-wave rectification.
FIG. 6 indicates the output unit 12. This output unit 12 is constituted as an interface circuit and is provided with detectors PC3, PC4 forming a pair with the output line S2 and being in opposite phase, and discriminating means PC5, PC6 forming a pair with the output line S3 and being in opposite phase. With such an arrangement, the output unit 12 discriminates positive or negative of the signal current sent through the respective transmitting lines S2, S3 and selects those signals to apply a signal current to comparators CR1, CR2, CR3, CR4 through an integrating circuit of a resistor and capacitor to a control inverter as operating current signals U, D; etc. (illustration omitted).
Namely, in this example, the two signals or the positive half-wave rectification signal and the alternating signal sent from the push-button switch PBR of the switch unit are transmitted to the output line 12 through one transmitting line S2 and the positive half-wave rectification signal and the alternating signal sent from the push-button switch PB4 are transmitted to the output line 12 through one transmitting line S3.
Next, FIG. 7 to FIG. 9 indicate the third example. The switch unit 21 of the push-button switch device 20 of this example is also provided with diodes D1, D2 forming pairs with 2-stage push-button switches PB3, PB4 in the same way as the preceding example. The diode D1 is provided in a forward direction in the first-stage switch 13 of the push-button switch and the diode D2 is provided in a reverse direction in the first-stage switch 15 of the push-button switch PB4 in series respectively. The two switches PB3, PB4 are connected to the first transmitting line S4. The second-stage switches 14, 16 are connected to the second transmitting line S5.
FIG. 8 indicates outputs produced upon closing of push-button switches of this example. The output waveform of those switches appears as shown in FIG. 5, W0 indicating 0 output, W1 the output current of the pulsation of positive half-wave rectification and W2 that of the alternating current of full wave, while W3 indicates the output current of the pulsation of negative half-wave rectification.
FIG. 9 indicates the output unit 22 of this example. This output unit 22 is also constituted as an interface circuit as in the previous example. Only an alternating current signal is applied to the transmitting line S5 and it is discriminated by the discriminating means PC7. To the other transmitting line S4, signal currents of positive and negative half-wave rectifications are applied and discriminated by 2 discriminating means PCS, PC9. Those signals are selected and applied to the comparators CR5, CR6 through an integrating circuit of resistors and capacitors to generate operating current signals U, D. Namely, the two signals are transmitted to the transmitting line S4 and are discriminated by the output unit.
Next, FIG. 10 and FIG. 12 indicate the fourth example of the push-button device. The switch unit 31 of the push-button switch device 30 of this example is provided with pair of 3-stage push-button switches PBS, PB6 and 3 diodes D1, D2, D3. The respective first contacts 33, 36 of the push-button switches PB5, PB6 are accompanied by normally closed contacts 33b, 36b. The said diode D1 is connected to the first contact 33 of the first push-button switch PB5 in series in a forward direction and the diode D2 is connected to the first contact 36 of the first push-button switch PB6 in a series in reverse direction, and both first contacts 33, 36 are connected to the output unit 32 through a common first transmitting line S6. Moreover, the diode D3 is connected to the second contact 37 of the second push-button switch PB6 in series in a forward direction, and the second contacts 34, 37 and third contacts 35, 38 of the respective push-button switches are connected to the output unit 32 through a common second transmitting line S7.
FIG. 11 indicates the outputs produced upon closing of the push-button switches of this example. According to this example, 2 different kinds of signals can be transmitted to each of the two transmitting lines S6, S7 or 4 different kinds of signals in total can be transmitted. FIG. 12 indicates an example of output unit according to this example. This output unit 32 is also realized as an interface circuit as in the previous example. Pulsating signal currents of positive and negative half-wave rectification are applied to the transmitting line S6 and discriminated by a pair of discriminating means PC10, PC11. To the other transmitting line S7, a pulsating signal current of positive half-wave rectification and an alternating signal current are applied and discriminated by 2 discriminating means PC12, PC13. These signals are selected and applied to the comparators CR7, CR8, CR9 and CR10 through an integrating circuit of resistors and capacitors. Namely, each of the two transmitting lines S6, S7 transmits 2 different kinds or signals, or 4 kinds of signals in total, and the output unit discriminates them with discriminating means and produces outputs corresponding to the signals.
Next, FIG. 13 and FIG. 15 indicate the fifth example of the push-button switch device. The switch unit 41 of the push-button switch device 40 of this example indicates utilization of a transformed 3-stage push-button switch. The switch unit 41 is provided with 2 push-button switches PB7, PB8. While the respective first contacts 43, 44 of those push-button switches PB7, PB8 close individually, the second and the third contacts 45, 46 are designed to close if either of the push-button switches is pressed down. An example is given in FIG. 15.
This switch unit 41 is realized by inserting push buttons 51, 52 at a certain distance between them in a case 50. The two push buttons have a same structure. Therefore, one push button 51 will be explained hereafter while the other push button 52 will be given with a suffix "a" attached to a same symbol for a same part, but the explanation for it will be omitted.
This push button 51 is provided with a contactor 54 of rectangular shape to be inserted in a slit 53. The contactor 54 is braced down into the slit by a spring 55 and the push button 51 itself is also braced at the head in the direction protruding from the case 50 by a spring 56. 57, 57a indicate left and right contacts. 58 indicates a projection protruding from the push button 51 to the side of the other push button 52 while 60 indicates an intermediate switch provided between the two push buttons 51, 52. The intermediate switch 60 is braced to the side of the projections 58, 58a by a spring 61. Long and short slits 62, 63 are formed in this intermediate switch 60 and rectangular contactors 64, 65 are inserted in those slits and braced to the bottom face side of the slits by springs 66, 67. 70, 70a indicate left and right contacts for the contactor 64 inserted in the slit 62 while 71, 71a indicate left and right contacts for the contactor 65 inserted in the slit 63, 59, 59a are left and right contacts for the contactor 54a on the side of the other push button 52.
In such a structure, the contactor 54 connects the contacts 57, 57a with pressing down of the first stage of the push button 51. Moreover, the contactor 54 connects the contacts 59, 59a with pressing down of the first stage of the push button 52. Next, pressing down of the second stage of the push button 51 or 52 presses down the intermediate switch 60, and the contactor 64 in the slit 62 connects the contacts 70, 70a. With further pressing down of the push button 51 or 52, the contactor 65 in the short slit 63 connects the contacts 71, 71a. The contacts 57, 57a in this case correspond to said contact 44, contacts 59, 59a to contact 44, contacts 70, 70a to contact 45 and contacts 71, 71a to contact 46. This case 50 houses diodes to be described later, but illustration of such diodes is omitted.
The switch unit 41 is provided with 3 diodes D1, D2, D3 in addition to the respective push-button switches PB7, PB8 and the respective diodes are connected as shown in the drawing. The outputs to transmitting lines S8, S9 by this connection are as shown in FIG. 14. The output unit 42 may be realized with a structure as shown in FIG. 12.
Next, FIG. 16 to FIG. 18 indicate the sixth example of the push-button switch device. The push-button switch device 80 of this example consists of a switch unit 81 and an output unit 82. The switch unit 81 is constituted by 3-stage push-button switches PB9, PB10, which make outputs by combination of 2 contacts, and 3 diodes D1, D2, D3. Namely, the push-button switches PB9, PB10 are 3-stage switches provided each with first contacts 83, 85 and second contacts 84, 86, and neither contact is turned on during a state (i.e., zero stage) in which the push-button switch PB9 is not pushed down. The first contact 83 is turned on with pressing down of the first stage of the push-button switch PB9 and the first and second contacts 83, 84 are turned on with pressing down of the second stage. With further pressing down of the third stage, the first contact is turned off and only the second contact 84 is turned on. The same is true with the other push-button switch PB10. The diode D1 is mounted in the direction opposite to that of the other diodes D2, D3.
With such a arrangement, the outputs obtained with the closing of respective contacts are those of pulsating signal current of positive half-wave rectification, alternating waveform signal current and pulsating signal current of negative half-wave rectification as shown in FIG. 17 which are obtained in order. The respective contacts 83, 84 of the push-button switch PB9 are connected to the output unit 82 through a common transmitting line S10 while respective contacts 85, 86 of the push-button switch PB11 are connected to the output unit 82 through a common transmitting line S11.
FIG. 18 indicates the output unit 82. In the interface circuit of this output unit 82, 2 discriminating means PC14, PC15 are provided on the transmitting line S10 and 2 discriminating means PC16, PC17 are provided on the transmitting line S11 respectively, to apply signals to comparators CR14-CR17 through an integrating circuit of resistors and capacitors, respectively. Namely, this example is realized in such a way that the 4 kinds of signals by the push-button switch PB9 are transmitted to the output unit through one transmitting line S11, the 4 kinds of signals by the push-button switch PB10 are transmitted to the output unit through one transmitting line S12 respectively and that the output unit 82 discriminates those signals and transmits output signals according to such signals.
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A switch unit receive an AC signal and includes first and second push-button switches and at least one rectifying diode. Each of the first and second push-button switches is a 2-stage switch or a 3-stage switch. The first and second push-button switches and the at least one rectifying diode are configured such that the switch unit selectively generates any one of a non-signal, a positive half-wave rectified signal, a negative half-wave rectified signal and a full wave alternating signal to each of first and second outputs. The first and second outputs of the switch units are transmitted to an output unit by way of two transmission wires, respectively. The output unit discriminates the switching state of the first and second push-button switches based on the signal received from the switch unit via the two transmission wires.
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BACKGROUND OF THE INVENTION
The field of this invention is that of removing blockages in remote subsea pipeline, typically from subsea gas well installations.
Hydrates are a porous solid which is formed primarily of water with a mixture of gases. It is effectively similar to ice. There is a tendency for hydrates to form in the pipelines departing from a subsea gas well, especially on well startup.
The temperature of seawater at depths will often approach 32° F., with the temperature in non-flowing pipelines being the same. When a subsea pipeline valve is opened, the gas expansion can cause substantial additional cooling. In these cold and high pressure conditions, hydrates of the gas and water can quickly form.
Frequently when the hydrate forms, it forms a blockage, the blockage will be somewhat porous. At that time, a high pressure will exist on the upstream side and a lower pressure will exist on the downstream side of the blockaged. This means that additional gas will move thru the hydrate and expand and therefore cool as it does. This means that not only can the expansion of this gas keep the formed hydrate cool, but can literally continue to grow additional hydrate blockage.
It is difficult to tell where the hydrates are actually located in deepwater pipelines, especially when the pipelines are buried.
Hydrates formed like this can last for weeks or months, with a substantial loss of gas flow and therefore revenue to the owner of the pipelines and subsea wells.
Paraffins can form blockages in pipelines by building up on the inner diameter of the cold pipelines as relatively warm oil circulates out of an oil well and cools as it flows down a subsea pipeline. As the layer of paraffin builds up on the subsea pipeline inner diameter, the inner diameter of the paraffin becomes smaller and smaller. Ultimately a pigging device intended to clean the paraffin will cause the paraffin to separate from the inner wall of the pipeline and become a plug. In some cases the paraffin will release from the subsea pipeline inner diameter without a pig and cause a blockage. In either case, if the pressure in the pipeline is enough to move the plug along the pipeline, it will continue to collect additional paraffin as it moves until the length of the blockage cannot be moved by the available pressure.
Some attempts have been made to enter the end of the pipeline with a somewhat flexible string of coiled tubing to get to the blockage and wash it out. This is an expensive operation, and in some cases the blockage can be 10 to 20 miles away.
Removal by use of coiled tubings can be further complicated if the pipeline has bends in it, making passage of the coiled tubing difficult if not impossible.
SUMMARY OF THE INVENTION
The object of this invention is to provide a system which will approach a subsea pipeline and remove hydrate and/or paraffin blockages from within the pipeline.
A second object of the present invention is to provide a method of removing the hydrate or paraffin without requiring that the pressure integrity of the pipeline be compromised.
A third object of the present invention is to provide for recirculation of seawater to allow the heat not absorbed into the pipeline to increase the inlet temperature to the seawater heating means—thereby increasing the outlet temperature of the seawater.
Another object of the present invention is to provide a means for applying heat to the outer surface of a subsea pipeline without uncovering the pipeline to minimize the disturbance to the pipeline.
Another object of the present invention is to provide means for applying heat to the outer surface of a subsea pipeline without uncovering the pipeline so that the insulating effects of the covering will retain the heat in the pipeline.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a section thru the pipeline and the thermal operating module showing the circulation thru the circulation chamber.
FIG. 2 is a larger section of the view of FIG. 1 including a trench dug to uncover the pipeline and the remotely operated vehicle (ROV).
FIG. 3 is a similar section thru the system, but showing wheels which might engage the exterior of the pipeline to drive the thermal operating module along the pipeline.
FIG. 4 is a partial section of the system taken axially along the pipeline showing a spatial relationship between the driving wheels and a heating chamber utilizing electric resistance heating of the seawater used for the heating.
FIG. 5 is a similar figure to FIG. 4 , but showing the heat being generated by a pressure drop across an orifice rather than electric resistance heating.
FIG. 6 . shows an alternate embodiment of this invention with the circulation chamber being disposed a distance away from the main portion of the system to allow the circulation chamber to follow the pipeline under the mudline without uncovering the pipeline.
FIG. 7 . shows the rollers of the alternate embodiment and their method of engaging the pipeline.
FIG. 8 shows a side view of the thermal operating module of the alternate embodiment with the circulation chamber spaced a distance away from the upper section by a pair of legs.
FIG. 9 is a section thru one of the legs of FIG. 8 .
FIG. 10 is a view of the alternate embodiment engaging the subsea pipeline below the mudline.
FIG. 11 is a section thru the alternate embodiment showing the heated seawater flowing down the rear leg, into an axial tube, and across the upper surface of the pipeline.
FIG. 12 is a section thru the alternate embodiment showing the heated seawater flowing across the upper surface of the pipeline, into an axial tube, and up the front leg.
FIG. 13 is a partial section thru the alternate embodiment showing the full circulation of the heated water down the rear leg, along the circulation chamber and back up the front leg.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to FIG. 1 , a subsea pipeline 10 has a blockage indicated at 12 . The subsea pipeline 10 is setting on the seafloor 14 and is covered by seawater 16 which may be as cold as 32° F. Arrows 18 indicate the flowing of heated seawater across the upper portion 20 of the subsea pipeline 10 for the purpose of disassociating the pipeline blockage 12 . The disassociation may be melting a hydrate, melting a paraffin blockage, or softening a paraffin blockage to the point that it will flow.
Two tubes 22 and 24 run parallel to the subsea pipeline and have a plurality of holes 26 and 28 which direct heated seawater into the circulation chamber 30 or out of the circulation chamber 30 respectively. Line 32 feeds heated seawater into tube 22 and return line 34 draws the seawater out of tube 24 . The return line 34 leads to pump 36 and then to heating element 38 and back to tube 32 . The heated seawater which is introduced into the combustion chamber by tube 22 is somewhat cooled by flowing across the upper portion 20 of subsea pipeline 10 before it enters tube 24 to return thru the pump and back into the heating element 38 . As the returning seawater is only partially cooled, the inlet to the heating element 38 is higher, so the output seawater from the heating element will be progressively higher each circulation until a temperature is reached in which the heat losses thru the insulation will equal the heat input and so a form of steady state will be achieved.
Resilient flap type seals 40 are placed around the perimeter of the circulation chamber 30 to restrict the mixture of the seawater 42 within the circulation chamber with the seawater 44 outside the circulation chamber.
Most conventional ROVs have a minimum of 100 horsepower of electricity which can almost all be converted into heat thru a resistance heater, so it can be readily seen that if the same seawater is circulated with only minimal leakage, it can be quickly brought to a high temperature.
Referring now to FIG. 2 , the apparatus of FIG. 1 is shown below an ROV 50 and operating in an area of the subsea pipeline 10 which has been uncovered in a ditch form 52 . By uncovering only the top portion of the pipeline, the lower portion of the seafloor is left intact to support the pipeline. The thermal operating module is generally referred to as 55 .
Referring now to FIG. 3 , an alternate section through the thermal operating module 55 showing rollers 60 and 61 mounted on motors 62 and 63 and pivoted about pin 64 . Cylinders 66 and 67 will move to push the rollers 60 and 61 against the pipeline 10 and the motors 62 and 63 will turn the rollers 60 and 61 to drive the thermal operating module along the pipeline.
Referring now to FIG. 4 , rollers 60 , 61 , 70 , and 71 are shown positioned to move the thermal operating module 55 along the pipeline 10 . The speed along the pipeline would be calculated to allow the hydrates and/or paraffin in the pipeline to melt during the heating cycle. Umbilical 74 typically provides 100 to 150 horsepower of electricity to operate the ROV, but in the case of the thermal operating module will use a majority of this electrical horsepower to generate heat.
Referring now to FIG. 5 , an alternate method of converting energy into heat is illustrated. Rather than providing electrical resistance heating, the energy is directed toward the pump 80 which is a high pressure pump (i.e. 10,000 p.s.i.) rather than a circulating pump like 36 (i.e. 15 p.s.i.). The high pressure output of pump 80 is directed across a pressure reducing means such as an orifice 90 to drop the pressure to a low pressure (i.e. 15 p.s.i.). In dropping the pressure in this “inefficient” manner, the horsepower required to operated the pump is lost into heat, which is our goal. In some situations it may be convenient to run a hose or pipe from the surface to simply provide high pressure fluid for heat generation at the subsea location in a similar manner. Using pressure to transport energy to a subsea location is practical, whereas attempting to directly pump high temperature fluid to a subsea location will result in substantial thermal energy losses.
Alternate methods of generating heat at the subsea location adjacent to the pipeline such as chemical reactions can also be used to provide the heat necessary for the task of pipeline blockage remediation.
Referring now to FIG. 6 , an embodiment is illustrated which can eliminate the requirement for uncovering and then recovering the subsea pipelines. Both uncovering and recovering subsea pipelines are expensive tasks. It is inherently true if the sea bottom is soft enough for the pipeline to be buried into it, it is relatively soft. FIG. 6 illustrates the circulation chamber 30 being streamlined and mounted on streamlined legs such that they will simply plow through the soft seafloor bottom. Leg 100 extends down from the heat generation section 101 and supports the circulation chamber 30 and a pair of rollers 102 and 104 . Operation of the rollers will be discussed in the next figure. Drive shafts 106 and 108 go up to motors 110 and 112 (not seen) which are mounted on cylinders 114 and 116 (not seen).
Referring now to FIG. 7 , roller 104 is supported on axle 120 which pivots about pivot 122 and extends to universal joint 124 and then upward by shaft 108 to motor 110 (not shown). When shaft 108 is pushed down by cylinder 114 (not shown), the roller 104 pivots away from the central opening 126 . When the cylinder 114 pulls up, the roller 104 is moved toward the central cavity 126 and toward subsea pipeline 10 when subsea pipeline 10 is in the central cavity 126 .
Referring now to FIG. 8 , a side view of the alternate embodiment is shown illustrating that two stream lined legs 130 and 132 connect the circulation chamber 30 to the heat generation section 101 .
Referring now to FIG. 9 , a cross section of leg 130 of FIG. 8 is shown illustrating the streamlined shape and the location of drive shafts 106 and 108 and the return line 34 .
Referring now to FIG. 10 , the circulation chamber 30 along with rollers 102 and 104 are shown engaging the pipeline 10 below the seafloor. Cylinders 114 and 116 are shown retracted to the position in which the rollers 102 and 104 are engaging the pipeline 10 .
Referring now to FIG. 11 , the rear leg 132 is shown with the heated seawater going down the tube 32 and across the circulation chamber 30 along arrow 140 .
Referring now to FIG. 12 , the front leg 130 is shown with the somewhat cooled seawater returning back to the pump for recirculation along arrow 141 .
Referring now to FIG. 13 , a partial section of the alternate embodiment is shown with the full circulation path. The components as discussed in FIG. 6 are shown within the front leg 130 , and matching components are shown in the rear leg 132 . Both the front leg 130 and the rear leg 132 would have similar streamlined profiles as illustrated in FIG. 9 .
The foregoing disclosure and description of this invention are illustrative and explanatory thereof, and various changes in the size, shape, and materials as well as the details of the illustrated construction may be made without departing from the spirit of the invention.
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The method of taking a remotely operated vehicle to the ocean floor to land on and move along a subsea pipeline above or below the seafloor and repeatedly circulate seawater which has been heated electrically, mechanically, or chemically across the outer surface of the pipeline to melt hydrates or paraffins which have formed on the inside of the pipeline.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to the field of brooms, including dust mops and brushes, and in particular to push brooms, handheld whiskbrooms and straight brooms.
2. Description of Related Art
Brooms in general are old and well known in the art. Push brooms are known and handheld whiskbrooms are known. However, while known and commonly used, there is a continuing need to develop brooms that handle sweeping dust and debris in a better, more efficient manner.
SUMMARY OF THE INVENTION
In one embodiment of the invention there is provided a broom comprising a broom head frame. The frame has a front edge terminating in a front left end and a front right end. The frame having a left section, a right section and a center section with a left portion of the front edge forming a part of said left section, a center portion of the front edge forming a part of the center section and a right portion of the front edge forming a part of the right section. The front edge having a front apogee point between the front left end and the front right end, and a front apogee tangent line. The front edge having a concave shape such that the left portion and the right portion each extend ahead of the front apogee tangent line by from 10 degrees to 60 degrees. The length from the front left end to the front right end defining a frame length.
In another embodiment of the invention there is provided a broom comprising a broom head frame having a straight center section, a straight left section and a straight right section. The straight center section has a first end and a second end. The straight left section has a left end forming the left end of the frame and a right end mounted to the first end so as to be rotationally adjustable. The straight right section having a right end forming the right end of the frame and a left end mounted to the second end so as to be rotationally adjustable.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a front elevation view of a push broom in accordance with one embodiment of the current invention.
FIG. 2 is a side elevation view of a push broom in accordance with the embodiment illustrated in FIG. 1 .
FIG. 3 is a top view of a dust mop in accordance with another embodiment of the current invention.
FIG. 4 is a front view of a tabletop brush or whiskbroom in accordance with yet another embodiment of the current invention.
FIG. 5 is a front view of a house broom or straight broom in accordance with still another embodiment of the current invention.
FIG. 6 is a top view of an adjustable push broom in accordance with a further embodiment of the current invention.
FIG. 7 is a front view of a curved frame broom with extended bristles in accordance with yet a further embodiment of the current invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The current invention concerns a sweeping broom or dust mop with a head that has an angled or curved concave design, but fabricated with a straight center or slightly curved section, and two forward-angled or curved end sections. The end sections are angled or curved at from 10 degrees to 60 degrees from the center section line or from an apogee tangent line as described below. This angle can be pre-formed in a fixed position, or it can be adjustable. The length of the center section can vary, as can the length of the end sections. The broom handle attaches to the broom head at the center or slightly offset to the center, or can protrude from the side, as in a counter top brush.
Referring now to FIGS. 1 and 2 a push broom 10 in accordance with the current invention can be seen. Push broom 10 comprises handle 12 , head or head frame 14 and bristles 16 . Handle 12 is connected to the head frame 14 . The connection can be by any conventional known means, such as by screw mounting or by the handle 12 being formed integrally with the head frame 14 . The bristles 16 are attached to the head frame in known conventional means for such push brooms. The frame 14 comprises a left section 18 , a center section 20 and a right section 22 . As illustrated in FIG. 1 , the left section 18 , center section 20 and right section 22 are integrally connected. At this point, it should be noted that herein the embodiments will be described with reference from the position of a user during normal broom operation and, thus, terms such as left, right, front and back are to be interpreted from that perspective. Additionally, the angling of the frame will be described with reference to an apogee point and an apogee tangent line. For a straight center section such as shown in FIG. 1 , the apogee point can lie longitudinally anywhere along the center section 20 and the apogee tangent line will be a parallel to the longitudinal axis of the center section 20 . For a curved frame such as shown in FIG. 7 , the apogee point will be the point along a curved front edge 54 of head frame 44 farthest from both the ends ( 56 and 58 ) of head frame 44 and the apogee tangent line 72 will be a line tangent to that front curved edge of head frame 44 at the apogee point. Laterally, the apogee point can lie any where along the width of the frame. Common choices would include choosing the apogee point at the front edge, back edge or center of the frame. The apogee points can be better understood with reference to the descriptions of FIG. 1 and FIG. 7 below.
Returning now to FIGS. 1 and 2 , the head frame 14 has front edge 24 . Front edge 24 terminates in front left end 26 and front right end 28 . Front edge 24 extends across left section 18 , center section 20 and right section 22 such that a left portion of the front edge 24 extends across left section 18 , a center portion of front edge 24 extends across center section 20 and a right portion of front edge 24 extends across right section 22 . As mentioned above, front edge 24 has front apogee point 30 , which can be anywhere along the center portion of front edge 24 . Front apogee tangent line 32 is parallel to the portion of front edge 24 at center section 20 and passes through the front apogee point 30 . The end sections (left sections 18 and right sections 22 will be angled such that they extend ahead of the front apogee tangent line 32 and, thus, the frame will have a concave configuration. As illustrated, the left portion of front edge 24 is at an angle α to the front apogee tangent line 32 and the right portion of front edge 24 is at an angle β to the front apogee tangent line 32 . Generally, angles α and β will be equal but it is within the scope of the invention for them to be different. Angles α and β can be from 10 degrees and 60 degrees, can be from 20 degrees to 40 degrees or can be from 22 degrees to 30 degrees.
For purposes of this disclosure, the frame length is defined as the length from the front left end 26 to the front right end 28 . The length of the center section 20 can vary, as can the length of the end sections. Generally, the center section 20 will comprise from 40 percent to 60 percent of the frame length and the left section 18 and the right section 22 will each comprise from 20 percent to 30 percent of the frame length. Often the center section 20 will comprise about 50 percent of the frame length and the left section 18 and the right section 22 will each comprise about 25 percent of the frame length.
The bristles 16 are positioned downward on the center section, and can be directed slightly inward on the end sections to help facilitate the debris being directed towards the center of the broom head. The bristles 16 are flared outward on each end (front left end 26 and front right end 28 ) of the frame to facilitate entry into confined spaces. These end bristles can generally be slightly longer than the other bristles to ensure contact with the floor. The amount of flaring of these end bristles depends on the type of broom and the length of the bristles. For typical push broom bristle lengths, the end bristles will generally flare outward from 0.5 inch to 3 inches from each end of the frame and can flare outward about 1 to about 2 inches. For example, if the bristles for the push broom are 3.5 inches then the end bristles can flare out about 1.5 inches from each end of the frame and the end bristles will be about a quarter of an inch longer than the non-end bristles.
Referring now to FIG. 7 , the design can also feature a semi-circular head, where the center section is slightly concave, and the end sections continue this curvature. This could be in a gradual curve or various degrees. In the embodiment of FIG. 7 , a straight broom 40 is illustrated; however, the discussion is applicable to other types of brooms. Straight broom 40 has a handle 42 , head or head frame 44 and bristles 46 . Handle 42 is connected to the head frame 44 . The connection can be by any conventional known means, such as by screw mounting or by the handle being formed integrally with the head frame. The bristles are attached to the head frame in known conventional means for such straight brooms. The head frame 44 comprises a left section 48 , a center section 50 and a right section 52 , which make a continuous curve.
Returning now to FIG. 7 , the head frame 44 has front edge 54 . Front edge 54 terminates in front left end 56 and front right end 58 . Front edge 54 extends across left section 48 , center section 50 and right section 52 such that a left portion of the front edge 54 extends across left section 48 , a center portion of front edge 54 extends across center section 50 and a right portion of front edge 54 extends across right section 52 . Front edge 54 has front apogee point 60 , which as mentioned above, is the point on front edge 54 farthest from both front left end 56 and front right end 58 . In the embodiment illustrated, the front apogee point 60 is in the middle of front edge 54 ; however, for asymmetrical brooms this may not be the case. Front apogee tangent line 62 is tangent to the curve of front edge 54 and passes through the front apogee point 60 . End sections (left section 48 and right section 52 will extend ahead of the front apogee tangent line 62 and, thus, the frame will have a concave configuration. As illustrated, both the left portion of front edge 54 and the right portion of front edge 54 extend an angle γ from the front apogee tangent line 62 ; however, it is with in the scope of the invention for the two sections to be different angles. The angle γ can be from 10 degrees and 60 degrees, can be from 20 degrees to 40 degrees or can be from 22 degrees to 30 degrees.
A house broom (also called a straight broom) or a dust mop (also called a dry mop) can utilize this same angled or curved design in both directions allowing the broom to be used in forward or backward sweeping motions. The center section remains the same but the angle/curved ends protrude in forward and backward directions, joining at the ends to form a loop. This can create a hollow center or remain solid. Referring now to FIG. 3 , a dust mop 80 utilizing the design in both directions can be seen. Dust mop 80 comprises handle 82 , head or head frame 84 and dry mop pad 86 . Handle 82 is connected to the head frame 84 . The connection can be by any conventional known means, such as by screw mounting or by the handle being formed integrally with the head frame. The dry mop pad is attached to the head frame in known conventional means for such dust mops. Typically, the pad will be a glove fitting over the frame. The head frame 84 comprises a left section 88 , a center section 90 and a right section 92 .
Head or head frame 84 has front edge 94 and back edge 104 . Front edge 94 terminates in front left end 96 and front right end 98 . Front edge 94 extends across left section 88 , center section 90 and right section 92 such that a left portion of the front edge 94 extends across left section 88 , a center portion of front edge 94 extends across center section 90 and a right portion of front edge 94 extends across right section 92 . Front edge 94 has front apogee point 100 , which can be anywhere along the center portion of front edge 94 since the center section 90 is straight. Front apogee tangent line 102 is parallel to the portion of front edge 94 at center section 90 and passes through the front apogee point 100 . The end sections (left section 88 and right section 92 ) will be angled such that they extend ahead of the front apogee tangent line 102 and thus the frame will have a concave configuration. As illustrated, the left portion of front edge 94 is at an angle α to the front apogee tangent line 102 and the right portion of front edge 94 is at an angle β to the front apogee tangent line 102 . Generally, angles α and β will be equal but it is within the scope of the invention for them to be different. Angles α and β can be from 10 degrees and 60 degrees, can be from 20 degrees to 40 degrees or can be from 22 degrees to 30 degrees.
Back edge 104 terminates in back left end 106 and back right end 108 . In the embodiment illustrated, the dust mop 80 has rounded ends thus the front left end 96 and the back left end 106 are at the same point. Also, front right end 98 and back right end 108 are at the same point. This may not be the case for other configurations. Back edge 104 extends across left section 88 , center section 90 and right section 92 such that a left portion of the back edge 104 extends across left section 88 , a center portion of back edge 104 extends across center section 90 and a right portion of back edge 104 extends across right section 92 . Back edge 104 has back apogee point 110 , which can be anywhere along the center portion of back edge 104 since the center section 90 is straight. Back apogee tangent line 112 is parallel to the portion of back edge 104 at center section 90 and passes through the back apogee point 110 . The end sections (left section 88 and right section 92 ) will be angled such that they extend behind the back apogee tangent line 112 and, thus, the frame will have a concave configuration. As illustrated, the left portion of back edge 104 is at an angle δ from the back apogee tangent line 112 and the right portion of back edge 104 is at an angle ε to the back apogee tangent line 112 . Generally, angles δ and ε will be equal but it is within the scope of the invention for them to be different. Angles δ and ε can be from 10 degrees and 60 degrees, can be from 20 degrees to 40 degrees or can be from 22 degrees to 30 degrees.
Similar to the embodiment of FIG. 1 , the length of the center section 90 can vary, as can the length of the end sections. Generally, the center section 90 will comprise from 40 percent to 60 percent of the frame length and the left section 88 and the right section 92 will each comprise from 20 percent to 30 percent of the frame length. Often the center section 90 will comprise about 50 percent of the frame length and the left section 88 and the right section 92 will each comprise about 25 percent of the frame length.
Turning now to FIG. 6 an embodiment is illustrated where a push broom 114 has an adjustable format. Push broom 114 generally comprises handle 116 , head frame 118 and bristles (not shown in FIG. 6 ). The head frame 118 has left section 120 , center section 122 and right section 124 . Center section 122 is a straight center section and has a first end 126 and a second end 128 . Center section 122 has a center line 127 as shown, which is an apogee tangent line taken at the center of the frame. Left section 120 has a left end 119 , which is the left end of the head frame 118 , and a right end 121 . Right end 121 of left section 120 is mounted to first end 126 of center section 122 so as to be rotationally adjustable. Similarly, right section 124 has a right end 123 , which is the right end of head frame 118 , and a left end 125 . Left end 125 of right section 124 is mounted to second end 128 of center section 122 so as to be rotationally adjustable. As illustrated left section 120 and right section 124 are mounted onto center section 122 by tension screws 130 and 132 , respectively. Left section 120 and right section 124 can be rotationally adjusted from an angle of 60 degrees in front of the center section to an angle 60 degrees behind the center section. Optionally, left section 120 and right section 124 can be rotationally adjusted from an angle of 40 degrees in front of the center section to an angle 40 degrees behind the center section. In other words the center line 129 of the left section 120 will be at an angle α to center line 127 of the center section and the center line 131 of the right section 124 is at an angle β to center line 127 . The angles α and β can be from 60 degrees behind the center line 127 to 60 degrees ahead of the center line 127 , or can be from 40 degrees behind the center line 127 to 40 degrees ahead of the center line 127 .
In the adjustable format, the operator can loosen tension screws 130 and/or 132 or similar mechanisms, such as tongue and groove design, and adjust the angle of the end sections to the desired shape. It can be used as a straight broom (as shown by the solid lines in FIG. 6 ), or the ends can be adjusted forward (as shown by the phantom lines in FIG. 6 ) or backwards (not shown). This allows the broom to be used in both directions, to reduce bristle memory and wear.
Similar to the embodiment of FIG. 1 , the length of the center section 122 can vary, as can the length of the end sections. Generally, the center section 122 will comprise from 40 percent to 60 percent of the frame length and the left section 120 and the right section 124 will each comprise from 20 percent to 30 percent of the frame length. Often the center section 122 will comprise about 50 percent of the frame length and the left section 120 and the right section 124 will each comprise about 25 percent of the frame length.
Other embodiments are illustrated in FIGS. 4 and 5 . FIG. 4 illustrates a table top brush 133 (also known as a dust broom or whisk broom). Brush 133 has a handle 134 , a head frame 135 and bristles 136 . Head frame 135 has left section 138 , center section 140 and right section 142 wherein left section 138 and right section 142 are angled as described above. FIG. 5 illustrates a house broom 150 (also known as a straight broom). Similar to the other embodiments, house broom 150 has a handle 152 , a head frame 154 and bristles 156 . Head frame 154 has left section 158 , center section 160 and right section 162 wherein left section 158 and right section 162 are angled as described for the other embodiments.
For the various embodiments of the current invention, the broom head can be of any suitable material (plastic, metal, wood composites, etc.) and the bristles can be of numerous materials (plastics, straw, wire, wool, yarn, etc.) and in various sizes and lengths. The bristles can be of various firmness, depending on the target material to be swept. The broom handle can be of wood, plastic or metal, and can be solid or hollow. Additionally, the bristles are positioned downward on the center section, and can be directed slightly inward on the end sections to help facilitate the debris being directed towards the center of the broom head. The bristles can be flared outward on each end tip to facilitate entry into confined spaces.
While the entire head sweeps the floor, the angled or curved ends also gather and direct the dirt and debris toward the straight center area of the head. This helps collect and control the debris during sweeping and minimizes loss of material to the sides. It also makes it easier to collect into a receptacle for disposal. This broom can be in the style of a push broom, a house broom, a whisk broom, dust mop or counter top brush.
It will be seen therefore, that the present invention is well adapted to carry out the ends and advantages mentioned, as well as those inherent therein. While the presently preferred embodiments of the apparatus has been shown for the purposes of this disclosure, numerous changes in the arrangement and construction of parts may be made by those skilled in the art. All of such changes are encompassed within the scope and spirit of the appended claims.
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The present invention relates to brooms, including dust mops and brushes, and in particular to push brooms and handheld whiskbrooms. The invention relates to a broom head frame having a left section, center section and right section where the left section and right section are at an angle to the center sections. The left and right sections can be adjustable.
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CROSS REFERENCES TO RELATED APPLICATIONS
This application claims priority from U.S. Provisional Application Ser. No. 61/688,931 filed on May 24, 2013 which is incorporated by reference herein.
TECHNICAL FIELD
The present invention relates to the field of machines capable of synthesizing selected peptides.
BACKGROUND OF THE INVENTION
Peptide synthesis is the process by which amino acids are linked by amide bonds to produce peptides. The biological process of making long peptides, that is proteins, is known as protein photosynthesis.
Liquid-phase peptide synthesis is a classical approach to peptide synthesis and has been replaced in most labs by solid-phase synthesis. However, liquid-phase peptide synthesis retains usefulness in large-scale production of peptides for industrial purposes.
Solid-phase peptide synthesis (SPPS), is now the accepted method for creating peptides and proteins in the lab in a synthetic manner. SPPS allows the synthesis of natural peptides which are difficult to express in bacteria, the incorporation of unnatural amino acids, peptide/protein backbone modification, and the synthesis of D-proteins, which consist of D-amino acids. The process typically utilizes small solid insoluble porous beads which are treated with functional units on which peptide chains can be built. The resulting peptide chain will remains covalently attached to the bead until cleaved from that bead by a reagent such as anhydrous hydrogen fluoride or trifluoroacetic acid. The peptide is thus ‘immobilized’ on the solid-phase media or bead and can be retained during a filtration process, whereas liquid-phase reagents and by-products of synthesis are flushed away.
Repeated cycles of coupling-wash-deprotection-wash creates the desired peptide chain. The free N-terminal amine of a solid-phase attached peptide is coupled to a single N-protected amino acid unit. This unit is then deprotected, revealing a new N-terminal amine to which a further amino acid may be attached. The ability to perform wash cycles after each reaction provides a means to remove excess reagent with all peptide product remaining covalently attached to the insoluble resin bead. The objective is to generate high yield in each step. Thus each amino acid is added in major excess (2˜10×) and coupling amino acids together is optimized by the selection of agents. There are two major forms of SPPS utilized in labs and industry, Fmoc and Boc. Unlike ribosome protein synthesis, solid-phase peptide synthesis proceeds in a C-terminal to N-terminal fashion. The N-termini of amino acid monomers is protected by either of these two groups and added onto a deprotected amino acid chain.
SPPS is limited by yields, and typically peptides and proteins in the range of 70 amino acids are pushing the limits of synthetic accessibility. Synthetic difficulty also is sequence dependent and amyloid peptides and proteins are difficult to make.
SUMMARY OF THE INVENTION
In accordance with the present invention, there is presented herein an automated peptide synthesizing machine comprising a cabinet or housing containing a plurality of reagent containers, a plurality of pre-reaction vessels, a plurality of reaction vessels, at least one waste container, a power supply, a plurality of motor controllers, a computer, a motorized amino acid syringe/needle probe assembly, a motorized rotatable amino acid carousel, a fluid metering assembly, and a plurality of fluid and gas control valves and lines connecting the fluid handling elements included above. The computer is capable of controlling valves, motors, and a pump for the purpose of delivering fluids and gases to particular vessels. The computer receives inputs from fluid sensing photo cells and flag sensing photo cells and is programmed to carry out given processes necessary for the synthesizing of peptides and for the delivering of particular selected fluids and gases to particular selected pre-reaction vessels and selected reaction vessels to resulting in synthesizing of distinct peptides within separate distinct reaction vessels so that a different and distinct peptide is synthesized in each of the reaction vessels.
The automated peptide synthesizer is capable of synthesizing differing and distinct peptides in the plurality of reaction vessels simultaneously, each distinct peptide being synthesized in a separate and distinct the reaction vessel. The motorized amino acid needle probe assembly is capable of moving a needle probe down into or up out of an amino acid bottle or a needle probe cleaning agent bottle whereupon fluid is drawn up into the needle probe and on through a connected line to a selected pre-reaction vessel. Further, the needle probe assembly is capable of rotating a needle probe arm to a horizontal position centered over the amino acid bottle or the needle probe cleaning agent bottle.
The needle probe is mounted on a first vertically movable carriage moved by a first motor and belt driven threaded rod. The first vertically moveable carriage is moved to a given vertical position by the motor, belt, and threaded rod wherein the rotation of the rod and therefore the vertical position of the first carriage is sensed by a photocell monitoring a slotted disc rotating on the end of the threaded rod. The motorized amino acid needle probe assembly is controlled by the computer.
The motorized rotatable amino acid carousel contains a plurality of bottles with various amino acids and wherein the rotary position of the carousel is controlled by the computer. The fluid metering assembly includes a clear metering tube with a fluid level sensing photocell fixed within a second vertically moveable carriage wherein the fluid sensing photocell is capable of sensing a fluid level visible through the clear metering tube. The vertical movement of the second vertically moveable carriage is controlled by a second motor, a second belt and a second threaded rod wherein the rotation of the second rod is sensed by a photocell monitoring a slotted disc on the end of the second threaded rod, and movement of the second motor is controlled by the computer.
A plurality of fluid and gas control valves and lines connect the pre-reaction vessels, the reaction vessels, the reagent bottles, the amino acid needle probe assembly, the at least one waste container and the metering vessel, for the purpose of delivering required fluids to vessels for the synthesizing of peptides. The pre-reaction vessels provide a location for the pre-reaction of amino acids and reagents prior to transfer of the amino acids and reagents to the reaction vessel. The reaction vessel provides a location for the reaction of the amino acids and the reagents with resins contained within the reaction vessel to produce desired peptides. The plurality of fluid and gas control valves are controlled by the computer.
It is an object of this invention to provide an automated peptide production machine which is programmed to produce a multiplicity of different peptides, each in an individual reaction vessel, simultaneously.
It is an object of this invention to provide an automated peptide production machine wherein selected amino acids and activators are transferred into a pre-reaction vessel for a selected period of time (for example approximately five minutes), then the mixture is transferred to a reaction vessel containing resin balls comprising small solid insoluble porous beads onto which peptides are grown.
It is an object of this invention to provide an automated peptide production machine including a carousel containing selected amino acids held within vessels and an amino acid transfer arm containing a needle probe which is inserted into a selected amino acid vessel, the amino acid is withdrawn from the vessel and transferred to a pre-reaction vessel to be mixed with other selected amino acids and activators for a selected amount of time which is around five minutes and the needle probe can be rinsed if required between selections.
It is an object of this invention to provide an automated peptide production machine which transfers a premixed combination of amino acids and activators to a reaction vessel containing resin beads which may or may not have amino acid chains grown thereon previously.
It is an object of this invention to provide an automated peptide production machine which contains a plurality of pre-reaction and reaction vessels wherein separate and possibly different peptides are being synthesized simultaneously according to a program contained within the computer wherein that program may be changed as desired. The number of different pre-reaction and reaction vessels is only limited by the practicality and capability of the hardware to mix, process, and transfer the elements within the machine in an effective amount of time. A preferable range is 4 to 12 pre-reaction and reaction vessels.
Other objects, features, and advantages of the invention will be apparent with the following detailed description taken in conjunction with the accompanying drawings showing a preferred embodiment of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
A better understanding of the present invention will be had upon reference to the following description in conjunction with the accompanying drawings in which like numerals refer to like parts throughout the views wherein:
FIG. 1 is a piping schematic of that portion of the automated peptide synthesizer which includes the pre-reaction vessels and the hardware used in the pre-reaction portion of the peptide synthesis and a top view of the amino acid carousel and transfer conduits in fluid connection with a selected number “twelve” pre-reaction vessels;
FIG. 2 is a piping schematic of the portion of the automated peptide synthesizer which includes the reaction vessels including the hardware which delivers the amino acids, activators, and reagents from the pre-reaction vessels to resins in reaction vessels for synthesizing peptides;
FIG. 3 is a rear view of the automated peptide synthesizer cabinet/housing showing the location of the stepper controller, interface boards, power supply cabinet vent, three way valves, amino acid needle delivery assembly, delivery pump location and waste block;
FIG. 4 is a view of the right side of the automated peptide synthesizer cabinet showing the reagent bottles, reagent bottles tube connections, connectors for DMF and PIP and nitrogen connector, access door to valves, waste blocks, and access door to the electronics;
FIG. 5 is a rear view of the automated peptide synthesizer showing the solvent measuring assembly;
FIG. 6 is a top view of the automated peptide synthesizer showing the amino acid containers, amino acid carousel for holding the bottles, and weight plates, reagent bottle block tube connections, and reagent bottles;
FIG. 7 is front view of the amino acid delivery assembly including the z-axis stop, home position sensor and holder block, rotary motor movement, z-movement assembly section, rotary probe holder, probe, guide rods and lead screw for z-axis, belt and pulleys;
FIG. 8 is front perspective view of the amino acid delivery assembly including the lead screw encoder and sensor (photo cell), stepper motor for rotary movement, belt for rotary needle movement, rotary home position sensor (photo cell), rotary movement/needle holder plate, and probe;.
FIG. 9 is a left side view of the amino acid delivery assembly showing the z-axis motor, lead screw encoder, motor for rotary action, liquid detection sensor, and motor mount, tube connection tho the pump, amino acid container vent, probe rotary holder, and probe;
FIG. 10 is a front view of the measuring vessel assembly shows the assembly guide rods, and lead screws, photocell/optical coupler with photo transistor housing, stepper motor and measuring vessel;
FIG. 11 is a right side perspective view from underneath the measuring vessel assembly showing the guide rods and lead screw, measuring vessel, and a photocell carriage member driven by a toothed pulley for the purpose of lifting and lowering the photocell carriage;
FIG. 12 is a left side perspective view from above the measuring vessel assembly showing the measuring vessel, photocell holder block, lead screw encoder, motor, lead screw nut holder block, bearing for guide rods, home photo cell, and home photo cell tang;
FIG. 13 is a right side perspective view of a reaction vessel and holder showing the top grip to release the reaction vessel, top seal spring loaded holder, reaction top seal, bottom reaction vessel seal, filter holder inside of the reaction vessel, glass reaction vessel, pivot rod and cabinet attachment block;
FIG. 14 is a front view of a reaction vessel and holder;
FIG. 15 is a front perspective view of a reaction vessel and holder showing the bottom seal and tube connection of the reaction vessel;
FIG. 16 is a perspective view of a reaction vessel and holder;
FIG. 17 is a perspective view of a bottle cap insert composed of TEFLON, the snap ring to hold the cap in place, the o-ring seal of the bottom and tube insert;
FIG. 18 is a piping schematic of the four reaction vessel embodiment of the present invention;
FIG. 19 is a perspective view of the peptide synthesizer;
FIG. 20 is a left side view of the peptide synthesizer of FIG. 18 showing the waste blocks, electronics access panel, pip bottle, DMF gas and liquid connections, and nitrogen connection;
FIG. 21 is a front view of the peptide synthesizer of FIG. 18 showing the nitrogen and DMF tube connections, robotic needle assembly, reaction vessel assembly, and amino acid carousel;
FIG. 22 is a top view of the peptide synthesizer of FIG. 18 showing the tube connections for the gas and DMF, reagent bottle PIP bottle, amino acids weight bottles, amino acid bottles, reaction vessel assembly, and robotic needle assembly for delivering amino acids and reagents;
FIG. 23 is a rear view of the peptide synthesizer of FIG. 18 showing the measuring vessel assembly, valve connections, bottom valve panel, waste block, power supply location, electronics location, stepper driver boards location, tube connections for the gas and DMF, amino acid pump location, robotic needle assembly and top valve panel;
FIG. 24 is a top view of the peptide synthesizer of FIG. 18 with to top cover removed showing the amino acid pump, robotic needle assembly, reagent bottle PIP bottle, amino acid weight guide, amino acid carousel, top valve panel, valve connections, waste block and photo cell connections;
FIG. 25 is a left side view of the peptide synthesizer showing the waste connection, USB connection, power entry module fan location, and reagent bottle tube connection;
FIG. 26 is a front view of the peptide synthesizer showing the cabinet vent, valve and robotics assembly compartment, waster connections, and electronics compartment;
FIG. 27 is a perspective view of the peptide synthesizer showing the reaction vessels and prereaction vessels, amino acid weight guide and amino acid carousel, amino acid needle assembly, reagent bottles;
FIG. 28 is a right side view of the peptide synthesizer showing the reagent bottles and tube connections, waste connection, electronic compartment, solvent and reagent bottle connection, and nitrogen connection;
FIG. 29 is a top view of the peptide synthesizer showing the valves compartment, reagent bottles and connections, vent cabinet and weight plate indicator and weight plates;
FIG. 30 is a front view of the peptide synthesizer showing the delivery valves, solvent/piperidine delivery assembly, stepper driver location, power supply location, waste connection, amino acid regents delivery needle assembly and waste connections;
FIG. 31 is a perspective view of the amino acid delivery system;
FIG. 32 is an enlargement of the of the amino acid rotary delivery system of FIG. 31 showing the z-axis stop, home position photo cell sensor, and liquid detection sensor;
FIG. 33 is a bottom perspective view of the amino acid rotary delivery system showing the drive belts;
FIG. 34 is an enlarged view showing the drive belt assembly of FIG. 33 ; and
FIG. 35 is a perspective view showing the amino acid delivery needle probe assembly and encoder wheel assembly;
FIG. 36 is a top view of a carousel holding amino acid containers within a subtray.
FIG. 37 is a front view of the automated peptide synthesizer cabinet showing the reaction vessel assembly for 12 units, pre-reaction vessels, reagent bottles, amino acid needle delivery assembly and amino acid turn table and containers therein of FIG. 3 ;
FIG. 38 is a view of the left side of the automated peptide synthesizer showing the cooling fan, power module switch, communication cable connection, and reagents bottle connections of FIG. 4 ;
FIG. 39 is a perspective view showing an enlarged view of the weight plate having cylindrical bores or sleeves for holding removable bottles therein of FIG. 6 ;
FIG. 40 is an enlarged view of the depth encoder and sensor (photo cell) of the amino acid delivery assembly of FIG. 7 ;
FIG. 41 is a perspective top and front view of the amino acid delivery assembly of FIG. 7 ;
FIG. 42 is a perspective bottom and front view of the amino acid delivery assembly of FIG. 7 ;
FIG. 43 is a perspective view of the photo cell holder and lead screw movement encoder consisting a wheel and photo cell of FIG. 10 ;
FIG. 44 is an enlarged view of the lower portion of the measuring vessel assembly of FIG. 11 showing the motor, motor mount, belt to drive the lead screw and pulleys;
FIG. 45 is a top view of a carousel subtray;
FIG. 46 is a side view of the reaction vessel of FIG. 15 ;
FIG. 47 is a perspective view of a bottle cap insert from just above; and
FIG. 48 is an enlarged view of the encoder wheel assembly of FIG. 35 .
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The automated peptide synthesizer 10 , shown in the figures includes a cabinet 7 , reaction vessels 101 - 112 , pre-reaction vessels 201 - 212 , reagent bottles 90 - 93 , a carousel 80 , a carousel motor 88 (shown in figure 36 ), an amino acid delivery needle probe assembly 85 , a metering assembly 120 , a fluid pump 5 , solenoid valves 1 - 4 , 8 , 9 and 11 - 75 , and a control system including a power supply 434 , and a computer 430 and stepper motor drivers 432 which control the motors in the carousel 80 , the amino acid delivery needle probe assembly 85 , the metering assembly 120 , and the fluid pump 5 .
In this specification, it is understood that the valves are all electrically controlled solenoid valves. Where shown in the schematics, the valves are drawn in the de-energized state. The valves have three ports: A, B and C. As drawn, fluid flows into port A and out through port Band port C is closed. If the valve becomes energized, fluid flows into port A and out through port C and port B is closed.
It is also understood that, as shown in FIGS. 13, 14, 15, 46, 16, 17 and 47 , the reaction vessels 101 - 112 are removably held within a bracket assembly 136 and are manually removed and replaced as follows: while holding the reaction vessel 106 , for example, with one hand, use the other hand to urge top seal holder 130 toward the top grip 132 to release and free the top of reaction vessel 106 , thus allowing vessel 106 to be removed. At this point, a user either replaces vessel 106 with another selected vessel or prepares vessel 106 to be returned to the original vessel holder 136 by emptying, cleaning and replacing new resins into vessel 106 for a new peptide synthesizing procedure. Replacing vessel 106 into vessel holder 136 is the reverse of the removal process. Reaction vessels of varying volumes are provided, all of which are capable of being held in vessel holder 136 . The reaction vessels 106 are cylindrical and the volumes depend on the particular diameter of a given reaction vessel. Pre-reaction vessels 201 - 212 are not intended to be removable but are used and cleaned automatically by the automated peptide synthesizer 10 by way of the connected fluid lines and valves.
A two part schematic of the automated peptide synthesizer 10 is shown in figures +a 36 and 2 . Figure 36 shows the pre-reaction portion of the synthesizer. Different amino acids are held in amino acid containers 82 within carousel 80 , shown in figure 36 . Carousel 80 holds up to 24 amino acid containers, each containing a different amino acid. Shown in FIGS. 6 and 39 , carousel 80 is a circular turn table tray holding four sub-trays 95 . Each sub-tray 95 includes a knob type handle for lifting the sub-tray 95 from or into the turn table tray. As shown in figures 6 and 39 , each sub-tray 95 is capable of holding up to six amino acid containers 82 within the acid container receptacles 96 . The sub-trays 95 provide a quick and easy method for a user to supply and replenish amino acids to synthesizer 10 . As shown in FIGS. 1 and 36 , carousel motor 88 causes carousel 80 to rotate on pin 81 whereby the tip of needle probe 84 is brought into horizontal alignment with the center of the top opening of a selected acid container 82 , thus selecting a particular amino acid to be drawn to a particular pre-reaction vessel, as shown in figure 37 . Sub-trays 95 are located and supported in the turn table tray by a lip 98 at the top marginal edge of sub-tray 95 .
The amino acid delivery needle probe assembly 85 , shown in FIGS. 7, 40, 41, 42, 8 , and 9 , includes a frame 184 , a threaded lead screw 194 , a threaded carriage block 191 , guide rods 187 , a lead screw toothed belt 186 , a toothed drive pulley 183 , a toothed driven pulley 189 , a z-axis motor 86 , and a sub-frame 193 which holds a rotary motor 182 , a rotary arm 188 , and an amino acid needle 84 . Amino acid needle 84 includes two nipples at the top, a suction line nipple 180 and a vent line nipple 177 as shown in FIG. 9 . Z-axis motor 86 turns to drive lead screw 194 which in turn moves carriage block 191 up or down. Carriage block 191 carries sub-frame 193 along with rotary motor 182 , rotary arm 188 and amino acid needle 84 , all as one unit, up and down. Therefore, when needle probe 84 needs to plunge downward into an amino acid container 82 , stepper rotary motor 86 runs, turning lead screw 194 , which causes sub- frame 193 to move needle probe 84 downward. There is a home flag or tang 199 which is sensed by home photocell 197 when the needle assembly is at the top of the range of vertical movement. There is also an encoder wheel 190 with slits 192 which are counted by photocell 185 to provide precise vertical positioning of needle 84 . With respect to the schematic in figure 1 , nipple 180 of needle probe 84 is connected by tubing 83 to valves 1 , 2 and 3 and to pump 5 . Pump 5 is, in turn, connected to a top inlet of a selected one of pre-reaction vessels 201 - 212 by energizing a selected one of valves 14 - 25 .
With respect to FIG. 39 , carousel 80 contains four sub-trays 95 , each with six amino acid containers 82 a and 82 b and a knob-type handle 87 . Looking at the overall carousel 80 , there are 16 outer amino acid container 82 a forming an outer circle and there are eight inner amino acid containers 82 b , forming an inner circle. As shown in FIG. 37 , rotary arm 188 is positioned, with amino acid needle 84 over amino acid container 82 a . In this position, carousel 80 can be rotated to locate any one of the 16 outer amino acid containers directly under needle 84 , at which time, Z-axis motor 86 can be driven to cause needle 84 to plunge down into the selected amino acid container 82 a . In order to access any one of the eight amino acid containers in the inner circle of the carousel 80 , rotary motor 182 is driven to rotate needle 84 out to a position where the carousel 80 can be rotated to a position where a selected one of the inner amino acid containers 82 b is directly under needle 84 .
When the amino acid has been drawn from any one of containers 82 a or 82 b , needle 84 needs to be removed from the container and cleaned. Z-axis motor 86 is driven in reverse to raise needle 84 from the container. A cleaning station 195 is located toward the rear side of synthesizer 10 just behind carousel 80 . Therefore, rotary motor 182 is driven to rotate rotary arm 188 toward the rear of the synthesizer 10 to a position directly over cleaning station 195 . At this time, z-axis motor 86 is driven to plunge needle 84 into a solvent within cleaning station 195 . Solvent is drawn in and out of needle 84 . Needle 84 is now raised out of cleaning station 195 and is ready to be used again. It can be seen that there are three stationary positions for rotary arm 188 : the first position being with needle 84 located over the cleaning station 195 , the second position being with the needle 84 over the outer circle of amino acid containers 82 a and the third position being with needle 84 over the inner circle of amino acid containers 82 b . FIG. 8 shows rotary arm 188 connected to a home position wheel 196 containing one slit. Home position wheel 196 therefore rotates with rotary arm 188 . Home position photocell 198 senses the slit in home position wheel 196 when rotary arm 188 causes needle 84 to be positioned over cleaning station 195 .
To deliver, for example, a selected amount of the amino acid in acid container 82 a into the pre-reaction vessel 206 , motor 88 rotates carousel 80 so that the selected amino acid container 82 a is directly under needle probe 84 . Motor 86 lowers needle probe 84 down into amino acid container 82 a . With respect to FIG. 36 , valve 19 is energized to open the top right inlet port of pre-reaction vessel 206 to the fluid line 83 . Valve 3 must also be energized to allow fluid to the pump 5 . Pump 5 is now started. Amino acid is drawn from amino acid container 82 a , through fluid line 83 , valves 1 , 2 , 3 , 4 , 11 , and 14 - 18 , whereupon energized valve 19 diverts the amino acid into the top right inlet of pre-reaction vessel 206 . Pump 5 runs until the desired amount of amino acid is delivered. The needle is then withdrawn from amino acid container 82 a , and is rotated and plunged into a solvent within cleaning station 195 to be cleaned. In this same manner, any of the amino acids contained within the 24 amino acid containers 82 held within carousel 80 may be added to any of the pre-reaction vessels 201 - 212 by energizing the proper one of the diverter valves 14 - 25 .
Further, to deliver a selected amount of Activator 1 or 2 , contained in vessels 91 and 90 respectively, to the pre-reaction vessel 206 , either valve 1 or valve 2 must be energized to allow the desired activator fluid to be pumped from either vessel 90 or 91 , after which, pump 5 is started to deliver the activator through valves 3 , 4 , 11 , 14 - 18 and then the fluid is diverted by valve 19 into the top right inlet port of pre-reaction vessel 206 . As stated in the paragraph above, Activators 1 or 2 may be pumped to any of the pre-reaction vessels 201 - 212 by energizing the proper one of the diverter valves 14 - 25 .
After the amino acids and activators are added to the selected pre-reaction vessel, vessel 206 in this example, the mixture is allowed a selected amount of time, approximately 5 minutes, to react.
A selected amount of resin has previously been placed within reaction vessel 106 by hand. Referring to FIGS. 13, 14, 15, 46, 16, 17 and 47 , this is accomplished by urging top seal holder 130 toward top grip 132 to release reaction vessel 106 . Reaction vessel 106 is then lifted and removed by hand and a selected amount of resin is added to the reaction vessel 106 . Reaction vessel top seal 134 is rigidly fixed to the bottom of the top seal holder 130 . As top seal holder 130 is urged upward and rotated about pivot pin 131 , top seal 134 is raise out of and above the top opening of reaction vessel 106 , for example. Now, reaction vessel 106 is grasped and raised up and out of the bottom of reaction vessel holder 136 . The bottom reaction vessel seal 135 includes a rubber stopper 137 with a central drain hole and a TEFLON filter 133 above the stopper 137 . When resin is added to reaction vessel 106 , the TEFLON filter 133 prevents resin from escaping through the drain hole in stopper 137 . Further, when amino acids and solvents are added and then drained from reaction vessel 106 , the TEFLON filter 133 prevents the resins and attached peptides from draining out of the reaction vessel 106 . Now, reaction vessel 106 , along with the resins which were added, is returned to reaction vessel holder 136 .
With reference to FIGS. 13, 14, 15, 46, 16, 17 and 47 , the top seal 134 comprises a TEFLON stopper-like seal with two parallel axial apertures to receive incoming fluid lines. TEFLON is trademark of the DuPont Corporation of Wilmington, Delaware. Top seal 134 includes an integral exterior shoulder 334 and parallel slot 353 with a snap ring 352 . Top seal 134 is inserted into an aperture within the top seal holder 130 and snap ring 352 is applied so that top seal 134 is captured between shoulder 334 and snap ring 352 to hold top seal 134 snugly onto top seal holder 130 . Below shoulder 334 is another slot 355 wherein resides an elastomeric O-ring 350 to form a pressure tight seal between the fluid lines and the reaction vessel.
After the pre-reaction time of five minutes or so, the fluid mixture is delivered from the pre-reaction vessel 206 to the reaction vessel 106 . To accomplish this, valves 4 and 11 must be energized to put pressurized nitrogen to the top port of valve 31 . Valves 31 and 43 are then energized to allow the pressurized nitrogen to force the mixture out of the bottom outlet of pre-reaction vessel 206 to a fluid line. In FIG. 2 , the fluid line is connected directly to the top right inlet port of reaction vessel 106 . Therefore, the mixture flows directly into the top right inlet port of reaction vessel 106 . It should be noted that valves 26 through 37 are dual valves with one half of the valve being connected above the adjoining pre-reaction vessel and the other half of the valve being connected below the adjoining pre-reaction valve. Therefore, it can be seen in FIG. 1 that valves 14 - 25 are energized to add fluid to the respective pre-reaction vessels 201 - 212 and that valves 26 - 37 are energized to remove or empty fluid from the respective pre-reaction vessels 201 - 212 .
After the fluid mixture has been added to the resin in reaction vessel 106 as described above, a reaction takes place wherein peptides are grown onto the resin particles. This reaction typically takes around 45 minutes to one hour or more. After this reaction is complete, the fluid residue is removed by opening drain valve 67 .
If desired, more amino acid fluid mixtures may be applied to the same resin and peptides to grow longer peptide polymers, using the same steps as described. Further steps in the process include cleaning vessels, resins and peptides with solvents such as DMF.(dimethylformamide).
Solvents and reagents such as DMF, MeOH, and piperidine are used in the process and delivered to reaction vessels by valves 51 - 75 . It can be noted that MeOH container 220 and piperidine container 222 can be vented or pressurized with nitrogen by control valves as needed but that DMF container 226 is always pressurized. As needed, any of these is routed to metering vessel 120 to be measured precisely, and then delivered to the desired reaction vessel. For example, to deliver a precise amount of piperidine to reaction vessel 106 , valve 55 is energized to pressurize piperidine vessel 222 . Valve 53 and 56 are energized to send piperidine through valve 53 , 54 and 56 into metering vessel 120 until a photocell 330 within the fluid measuring assembly 300 senses the liquid, indicating that enough liquid has been sent into metering vessel 120 . Photocell 330 was previously placed at the proper vertical position with respect to vessel 120 by stepper motor 301 as follows. Now valve 56 is de-energized, valve 58 is energized to apply pressurized nitrogen to the top of metering vessel 120 and valves 57 , 59 and 67 are energized to route the fluid from metering vessel 120 to reaction vessel 106 .
As best shown in FIGS. 10, 43, 11, 44, and 12 10 a - 12 , metering assembly 300 includes a frame 300 , a metering vessel 120 which is a vertical clear tube, a photocell carriage frame 320 which surrounds metering vessel 120 and moves vertically while carrying an internal photocell 330 capable of sensing the fluid level within vessel 120 , a photocell carriage member 302 with female threads being threaded onto a threaded vertical rod 312 driven by a toothed pulley 311 for the purpose of lifting and lowering the photocell carriage 320 , and a stepper motor 301 with a toothed driving pulley 316 , a toothed belt rotatably connecting pulleys 311 and 313 . At the top of threaded rod 312 is a disc 306 with eight slots 310 and a photocell 308 for the purpose of counting revolutions of threaded rod 312 and therefore providing feedback as to the distance which the photocell carriage has moved. There is also a home tang or flag 320 which is sensed by a home photocell 318 when the carriage is at a bottom position. Upon power up, the stepper motor 301 drives the carriage to the home photocell 318 . From this point forward, the computer drives the motor 301 and counts pulses from photocell 308 to determine the precise vertical position of the photocell carriage. When a specific amount of fluid is required, the computer causes the stepper motor 301 to drive the metering photocell 330 to the proper height corresponding to the specific amount of fluid required, then, the proper valves are energized to fill the metering tube 120 until photocell 330 senses the fluid. Then the valves are de-energized because the proper amount of fluid has been delivered to the metering vessel.
As can be seen in FIGS. 36 and 2-6 , there are 12 sets of pre-reaction vessels, reaction vessels, and fluid control valves which provide the user with the capability of programming 12 separate and different processes for synthesizing 12 different peptides. One such set of the mentioned twelve sets has been used as an example process in the preceding discussion and includes:
Set 6. pre-reaction vessel 206 with connected valves 19 , 31 , and 43 , reaction vessel 106 with connected valve 67 .
The other eleven sets are as follows:
Set 1. pre-reaction vessel 201 with connected valves 14 , 26 , and 38 , reaction vessel 101 with connected valve 62 ;
Set 2. pre-reaction vessel 202 with connected valves 15 , 27 , and 39 , reaction vessel 102 with connected valve 63 ;
Set 3. pre-reaction vessel 203 with connected valves 16 , 28 , and 40 , reaction vessel 103 with connected valve 64 ;
Set 4. pre-reaction vessel 204 with connected valves 17 , 29 , and 41 , reaction vessel 104 with connected valve 65 ;
Set 5. pre-reaction vessel 205 with connected valves 18 , 31 , and 42 , reaction vessel 105 with connected valve 66 ;
Set 7. pre-reaction vessel 207 with connected valves 20 , 32 , and 44 , reaction vessel 107 with connected valve 68 ;
Set 8. pre-reaction vessel 208 with connected valves 21 , 33 , and 45 , reaction vessel 108 with connected valve 69 ;
Set 9. pre-reaction vessel 209 with connected valves 22 , 34 , and 46 , reaction vessel 109 with connected valve 70 ;
Set 10. pre-reaction vessel 210 with connected valves 23 , 35 , and 47 , reaction vessel 110 with connected valve 71 ;
Set 11. pre-reaction vessel 211 with connected valves 24 , 36 , and 48 , reaction vessel 111 with connected valve 72 ;
Set 12. pre-reaction vessel 212 with connected valves 25 , 37 , and 49 , reaction vessel 112 with connected valve 73 .
These 12 sets of vessels and valves are intended to operate independent of one another according to the program which is stored within the onboard computer 434 to synthesize as many as twelve separate and different peptides simultaneously.
Other embodiments of this peptide synthesizer include the same elements but have fewer sets of pre-reaction vessels, reaction vessels and connected valves. For example, one embodiment has only four such sets and therefore can only be used to synthesize four independent peptides simultaneously. Another embodiment contains 16 sets of pre-reaction vessels, reaction vessels and connected valves and therefore can be used to synthesize up to sixteen independent peptides simultaneously. An even higher number of sets of pre-reaction vessels, reaction vessels and connected valves is possible but higher numbers of components become impractical when there are too many processes taking place for the moving mechanical components such as the carousel, needle probe and metering assembly to keep satisfied. In other words, in order to keep 12 processes running simultaneously, each individual process needs amino acids and reagents delivered to pre-reaction and reaction vessels at the proper times. This requires a minimum amount of time to perform each of these deliveries. If the amount of time to deliver these to each pre-reaction and reaction vessel is, on average, five minutes per process, and each synthesizing process takes, on average, one hour (60 minutes), then at most, 12 processes can be simultaneously satisfied by the automated synthesizer of the present invention (5×12=60). If, however, the average amount of time to deliver these amino acids and reagents is four minutes, then an automated synthesizer of the present invention with 15 sets of pre-reaction vessels, reaction vessels and connected valves is practical (4×15=60). Thus, it can be seen that there is a practical upper limit to number of simultaneous processes, and therefore, the number of sets of pre-reaction vessels, reaction vessels and connected valves which are practical to include in any embodiment of the present invention.
The schematic of still another embodiment of the automated peptide synthesizer 400 is shown in FIG. 18 . This automated peptide synthesizer 400 contains a cabinet 407 , only 4 sets of reaction vessels RV 1 - 4 and connected valves 1 - 10 , 18 and 19 , a pump 23 , a motorized amino acid carousel 80 , a needle probe assembly 85 , a fluid metering assembly 303 , reagent bottles 90 and 91 , and flow monitoring photo cells PC 2 - 9 , but does not include pre-reaction vessels as do the previously discussed embodiments. The omission of the pre-reaction vessels simplifies the processing and is the primary difference between peptide synthesizer 400 and peptide synthesizer 10 of FIGS. 3 a. The down side, however, is the loss of the advantageous pre-reacting of the amino acids and reagents.
With reference to FIGS. 18-24 , in order to process peptides within reaction vessel 402 , for example, the user must first remove reaction vessel 402 from vessel holder 136 , and place a selected amount of resin in the vessel 402 . The user then returns the vessel 402 to holder 136 . Now the computer 434 causes the carousel to align a particular amino acid bottle 82 a directly under the needle probe of the amino acid delivery needle probe assembly 85 . The needle probe is thrust downward into the amino acid bottle 82 a by driving needle probe motor 86 . Now, valves 5 , 10 and 20 are energized to open a fluid path from the needle probe assembly 85 to reaction vessel 402 , and pump 23 is started until the amino acid is delivered to vessel 402 .
Now, the needle probe is withdrawn and rotated and plunged into a cleaning solution whereupon fluid is pumped into and out of the probe. If another amino acid is needed, the carousel 80 is rotated to the proper position and the needle probe assembly 85 thrusts the needle probe into the next amino acid bottle 82 a to draw the proper amount of the that amino acid into vessel 402 . Then the needle is cleaned as before. If a reagent is needed in vessel 402 , valves 5 , 10 and either 21 (for bottle 91 ) or 22 (for bottle 90 ) are energized and pump 23 is started until the proper amount of reagent is pumped into vessel 402 . Now, the mixture in reaction vessel 402 is allowed to react for a specific amount of time (around 45 minutes to one hour) during which time peptides will grow on the resin beads. Now, the remainder of fluid in vessel 402 is drained by energizing valve 1 and 18 . Valve 18 supplies pressurized nitrogen and valve 1 provides a fluid path from vessel 402 to a waste bottle.
At this point, the resins along with the attached peptides may be removed from the vessel 402 or, if needed, additional peptides may be grown onto the peptides already on the resins. To do this, repeat the previous paragraph.
The foregoing detailed description is given primarily for clearness of understanding and no unnecessary limitations are to be understood therefrom, for modification will become obvious to those skilled in the art upon reading this disclosure and may be made upon departing from the spirit of the invention and scope of the appended claims. Accordingly, this invention is not intended to be limited by the specific exemplification presented herein above. Rather, what is intended to be covered is within the spirit and scope of the appended claims.
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A device capable of synthesizing a plurality of selected peptides by automatically mixing various amino acids, solvents, and activators and adding these to resins contained in a plurality of individual reaction vessels. A plurality of amino acids are contained in vessels within a carousel which is rotated into position where a syringe is inserted into a selected vessel to transport the amino acid within to a pre-reaction vessel for mixing with other selected amino acids which were previously drawn from the carousel. The mixture of amino acids is then transported to a reaction vessel containing the resin balls for growth of the selected peptide. The device includes a computer, controllable valves, at least one pump, pressurized gas such as nitrogen for transporting fluids, various vessels containing amino acids, solvents, activators, resins, and tubing connecting these elements. The computer is programmable to sample, mix selected components, and apply the mixture to resins for growing peptides.
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CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional of U.S. application Ser. No. 10/892,530 filed Jul. 15, 2004, now allowed.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The invention relates to an apparatus for treating workpieces with fluids in general and for coating hollow bodies in particular.
[0004] 2. Description of Related Art
[0005] Plastics, in particular transparent plastics, are becoming increasingly important, and in many fields are displacing glass as the preferred material.
[0006] One such example is drinks bottles, which a few years ago were almost exclusively made from glass but nowadays are to a large extent made from PET plastic. The reason for this is the huge weight saving.
[0007] However, plastic bottles may have a number of drawbacks with respect to glass bottles, for example the plastics used, for example PET, are not sufficiently gas-impermeable, and consequently, in particular in the case of beverages containing carbon dioxide, the shelf life is shorter than with glass bottles unless special precautions are taken.
[0008] For this reason, the plastic bottles are internally and/or externally provided with a barrier layer by means of PICVD processes, which lengthens the shelf life.
[0009] Since drinks bottles are mass-produced products, there is a huge pressure on costs, and consequently there is a perpetual demand for improvements to the coating processes and apparatus used for this purpose.
[0010] Consequently, for efficient coating of PET bottles and other workpieces made from dielectric material, preferably plastics, it is desirable to develop an apparatus which allows very short cycle times and therefore a high throughput. Throughputs which are typically required are in the region of 10,000 bottles per hour.
[0011] WO 00/58631 has disclosed a machine of this type with a conveyor carousel for the treatment of hollow bodies in which 20 identical treatment stations are arranged on the conveyor carousel.
[0012] The invention defined in the abovementioned document works on the basis that the weight and volume of the pumps prevent them from being carried along on the carousel. Consequently, the pumps are in a fixed position and a rotary connection or distributor is used to connect the pumps to the stations.
[0013] Furthermore, the 20 stations are divided into two groups, with each group being assigned to an independent, equivalent pressure source, or the groups being differentiated on the basis of the pumps to which they are connected. The rotary distributor determines the times during the rotary motion of the conveyor carousel at which a certain pump is in communication with a certain treatment station, the distributor for this purpose having a rotating ring with 20 openings and a stationary ring with in each case 3 slots for the two groups.
[0014] However, this machine has a number of serious drawbacks.
[0015] The stationary arrangement of the pumps is disadvantageous, since the distances from the stations to the pump are relatively long, and consequently the pump power is reduced.
[0016] Furthermore, dusts or flaked-off coating fragments may accumulate in the evacuation lines and the distributor, which has an adverse effect on sealing and entails high levels of maintenance outlay.
[0017] However, a particular drawback is the use of a rotatable distributor with axially arranged disks. Distributors of this type are extremely difficult to seal and are particularly susceptible to faults caused by foreign bodies. Furthermore, on account of the fixed opening arrangement, the distributor does not allow the process sequence to be varied in any way, making it an inflexible concept.
BRIEF SUMMARY OF THE INVENTION
[0018] The invention is therefore based on the object of providing an apparatus for treating workpieces which avoids or at least alleviates the drawbacks of known apparatuses.
[0019] A further object of the invention is to provide an apparatus for treating workpieces which operates reliably and with low maintenance.
[0020] Yet a further object of the invention is to provide an apparatus for treating workpieces which can be flexibly matched to the user's requirements or to the requirements of the desired process sequence.
[0021] Yet another object of the invention is to provide an apparatus for treating workpieces which allows efficient evacuation.
[0022] One embodiment of the invention provides an apparatus for treating workpieces, in particular for the plasma coating of hollow bodies under the application of fluid, which comprises at least one treatment device, preferably a plurality of treatment devices, for receiving in each case at least one workpiece. In particular, the workpieces are internally and/or externally coated by means of a PICVD (plasma impulse chemical vapor deposition) process. The treatment devices are secured to a rotor or conveyor carousel and, in operation, rotate about the rotor axis, with one treatment cycle preferably being correlated to one rotor rotation of 360°.
[0023] Furthermore the apparatus comprises a fluid rotary leadthrough for feeding at least one fluid onto the rotor and/or for discharging at least one fluid from the rotor. It is preferable for the treatment devices to be evacuated gradually in a plurality of stages by means of vacuum pumps, with in particular at least some of the vacuum pumps being arranged in a stationary position, i.e. outside the rotor. Therefore, by way of example, vacuum passages or lines are routed onto the rotor, which is effected by means of the fluid rotary leadthrough.
[0024] On the other side, the treatment devices are supplied with fluids or process gases, in order, for example, to carry out a plasma coating of the workpieces, in particular plastic drinks bottles. These fluids are also preferably routed onto the rotor via the fluid rotary leadthrough, for example from a stationary fluid supply device. In particular, the journal and the sleeve have one or more fluid passages, through which the fluid(s) is/are fed to the treatment device on the rotor and/or discharged from the treatment device on the rotor. Accordingly, the fluid rotary leadthrough preferably defines one or more fluid passages via which the fluid(s) is/are passed from connections at the sleeve to associated connections at the journal and/or vice versa.
[0025] The fluid rotary leadthrough according to the invention has a preferably substantially cylindrical journal or shaft pin and a preferably substantially hollow-cylindrical sleeve or annular sleeve. The journal is arranged rotatably in the sleeve and, at least in sections on its lateral surface, is sealed off with respect to the sleeve.
[0026] Furthermore, the journal is preferably arranged concentrically in the sleeve, and the fluid rotary leadthrough extends along the rotor axis.
[0027] The radial or concentric design of the fluid rotary leadthrough in accordance with the invention has a number of advantages.
[0028] The fluid rotary leadthrough is of simple and reliable design. Furthermore, it is possible to use inexpensive standard seals. Furthermore, a continuous fluid connection over the entire rotary angle of 360° between the stationary part and the rotating part is possible.
[0029] Furthermore, the fluid rotary leadthrough according to the invention is suitable for a plurality of fluids to be passed through, since the diameter is, within certain limits, independent of the number of fluid passages which are implemented. Furthermore, the fluid rotary leadthrough is distinguished by a compact structure and can therefore be arranged in a readily accessible manner. This reduces the outlay involved in changing the seals. The improved accessibility also makes it easier to locate and eliminate leaks.
[0030] Therefore, the invention provides a rotary apparatus with a continuously rotating rotor and radially arranged identical coating stations with a high performance for the industrial coating process.
[0031] The fluid rotary leadthrough is particularly preferably fitted to the apparatus in such a manner that the sleeve is secured to the rotor in a rotationally fixed position and rotates with the rotor and the journal is in a fixed position. In this case, it is particularly simple to match the arrangement of the connections to the coating apparatus. However, the reverse design, with a journal which rotates in operation and a sleeve which is stationary, is also possible.
[0032] It preferable for the journal to have a substantially L-shaped or U-shaped passage with at least one axial and at least one radial passage section for each fluid, in which case the radial passage section opens out in the lateral surface of the journal in order to produce a connection to passage sections in the sleeve.
[0033] Furthermore, the sleeve and/or the journal preferably have at least one annular passage, which surrounds the journal, the annular passage being connected at least from time to time, and preferably continuously, to the radial passage section of the journal, the axial passage section, the radial passage section and the annular passage together forming a fluid passage in the fluid rotary leadthrough or being part of such a fluid passage.
[0034] On both sides of the annular passage, the journal and the sleeve are sealed, preferably by means of in each case one radially arranged seal, in particular a ring seal, i.e. the seals prevent fluid from flowing in or out in the axial direction between the journal and the sleeve. The ring seals are, for example, realized as metal or rubber seals and are preferably lubricated with a sealant, e.g. an oil suitable for vacuum applications.
[0035] This forms the basis of a further advantage of the fluid rotary leadthrough according to the invention, since it is possible in a simple way to provide sealant lines, via which, even when the apparatus is operating, it is possible to effect a possibly continuous or long-term supply of sealant or to provide lubrication for the seals. Consequently, the fluid rotary leadthrough has a longer service life and requires less maintenance.
[0036] According to a particular refinement of the invention, the sleeve has a plurality of radially arranged line connections which are distributed in a star shape in an axial plane, each treatment device being assigned a dedicated line connection. As an alternative, however, it is also possible for just one line connection to be provided on the fluid rotary leadthrough on the rotor side, and for the fluid lines to branch off between the fluid rotary leadthrough and the treatment devices, in order to distribute the fluid or vacuum to the treatment devices.
[0037] It is preferable for the fluid rotary leadthrough to have a plurality of fluid passages. This is realized, for example, by virtue of the journal having a plurality of passages with in each case one axial and one radial passage section, with the radial passage sections diverging in a star shape and opening out in the lateral surface of the journal, and the sleeve in each case having corresponding passage sections and line connections.
[0038] The axial passage sections are preferably arranged offset in the form of a ring around the axis of rotation.
[0039] In operation, it is particularly preferable for the treatment device to pass through at least one evacuation phase, in which the treatment devices are evacuated from standard pressure by a few orders of magnitude, and at least one coating phase, in which the plasma internal coating of the hollow workpieces is carried out under the activation of a process fluid or gas. In particular, the coating is carried out in through-flow mode, so that the treatment device, during the evacuation phase, is connected via a first fluid passage in the fluid rotary leadthrough to a first vacuum pump or delivery device and, during the coating phase, is connected via a second, separate fluid passage in the fluid rotary leadthrough or rotary coupling to a second vacuum pump.
[0040] For this purpose, the sleeve and/or the journal have a plurality of annular passages, which are connected to in each case one of the radial passage sections, with in each case one radial passage section and an associated annular passage lying on one plane, so as to form a pair of transition passages, and the various pairs of transition passages being axially offset with respect to one another. It is preferable for in each case at least one ring seal to be provided between the annular passages, in order to seal off the passages with respect to one another.
[0041] The annular passages are preferably designed to run all the way around, and the line connections of the journal and the sleeve are continuously connected to one another during the rotation of the rotor through 360°, which is not readily possible, for example, with a disk arrangement.
[0042] On first impressions, the continuous connection may appear disadvantageous, since the treatment devices are subject to different process phases, requiring different process parameters. However, according to a preferred refinement of the invention, the supply and/or discharge of the fluid are controlled by means of one or more valve arrangements, which are preferably arranged on the rotor. Consequently, the process control is temporally controlled by means of the valves independently of the fluid rotary leadthrough.
[0043] This results in a dual benefit: firstly, the mechanically demanding rotary leadthrough is greatly simplified, making it less susceptible to faults, and secondly the process control is made more flexible.
[0044] With regard to the valve arrangement and control, reference is made to the application entitled “Vorrichtung und Verfahren zur Behandlung von Werkstücken” [apparatus and process for treating workpieces] PCT/EP03/05473, applied for on May 26, 2003, and to the application entitled “Mehrplatz-Beschichtungsvorrichtung und Verfahren zur Plasmabeschichtung” [multi-position coating apparatus and process for plasma coating], DE 102 53 513.2, applied for on Nov. 16, 2002, in the name of the same Applicant, which are hereby incorporated in their entirety by reference in the subject matter of the present disclosure.
[0045] It is particularly preferable for the fluid rotary leadthrough to have at least one or more gas feed passages and one or more evacuation passages, a fluid being fed via the gas feed passages to the treatment device on the rotor, and the treatment devices being evacuated by means of one or more vacuum pumps via the evacuation passage during the evacuation phase(s) and/or the coating phase(s), in which context it is preferable to provide a separate pressure regulator for each phase.
[0046] It is advantageous for both the process gas supply and the evacuation to be realized using the same fluid rotary leadthrough.
[0047] Furthermore, for functional reasons the gas feed passages and evacuation passages differ in terms of their diameter. Therefore, the evacuation passages preferably have an internal diameter of at least 25 mm, preferably between 50 mm and 250 mm, and particularly preferably between 100 mm and 160 mm. The gas feed passages preferably have an internal diameter of from 5 mm to 50 mm, particularly preferably between 10 mm and 30 mm, in particular approximately 25 mm.
[0048] It is preferable for the treatment devices to be evacuated at least from time to time during the treatment of the workpieces, by means of vacuum pumps, the evacuation being carried out in a plurality of stages and at least one of the vacuum pumps being arranged on the rotor. In this case, in particular, in at least one evacuation passage there is a vacuum pump upstream and a vacuum pump downstream of the fluid rotary leadthrough.
[0049] The fluid rotary leadthrough may advantageously therefore be designed for a vacuum range>1 mbar and may be designed with relatively small line cross sections. Therefore, the demands imposed with regard to the leakage rates in the pressure range>1 mbar are advantageous relatively low. The fluid rotary leadthrough therefore makes do with a leak rate of <10 −2 mbar*l/sec. It can therefore be produced at low cost.
[0050] Furthermore, the smaller cross sections mean that the fluid rotary leadthrough can also be produced with a plurality of fluid passages, i.e. 2, 3, 4, 5, 6 or more, in an economic and compact design.
[0051] The text which follows provides a more detailed explanation of the invention on the basis of exemplary embodiments and with reference to the drawings, in which identical and similar components are provided with the same reference numerals and the features of the various exemplary embodiments can be combined with one another.
BRIEF DESCRIPTION OF THE FIGURES
[0052] In the drawings:
[0053] FIG. 1 shows a diagrammatic side view of a treatment apparatus,
[0054] FIG. 2 shows a longitudinal section through a fluid rotary leadthrough in accordance with a first embodiment of the invention,
[0055] FIG. 3 shows a longitudinal section through a fluid rotary leadthrough in accordance with a second embodiment of the invention,
[0056] FIG. 4 shows a cross section on section line A-A in FIG. 3 ,
[0057] FIG. 5 shows a cross section on section line B-B in FIG. 3 , and
[0058] FIG. 6 shows a block diagram illustration of a vacuum pump arrangement.
DETAILED DESCRIPTION OF THE INVENTION
[0059] FIG. 1 shows an apparatus 1 for the plasma coating of hollow plastic bodies which are coated in a plurality of treatment devices 101 by means of the PICVD process.
[0060] The apparatus 1 comprises a plasma wheel or a rotor 32 , on which the treatment devices 101 or plasma stations are secured. The rotor 32 , in operation, rotates with respect to a stationary base 30 . In the center of the apparatus 1 there is a fluid rotary leadthrough or gas rotary leadthrough 82 , via which an operating medium or process gas is fed to the rotating treatment devices 101 and the treatment devices 101 can be evacuated by means of pumps arranged on the rotor and in a stationary position.
[0061] FIG. 2 shows a first embodiment of the fluid rotary leadthrough or rotary leadthrough 82 .
[0062] The rotary leadthrough 82 comprises a journal or shaft pin 2 connected to the base 30 in a manner fixed in terms of rotation and a sleeve or annular sleeve 4 connected to the rotor 32 in a manner fixed in terms of rotation. The annular sleeve 4 is mounted rotatably on the journal 2 by means of rotary bearings 6 .
[0063] The sleeve 4 has four annular passages 41 , 42 , 43 , 44 , which are arranged axially offset with respect to one another. The distance 45 between the annular passages is in the mm range. A plurality of connection bores are connected to each annular passage, with in each case one connection bore being assigned to one treatment device 101 . FIG. 2 shows in each case two opposite connection bores 511 , 512 , 521 , 522 , 531 , 532 , 541 , 542 per annular passage.
[0064] The journal 2 has two fluid or evacuation passages, 21 , 22 with an internal diameter D of 102 mm. The evacuation passages 21 , 22 are continuously connected to the annular passages 41 and 42 , respectively, since the latter are designed to run all the way around. Consequently, the rotary supply produces a continuous connection over the entire rotary angle of 360°.
[0065] Two further evacuation passages for connection to the annual passages 43 and 44 are likewise present in the journal 2 but cannot be seen in the sectional illustration presented in FIG. 2 , since in the position of the rotary leadthrough 82 which is shown these passages are positioned perpendicular to the plane of the drawing.
[0066] The evacuation passages 21 , 22 each have an axial passage section 23 or 24 , respectively, and a radial passage section 25 or 26 , respectively, connected thereto, these radial passage sections opening out in the lateral surface 28 of the journal 2 and in the associated annular passage 41 or 42 , respectively.
[0067] There is a ring seal 30 on both sides of the annular passages.
[0068] Reference will now be made to FIG. 3 , which illustrates a further embodiment of the rotary leadthrough 182 . The journal 102 has six fluid passages, of which two differently dimensioned fluid passages 121 , 122 are illustrated. Each fluid passage is assigned one of six annular passages 141 to 146 .
[0069] The treatment devices are evacuated via the fluid passage 121 , and process gas is fed to the treatment devices via the fluid passage 122 . The fluid passages are substantially U-shaped in form and each comprises an axial section which extends along the axis of rotation 7 .
[0070] The treatment devices are connected via tubes, if appropriate with the addition of a vacuum pump, to a connection flange 134 . Stationary pumps are connected to a lower connection flange 136 on the other side of the passage 121 . Accordingly, on the gas supply side, a gas supply device is connected to the treatment devices via a connection flange 138 , the gas supply passage 122 and a connection flange 140 .
[0071] All the seals 30 are continuously lubricated with vacuum oil via sealant lines. For the sake of clarity, just one sealant line 31 at the top seal is illustrated.
[0072] Referring now to FIG. 4 , the rotary leadthrough 182 has three evacuation passages 121 , 123 and 125 . The evacuation passages are distributed around the axis at angular intervals of approximately 120°. Between the evacuation passages there are three gas supply passages 122 , 124 and 126 .
[0073] Referring now to FIG. 5 , the encircling annular passage 141 is illustrated. If the sleeve 104 rotates about the journal 102 , there is a permanent fluid connection between the evacuation passage 121 and the connection flange 134 via the annular passage 141 .
[0074] Referring now to FIG. 6 , a coating cycle is carried out as follows. During a first pumping phase, the treatment device is evacuated to a preliminary vacuum of between approximately 100 mbar and 1 mbar by means of a first pump arrangement comprising two rotary slide preliminary vacuum pumps 202 , 204 connected in parallel. The feed lines are routed onto the rotor 32 via the evacuation passage 121 in the rotary leadthrough 182 . The rotary slide pumps 202 and 204 have a pump power of in each case 1200 standard m 3 /h.
[0075] At the required machine power, the time needed to deliver the next vessel is very short. Therefore, a second evacuation phase is provided, in order for the evacuation to be carried out in stages. During the second evacuation phase, the treatment devices are evacuated via a serial second pump arrangement, comprising a first Roots pump 206 , a second Roots pump 208 and a rotary slide pump 210 .
[0076] The Roots pump 206 has a pump power of 4000 standard m 3 /h, the second Roots pump 208 has a pump power of 1000 standard m 3 /h, and the rotary slide pump has a pump power of 100 standard m 3 /h. During the second evacuation phase, the treatment devices are evacuated from the preliminary vacuum to a base pressure of approximately 0.05 to 0.8 mbar, which represents the pressure prior to the start of coating.
[0077] Then, during a first coating phase, the workpieces are provided with a first coating while a first process gas, which is supplied via the passage 124 , is passing through.
[0078] The first coating phase is followed by a second coating phase, in which the workpieces are coated with a barrier layer while a second process gas is passing through via the passage 126 .
[0079] During the first and second coating phases, the treatment devices are connected to a serial third pump arrangement, comprising a first Roots pump 212 , a second Roots pump 214 and two parallel-connected rotary slide preliminary pumps 216 and 218 .
[0080] The Roots pump 212 has a pump power of 5550 standard m 3 /h, the Roots pump 214 has a pump power of 2000 standard m 3 /h, and the rotary slide preliminary pumps 216 and 218 each have a pump power of 100 standard m 3 /h.
[0081] It is advantageous for separate pump arrangements to be used for the evacuation and coating phases. This is advantageous on account of the fact that dust produces deposits in the lines and pumps during the coating process. In the exemplary embodiment, these deposits are restricted to the pumps 212 , 214 , 216 and 218 , and contamination in the pump arrangements for the evacuation phases is avoided. Consequently, dust from the coating phases is also prevented from penetrating as far as the seals 30 of the evacuation passages 121 and 123 . The wear on the seals there is reduced accordingly, thereby avoiding leaks.
[0082] The pumps 202 , 204 , 208 , 210 , 214 , 216 and 218 are arranged in a stationary position outside the rotor, whereas the pumps 206 and 212 are arranged at the rotor and rotate therewith. Therefore, for at least one process phase (evacuation phase or coating phase), the fluid rotary leadthrough is arranged between at least two vacuum pumps connected in series.
[0083] This has the resultant advantage that the rotary leadthrough 182 only operates in a pressure range of >1 mbar, since the two Roots pumps 206 and 212 on the rotor are already responsible for preliminary compression. Consequently, sealing of the rotary leadthrough is greatly simplified. A leak rate of approximately <10 −2 mbar*l/sec is sufficient for the apparatus to operate without problems. Furthermore, line cross sections of approximately 100 mm are sufficient.
[0084] After the intended base pressure has been reached, the coating process is carried out. At least during the second coating phase, a plurality of treatment devices are simultaneously connected to the pump arrangement 212 , 214 , 216 , 218 .
[0085] After coating, the treatment devices are vented to ambient pressure, opened and the workpiece is conveyed out of the apparatus.
[0086] For details as to the control of the process phases, reference is made to the application entitled “Vorrichtung und Verfahren zur Behandlung von Werkstücken” [Apparatus and process for treating workpieces] in the name of the same Applicant, applied for on the same day.
[0087] The pressure, or more specifically the subatmospheric pressure, in the vacuum lines 222 , 224 and 226 is in each case set by means of a separate pressure regulator 223 , 225 , 227 and is distributed to the treatment devices via in each case one annular distributor 232 , 234 and 236 , respectively. The temporal control is effected by means of two valve arrangements or valve blocks comprising valves 240 , each treatment device being assigned a valve for each pump arrangement. This allows variable programming of the process control, matched to the coating requirements.
[0088] The supply of gas to the treatment devices is of similar construction. The process gas for the first and second coating phases is provided by a first and second fluid source 242 and 244 , respectively. The process gas is delivered to the rotor via the passages 122 and 124 in the rotary leadthrough 182 , and it is then available at the rotor continuously for further distribution and control. A purge gas from a source 246 is conveyed onto the rotor via the remaining passage 126 in order to purge the treatment devices.
[0089] Downstream of the rotary leadthrough 182 , the process gases and the purge gas are distributed to the treatment devices by means of distributors 252 , 254 and 256 . The temporal control is effected by means of valves 260 which are arranged between the treatment devices and the distributors 252 , 254 and 56 .
[0090] It will be clear to the person skilled in the art that the embodiments described above are to be understood purely as examples, and that the invention is not restricted to these examples, but rather can be varied in numerous ways without departing from the scope and spirit of the invention.
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The invention relates to a fluid rotary leadthrough having a journal and a sleeve. The sleeve and the journal are sealed off with respect to one another. The journal and the sleeve each have a line connection. The line connections, at least from time to time, are connected to one another via a fluid passage so that a flow of fluid through the fluid rotary leadthrough is made possible. The journal is arranged rotatably in the sleeve.
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BACKGROUND OF THE INVENTION
The present invention relates to a closure cover for an opening providing access to sewing machine mechanisms, more particularly, to the thread control elements for the lower hook; these elements being housed, for example, in sewing machines having a cylindrical base or a U-shaped base.
In conventional sewing machines of this type the covers which have hitherto been employed have been shaped so as to conform at least partially to the shape of the base to which the covers are hinged.
These covers are, for the large part, pivotable towards the sewing machine operator.
Owning to the fact that the covers conform to the shape of the base, they are not provided with means for facilitating opening of the same so as not to obstruct the free sliding of the workpiece during the stitching operation.
Consequently, the covers used on conventional machines have the disadvantage of being bulky and difficult to grip in order to open the same.
The object of the present invention is to obviate these disadvantages and to facilitate rapid opening of the cover so as to render the thread control elements readily accessible.
SUMMARY OF THE INVENTION
To attain this object it was necessary to provide an opening means which does not require integral gripping devices that would be capable of obstructing the sliding of the workpiece on the sewing machine during the stitching operation.
The solution provided by the present invention consists in a closure cover of the aforementioned type which is characterized in that it comprises flexible retaining means adapted to keep the cover in a closed position, combined with lifting means that is adapted to move the cover into an open position.
In addition, the cover is pivotable about a vertical pin such that in the closed position the cover is level and forms a continuation of the sliding surface for the workpiece on the base of the sewing machine and in the open position it may be rotated rearwardly with respect to the base.
The advantage provided by the present invention is that of being able to open the cover in response to the mere pressure of the flexible cover retaining means. The cover is then raised from the seat on which it is held and it is connected to a part that is effective in rotating it to a suitable position in a zone in which it will not obstruct the operator's movements.
Other objects, features and advantages of the present invention will be made apparent in the following description thereof provided with reference to the accompanying drawings by way of example only, in which:
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a sewing machine to which the device according to the invention is applicable;
FIG. 2 is a plan view of a portion of the base of the sewing machine shown in FIG. 1;
FIG. 3 is an elevational view of an enlarged section along line III--III in FIG. 1.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to FIG. 1 a sewing machine of the type having a U-shaped base comprises a casing 1 consisting of a base which generally is made up of three parts, 2, 3 and 4 disposed at right angles to one another so as to form an essentially horizontal "U"-shaped base having a vertical upright 5 mounted on the first of these parts and on which is mounted a projecting arm 6 terminating in a head 7 which is disposed above the free end 8 of the third part 4 of the base.
A conventional presser device consisting of a presser bar 9 and a presser foot 10 as well as the usual upper sewing elements including a needle bar 11 and a needle 12 are mounted in the head 7.
The arm 6 houses the actuating members for the presser device and for the upper sewing elements.
The actuating members for the sewing elements also include a handwheel 13 located on one end of arm 6 (FIG. 1). The second and third parts of the base house the elements for actuating the conventional lower sewing elements, which are those for driving the workpiece advancement device and also lower sewing elements for controlling the lower thread.
More specifically, the above-mentioned thread control elements are contained in the second part.
All the elements and actuating devices -- with the exception of those mentioned above -- have been omitted from the accompanying drawings as they do not contribute to the present invention.
To obtain ready access to the elements contained in the second part 3 -- and represented in FIG. 2 by a shaft 14 of the machine, an opening 15 is provided in the upper surface of part 3. A closure cover 16 is mounted in this opening in such a way that when the cover is closed over this opening, it is flush with all adjacent surfaces of part 3.
This condition is necessary to avoid obstructing the operator's movements when manipulating the workpiece to be sewn.
In addition, to avoid obstructions when performing some function on the elements connected to the shaft 14, by way of the opening 15, the closure cover 16 includes a lifting means 17 for raising it from its seat so that it can be rotated towards the rear part of the second part 3 (FIGS. 2 and 3).
The lifting means 17 includes a rod 18 depending from and having one end fixed in the lower surface of the cover 16. Pin 18 is slidably assembled in a seat 19 formed in the rear wall 20 of the second part 3. The rod 18 includes an axial bore 21 which houses a compression spring 22. This spring being partially compressed causes end 23 to apply an upward biasing force on the cover 16 and a downward force by the end 24 on a threaded plug 25 which assemblies in the lower surface 27 of the second part 3. As shown in FIG. 3, the threaded plug 25 is provided with an integrally formed and upwardly extending pin 26 which serves as a positioning and guide element for the compression spring 22.
The pin 18 is provided on its external surface with a longitudinal channel or groove 28 which terminates in a circumferential channel or groove 29 located adjacent the lower end of said pin.
The grooves are provided to limit the movements of the closure cover 16.
Assembled in the rear wall 20 of the second part 3 is a guide screw 30 having an end portion 31 of which is positioned in either of the grooves 28 or 29 depending on the position of the cover.
More specifically, the longitudinal groove is so disposed on the pin 18 that it is only in engagement with the guide screw when the closure cover is aligned with the opening 15, thus permitting the cover to be raised and lowered.
The circumferential groove 29 is so positioned on the pin that it is only in engagement with the guide screw 30 when the closure cover is fully raised above the surface of the second part 3, thus enabling this cover to be rotated about its pivot point.
The combination of the two longitudinal and circumferential grooves thus controls the action of the compression spring 22 which when permitted to expand raises the cover from its seat until the end portion 31 of the guide screw 30 enters into the groove 29.
To retain the closure cover on the opening 15 against the action of the compression spring 22, a retaining and release means 33 is provided in the forward portion 32 of this part. The retaining means includes a knob 34 disposed opposite a coil spring 35. This knob is provided with a bore 36 that traverses the axis thereof into which a pin 37 extending downwardly from the closure cover 16 is adapted to be inserted.
The knob 34 is assembled in a bore 38 formed at a right angle to the forward portion 32 and is held in its bore by a check screw 39 having an end portion 40 of which is located in a slot 41 provided in the upper surface of the knob.
By virtue of this coupling, the knob is continuously urged outwardly by the biasing force of spring 35 and is maintained within the bore 38 by means of the check screw 39.
When the pin 37 carried by the closure cover 16 is inserted in a bore 42 provided in the part 3 it extends through the bore 38 housing the knob 34 as well as the bore 36 in the knob 34. The pin 37 is provided with a recess 43 which faces towards the pressure spring 35 and, under the thrust of the latter, the knob is engaged therein to retain the cover in the closed position.
If pressure is exerted on the outside of the knob 34, thus moving it inwardly, the pin 37 will obviously be disengaged, thus releasing the cover which is raised by the biasing force of the compression spring 22.
The cover is closed by rotating it manually in the opposite direction and simultaneously exerting slight downward pressure thereon.
As a result, and by virtue of a reciprocal movement, the guide screw 30 is slid into the circumferential groove and, as soon as the longitudinal groove is aligned with the screw, the end 31 of the latter penetrates it, thus enabling the cover to be fully lowered.
The pin 37 simultaneously becomes coupled to the knob 34 as the position of the longitudinal groove 28 with respect to the pin 37 is such that the latter is aligned with the bore 42 when this groove 28 is engaged by the checking screw 30.
Although the present invention has been described in connection with a preferred embodiment, it is to be understood that modifications and variations may be resorted to without departing from the spirit and scope of the invention as those skilled in the art will readily understand. Such modifications and variations are considered to be within the purview and scope of the invention and the appended claims.
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A closure cover for the opening in the base of a sewing machine which provides access to the thread control members for the lower hook. The cover is carried on a rod which is vertically slidable and rotatably carried in the base and includes a combined spring biased locking and release arrangement the first of which maintains the cover in operating position on the base, and the second which releases the cover. Upon release the cover is automatically raised by a spring member and can be pivoted to a position to facilitate access to the members within the opening.
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FIELD OF THE INVENTION
This invention relates to a method of operation of a hydrogen fuel cell powered vehicle. More particularly, this invention is directed to a method of refueling a hydrogen fuel cell powered vehicle.
BACKGROUND OF THE INVENTION
Vehicle fueling stations typically require that vehicles be turned off during refueling to minimize the risks of vehicle damage associated with vehicle operation during the refueling process. Ensuring vehicles are not operated during refueling is primarily accomplished through enforcement by fueling station attendants, or is a voluntary process depending upon the cooperation of the vehicle operator.
As hydrogen fuel cell power plants are increasingly being integrated into vehicles, preventing operators from driving away during refueling is becoming increasingly important in order to prevent damage to both the vehicle and fuel station equipment.
It would be desirable to have a hydrogen refueling system that automatically disables vehicle systems in order to militate against damage to the vehicle when refueling is occurring. It would be further desirable to have a hydrogen vehicle refueling system that resets the vehicle systems after the refueling event is complete. Also, it would further be desirable to have a hydrogen refueling system that determines if a faulty refueling event has been detected and maintains typical vehicle operation.
SUMMARY OF THE INVENTION
According to the present invention, a hydrogen fueling system that automatically disables vehicle systems when refueling is occurring, resets the vehicle systems after the refueling is complete, and determines if a faulty refueling event has been detected has surprisingly been discovered.
In one embodiment, the method of refueling a hydrogen fuel cell powered vehicle, includes the steps of providing a traction drive system, a control system in electrical communication with the traction drive system, and at least one refueling sensor in electrical communication with the control system; determining the vehicle is refueling using the refueling sensors; communicating a vehicle refueling signal from the refueling sensors to the control system; and disabling the traction drive system using the control system when a vehicle refueling signal is received.
In another embodiment, the method of refueling a hydrogen fuel cell powered vehicle, includes the steps of providing a traction drive system, a control system in electrical communication with the traction drive system, at least one fuel inlet sensor in electrical communication with the control system, and at least one fuel tank sensor in electrical communication with the control system; determining vehicle refueling using the fuel inlet sensor; determining vehicle refueling using the fuel tank sensor; communicating a first vehicle refueling signal from the fuel inlet sensor and a second refueling signal from the fuel tank sensor to the control system; disabling the traction drive system using the control system when a vehicle refueling signal is received; and re-enabling the traction drive system using the control system when the refueling is complete.
In another embodiment, the method of refueling a hydrogen fuel cell powered vehicle, includes the steps of providing a traction drive system, a control system in electrical communication with the traction drive system, at least one fuel inlet sensor in electrical communication with the control system, and at least one fuel tank sensor in electrical communication with the control system; determining vehicle refueling using the fuel inlet sensor; determining vehicle refueling using the fuel tank sensor; communicating a first vehicle refueling signal from the fuel inlet sensor and a second refueling signal from the fuel tank sensor to the control system; determining a faulty refueling signal when the first refueling signal and the second refueling signal do not both communicate a refueling signal to the control system within, a predetermined time period; disabling the traction drive system using the control system when the vehicle refueling signal received is not faulty; and re-enabling the traction drive system using the control system when the refueling is complete.
DESCRIPTION OF THE DRAWINGS
The above, as well as other advantages of the present invention, will become readily apparent to those skilled in the art from the following detailed description of a preferred embodiment when considered in the light of the accompanying drawings in which:
FIG. 1 is a schematic illustration of a hydrogen powered vehicle with refueling system components of the present invention;
FIG. 2 shows a fragmentary perspective view of a fuel door in the open position and showing the control systems schematically according to the embodiment of the invention shown in FIG. 1 ; and
FIG. 3 is a flow diagram illustrating a method of operation of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The following detailed description and appended drawings describe and illustrate various exemplary embodiments of the invention. The description and drawings serve to enable one skilled in the art to make and use the invention, and are not intended to limit the scope of the invention in any manner. In respect of the methods disclosed, the steps presented are exemplary in nature, and thus, the order of the steps is not necessary or critical.
In the exemplary embodiment described herein, the hydrogen powered vehicle refueling strategy is provided in a vehicle 2 , as shown in FIG. 1 . The vehicle 2 includes a traction drive system or vehicle system 10 . It is understood that other vehicle systems can be used as desired. A plurality of wheels 4 are mechanically coupled to the traction drive system 10 . The traction drive system 10 is electrically linked to a control system 16 via a connection 12 . The connection 12 may be any conventional means of electrical communication.
A fuel inlet 24 is formed in the vehicle 2 and is in fluid communication with a fuel tank 20 . The fuel inlet 24 includes at least one fuel inlet sensor, such as a fuel door switch 40 , and a fuel nozzle sensor 42 , for example, as clearly shown in FIG. 2 . The fuel inlet sensor is in electrical communication with the control system 16 via an electrical connection 14 . The fuel tank 20 includes at least one fuel tank sensor, such as a temperature sensor 26 , and a pressure sensor 27 . The fuel tank sensor is in electrical communication with the control system 16 via an electrical connection 18 . Additionally, the vehicle 2 may include other sensors without departing from the scope of this invention.
Referring now to FIG. 2 , a fuel inlet door 34 is pivotally connected to the fuel inlet 24 via a hinge 32 . An aperture 30 is formed in the fuel inlet 24 . The aperture 30 is adapted to receive a hydrogen fuel pump nozzle (not shown). The fuel door switch 40 is disposed adjacent the fuel inlet 24 to sense when the fuel door 34 is in an open or closed position. The fuel inlet sensor 42 is disposed near the aperture 30 to sense when a hydrogen fuel pump nozzle is inserted in the aperture 30 . The fuel door switch 40 and the fuel nozzle sensor 42 generate and transmit a refueling signal to the control system 16 via the connection 14 . Other sensors may be used without departing from the scope of this invention.
In operation, the traction drive system 10 controls whether power generated by a fuel cell is sent to the vehicles wheels 4 and/or whether the traction drive system converts the available power to mechanical work. The control system 16 selectively controls the traction drive system 10 via the communication 12 .
The control system 16 disables the traction drive system 10 when vehicle refueling occurs (Y at 52 ), shown in FIG. 3 . Disabling the traction drive system 10 prevents a user from driving away while the vehicle 2 is being refueled. The control system 16 enables the traction drive system 10 when refueling is not occurring (N at 52 ). Additionally, it may be desirable for the control system 16 to disable other vehicle 2 systems, such as the fuel cell power system (not shown), when refueling is detected.
In the embodiment shown and described herein, refueling is communicated to the control system 16 in several methods. A first refueling signal is communicated to the control system 16 from the at least one fuel inlet sensor via the connection 14 . It may be desirable to communicate the first refueling signal from the fuel nozzle sensor 42 . When a hydrogen fuel pump nozzle is detected in the aperture 30 the fuel nozzle sensor 42 generates and transmits a signal that refueling is occurring (Y at 52 ) to the control system 16 . Alternatively, it may be desirable to communicate the first refueling signal from the fuel door switch 40 . When the fuel door 34 is an open position the fuel door switch 40 generates and transmits a signal that refueling is occurring (Y at 52 ) to the control system 16 . It may desirable for the fuel door switch 40 , and the fuel inlet sensor 42 to be contact sensors such as micro-switches, or non-contact sensors such as proximity sensors. Additionally, other types of sensors or combinations of sensors may be used without departing from the scope of this invention.
A second refueling signal is sent to the control system 16 from the at least one fuel tank sensor via the connection 18 . It may be desirable to send the second refueling signal from the temperature sensor 26 . When a sudden drop in fuel tank 20 temperature is detected the temperature sensor 26 generates and transmits a signal to the control system 16 . It may be further desirable to communicate the second refueling signal from the pressure sensor 27 . When rapidly rising fuel tank 20 pressure is detected, the pressure sensor 27 generates and transmits a signal to the control system 16 . Additionally, other types of sensors may be used without departing from the scope of this invention.
Additionally, it may be desirable to use both the first refueling signal and the second refueling signal together in order to determine whether a faulty refueling signal has been communicated to the control system 16 . For example, if the control system 16 receives the first refueling signal from the fuel door switch 40 , and does not receive a second refueling signal from the pressure sensor 27 within a predetermined time period, the control system 16 could determine that the fuel door switch 40 sent a faulty signal and the system may be re-enabled because refueling is not taking place.
When the control system 16 determines that refueling is complete or not occurring (N at 52 ) the traction drive system 10 is re-enabled. It may be desirable to implement a time delay before re-enabling the traction drive system 10 in order to ensure that the refueling process is complete.
From the foregoing description, one ordinarily skilled in the a can easily ascertain the essential characteristics of this invention and, without departing from the spirit and scope thereof, make various changes and modifications to the invention to adapt it to various usages and conditions.
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A method for refueling hydrogen fuel cell powered vehicles is disclosed, that is capable of automatically disabling the vehicle systems, resetting the vehicle systems to allow for normal vehicle operation after the refueling event is complete, and determining if a faulty refueling event has been detected and allows normal vehicle operation.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The invention disclosed herein relates to the field of gas turbines. In particular, the invention is used to provide control of turbine blade tip clearance.
[0003] 2. Description of the Related Art
[0004] A gas turbine includes many parts, each of which may expand or contract as operational conditions change. A turbine interacts with hot gases emitted from a combustion chamber to turn a shaft. The shaft is generally coupled to a compressor and, in some embodiments, a device for receiving energy such as an electric generator. The turbine is generally adjacent to the combustion chamber. The turbine uses blades, sometimes referred to as “buckets,” for using energy of the hot gases to turn the shaft.
[0005] The turbine blades rotate within a shroud ring. As the hot gases impinge on the turbine blades, the shaft is turned. The shroud ring is used to prevent the hot gases from escaping around the turbine blades and, therefore, not turning the shaft.
[0006] The distance between the end of one turbine blade and the shroud ring is referred to as “clearance.” As the clearance increases, efficiency of the turbine decreases as hot gases escape through the clearance. Therefore, an amount of clearance can affect the overall efficiency of the gas turbine.
[0007] If the amount of clearance is too small, then thermal properties of the turbine blades, the shroud ring, and other components can cause the turbine blades to rub the shroud ring. When the turbine blades rub the shroud ring, damage to the turbine blades, the shroud ring and the turbine may occur. It is important, therefore, to maintain a minimal clearance during a variety of operational conditions.
[0008] Therefore, what are needed are techniques to reduce clearance between turbine blades and a shroud ring in a gas turbine. The techniques should be useful for a variety of operational conditions.
BRIEF DESCRIPTION OF THE INVENTION
[0009] Disclosed is one embodiment of an inner shell for a rotating machine including at least one segment; and at least one complementary segment in operable communication with the at least one segment, the segments forming a support structure for a shroud ring; wherein the at least one segment and the at least one complementary segment are individually moved to change a set of dimensions defined by the at least one segment and the at least one complementary segment.
[0010] Also disclosed is one embodiment of a rotating machine including a housing; a rotating component disposed at the housing; a shroud ring disposed adjacent to the rotating component; a shell comprising segments, at least one segment in operable communication with the shroud ring, wherein at least one dimension of the shroud ring is adjustable by the shell.
[0011] Further disclosed is one example of a method for controlling a dimension of a shroud ring in a rotating machine, the method including receiving information from a control system; moving one or more segments of a segmented shell using the information, the shell in operable communication with the shroud ring; and deforming the shroud ring with the one or more segments.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] The subject matter which is regarded as the invention is particularly pointed out and distinctly claimed in the claims at the conclusion of the specification. The foregoing and other features and advantages of the invention are apparent from the following detailed description taken in conjunction with the accompanying drawings, wherein like elements are numbered alike, in which:
[0013] FIG. 1 illustrates an exemplary embodiment of a gas turbine;
[0014] FIGS. 2A and 2B , collectively referred to FIG. 2 , illustrate an exemplary embodiment of a turbine stage and an inner turbine shell;
[0015] FIGS. 3A , 3 B, and 3 C, collectively referred to as FIG. 3 illustrate an exemplary embodiment of a slot between adjacent segments and an inter-segment seal;
[0016] FIGS. 4A and 4B , collectively referred to as FIG. 4 , illustrate an exemplary embodiment of a segment of the inner turbine shell;
[0017] FIG. 5 illustrates an exemplary embodiment of the inner turbine shell with actuators coupled to a plurality segments;
[0018] FIG. 6 illustrates an exemplary embodiment of the inner turbine shell with a sleeve;
[0019] FIG. 7 illustrates an exemplary embodiment of the segment with a nozzle;
[0020] FIG. 8 presents an exemplary method for controlling a dimension of the shroud ring.
DETAILED DESCRIPTION OF THE INVENTION
[0021] Various embodiments of apparatus and methods for controlling a clearance between a plurality of blades and a shroud ring in a rotating machine are disclosed herein. While the illustrated embodiments are devoted to controlling the clearance between a plurality of turbine blades and the shroud ring in a gas turbine, it is to be appreciated that the general teachings herein are applicable to other types of machines such as compressors and pumps.
[0022] Specifically taught herein are apparatus and methods for controlling a dimension of the shroud ring, such as the diameter, to maintain a desired amount of clearance between the shroud ring and a set of turbine blades. In one embodiment, the desired amount of clearance is a minimum amount of clearance that avoids rubbing of the blades against the shroud ring.
[0023] For convenience, certain definitions are provided. The term “rotating machine” relates to machinery that includes blades disposed circumferentially about a shaft. The shaft and blades rotate together to at least one of compress a gas, pump a fluid, convert a fluid flow to rotational work, and convert a gas flow to rotational work. The term “gas turbine” relates to a rotating machine that is a continuous combustion engine. The gas turbine generally includes a compressor, a combustion chamber and a turbine. The combustion chamber emits hot gases that are directed to the turbine. The term “turbine blade” relates to a blade included in the turbine. Each turbine blade generally has an airfoil shape for converting the hot gases impinging on the bucket into rotational work. The term “turbine stage” relates to a plurality of turbine blades disposed circumferentially about a section of a turbine shaft. The turbine blades of the turbine stage are arranged in a circular pattern about the shaft. The term “shroud ring” relates to a structure for preventing the hot gases from escaping, unimpeded, around the turbine blades of the turbine stage. The structure is disposed radially outward from the turbine stage and may be at least one of cylindrical and conical. In general, there is one shroud ring for each turbine stage. The term “clearance” relates to an amount of distance between a tip of the turbine blade and the shroud ring. The term “inner turbine shell” relates to a structure coupled to the shroud ring. The inner turbine shell surrounds the shroud ring and holds the shroud ring in place. The inner turbine shell may be coupled to several shroud rings as well as nozzles between turbine stages. The term “casing” (or “housing”) relates to a structure surrounding the inner turbine shell. The casing provides structural integrity for the entire rotating machine. The casing also provides a pressure boundary between the external pressure and the internal pressure of the gas turbine. The term “circularity” relates to a degree to which a structure is round. For example, a structure with a high degree of circularity has more roundness than a structure with low circularity. The term “perimetrically” relates to a perimeter.
[0024] FIG. 1 schematically illustrates an exemplary embodiment of a gas turbine 1 . The gas turbine 1 includes a compressor 2 , a combustion chamber 3 , and a turbine 4 . The compressor 2 is coupled to the turbine 4 by a turbine shaft 5 . In the non-limiting embodiment of FIG. 1 , the turbine shaft 5 is also coupled to an electric generator 6 . (In other embodiments, the turbine shaft 5 may be coupled to other types of machinery such as a compressor or pump.) The turbine 4 includes turbine stages 7 , respective shroud rings 8 , an inner turbine shell 10 and a casing 9 . The inner turbine shell 10 surrounds the shroud rings 8 . In general, the inner turbine shell 10 has a tapered or conical shape to conform to the sizes of the turbine stages 7 . Also depicted in FIG. 1 is a longitudinal axis 11 in line with the shaft 5 and a radial direction 12 representative of radial directions normal to the shaft 5 . The turbine 4 is described in more detail next.
[0025] FIG. 2 illustrates an exemplary embodiment of the turbine 4 . FIG. 2A illustrates an end view of the turbine 4 . Referring to FIG. 2A , a clearance 20 is shown. The shroud ring 8 shown in FIG. 2A encloses a plurality of turbine blades 27 by about 360 degrees. In some embodiments, the shroud ring 8 is built from a plurality of shroud ring segments that include a plurality of arc segments, each arc segment less than 360 degrees. The shroud ring 8 may be made from a material that allows the shroud ring 8 to expand and contract. The arc segments of the shroud ring 8 are affixed to the inner turbine shell 10 such that, as the inner turbine shell 10 expands and contracts, the shroud ring 8 will also expand and contract. The “free” end of the inner turbine shell 10 (affixed to the shroud ring 8 ) contracts radially in accordance with an amount of force imposed radially upon the free end. By controlling the diameter of the inner turbine shell 10 and, thus, the shroud ring 8 , the clearance 20 can be minimized without an increase in a risk of rubbing.
[0026] FIG. 2B illustrates a side view of the turbine 4 . Referring to FIG. 2B , the inner turbine shell 10 includes an assembly of sections 21 . The sections 21 are held together by a hoop 22 . The inner turbine shell 10 also includes a plurality of segments 24 . Each segment 24 can move substantially in the radial direction 12 . By moving in the radial direction 12 , each segment 24 can expand or contract the shroud ring 8 . A force imposed on one segment in the radial direction 12 will cause part the shroud ring 8 to expand or contract substantially in the radial direction 12 . A radial force imposed on all the segments in unison (or collectively) will cause the shroud ring 8 to expand or contract and maintain a degree of roundness. In general, as the number of segments 24 increase, the degree of roundness imposed upon the shroud ring 8 also increases. Each segment 24 is separated from an adjacent segment 24 by a slot 23 . The slot 23 affords free displacement between adjacent segments 24 without contact. A hole 25 is provided at one end of the slot 23 to limit stress to the inner turbine shell 10 imposed by moving the segments 24 at least one of radially inward and radially outward, either individually or in unison.
[0027] Referring to FIG. 2A , an inter-segment seal referred to as a “slot seal 26 ” is provided to seal the opening caused by each slot 23 in the inner turbine shell 10 . The slot seal 26 is disposed between two adjacent segments 24 . FIG. 3A illustrates a three dimensional view of the slot 23 and the hole 25 . FIGS. 3B and 3C illustrate a detailed view of an exemplary embodiment of the slot seal 26 that seals the slot 23 depicted in FIG. 3A . The slot seal 26 includes a strip seal 30 welded to an inner pressure seal 31 and an outer pressure seal 32 . In general, the inner pressure seal 31 and the outer pressure seal 32 has folds to provide sealing. Because of the folds, an increase in pressure to the seals 31 and 32 results in an increase of sealing effectiveness. The inner pressure seal 31 seals against hot turbine gases 33 in the turbine 4 . The outer pressure seal 32 seals against any leakage 34 by the inner pressure seal 31 . The slot seal 26 is inserted into a sealing slot 29 in each of the adjacent segments 24 shown in FIG. 2A and FIG. 3A . In the embodiments of FIGS. 2A and 3A , the sealing slot 29 is generally perpendicular to each slot 23 . However, the sealing slot 29 may be of any angle and shape necessary to optimize sealing.
[0028] FIG. 4 depicts another exemplary embodiment of one segment 24 . In the embodiment of FIG. 4 , each segment 24 is also one section 21 . Assembling the sections 21 into a circular pattern provides the inner turbine shell 10 . Referring to FIG. 4A , each segment 24 has a generally curved shape about the longitudinal axis 11 . The segment 24 shown in FIG. 4 has two flat surfaces to form a flat beam 41 . The flat beam 41 provides for bending of a portion of the segment 24 . The portion that moves is coupled to the shroud rings 8 associated with two turbine stages 7 (depicted at 42 and 43 in FIG. 4B ). As depicted in FIG. 4 , the flat beam 41 has a reduced thickness to increase flexibility of the free end of the segment 24 affixed to the shroud ring 8 .
[0029] The teachings provide that the segments 24 move in one of unison and individually. In general, when the segments 24 move individually, each segment 24 is coupled to an actuator. FIG. 5 illustrates an exemplary embodiment of the inner turbine shell 10 in which each segment 24 is coupled to an actuator 50 . The actuator 50 may be one of an electrical actuator such as a solenoid, an electro-mechanical actuator such as an electrically operated screw, and a mechanical actuator such as a hydraulic piston. The mechanical actuator may be any actuator not including electrical actuation. In one embodiment, the actuator 50 may operate using pressure applied to a piston. In another embodiment, the actuator 50 may operate thermally using the temperature of a gas to cause movement of the actuator 50 as is known to those skilled in the art of actuators. In another embodiment, the actuator 50 may operate chemically. The actuator 50 may move in at least one of along the longitudinal axis 11 and the radial direction 12 . When the actuator 50 moves along the longitudinal axis 11 , a mechanical device is used to convert motion to the radial direction 12 . When the actuator 50 moves along the radial direction 12 , no conversion of motion is required. The actuator 50 may be one of a single acting actuator and a double acting actuator. A single-acting actuator 50 provides force in one direction. The single acting actuator 50 relies on a counteracting force provided by the turbine gases 33 or stiffness of the segments 24 to move in the other direction. A double acting actuator 50 provides force in two directions.
[0030] Moving the segments 24 in unison is used to maintain roundness of the shroud ring 8 . When the segments 24 move in unison, at least one actuator 50 is used to move a device that moves the segments 24 in unison. In one embodiment the device is a ring or sleeve surrounding the segments 24 of the inner turbine shell 10 . FIG. 6 illustrates a sleeve 60 surrounding the segments 24 . By moving the sleeve 60 along one direction of the longitudinal axis 11 , the conical shape of the inner turbine shell 10 will force the segments 24 to move in unison and contract the shroud ring 8 . By moving the sleeve 60 in the opposite direction, pressure from the turbine gases 33 or stiffness of each segment 24 will cause the segments 24 to move in unison to expand the shroud ring 8 . In one embodiment, the sleeve 60 may make contact directly with the segments 24 . In another embodiment, the sleeve 60 may use at least one of rollers, cams, linear bearings, and mechanical linkages to make contact with the segments 24 . In another embodiment, the sleeve 60 may engage circumferential threads of the inner turbine shell 10 . In this embodiment, as the sleeve 60 is rotated, the sleeve moves along the longitudinal axis 11 to one of expand and contract the shroud ring 8 . Moreover, longitudinal actuation may also be double acting wherein motion of the ring or the sleeve 60 in either direction forces the shroud ring 8 to expand or contract accordingly.
[0031] The segments 24 may also be moved in unison by applying the same pressure of a gas to an outside surface of all the segments 24 . When gas pressure is used to move the segments 24 , the pressure of the turbine gases 33 or stiffness of each segment 24 is used to move the segments 24 in a direction opposing the gas pressure. Movement of the segments 24 can also be accomplished by using the pressure differential between the exterior and the interior of the inner turbine shell 10 . When the exterior pressure of the inner turbine shell 10 is greater than the interior pressure, the net effect is to move the segments 24 radially inward. Conversely, when the exterior pressure of the inner turbine shell 10 is less than the interior pressure, the net effect is to move the segments 24 radially outward.
[0032] Another embodiment of the inner turbine shell 10 uses passive actuation to move the segments 24 . With passive actuation, a relative pressure drop across components internal to the inner turbine shell 10 provides a force for moving the segments 24 . One example of a component causing a pressure drop is a nozzle 70 illustrated in FIG. 7 . Referring to FIG. 7 , the nozzle 70 is attached to the inner turbine shell 10 . The nozzle 70 is disposed between two turbine stages 7 . The nozzle 70 redirects gas flow from one turbine stage 7 before the gas flow impinges the next turbine stage 7 . There is a pressure drop across the nozzle 70 proportional to the mass flow rate of the gas turbine 1 . During operation of the gas turbine 1 , the mass flow rate varies with the speed and output of the gas turbine 1 . The maximum pressure drop occurs at full speed and full load. In this embodiment, the maximum pressure drop across the nozzle 70 imparts a maximum bending moment 71 on each segment 24 as shown in FIG. 7 . The maximum bending moment 71 will cause the segment 24 to move or bend inwardly reducing the diameter of the shroud ring 8 . The stiffness of each segment 24 and a reduction of the pressure drop are used move the segments 24 outwardly increasing the diameter of the shroud ring 8 . The actuator 50 may not be required with passive actuation. In other embodiments, a combination of passive and active actuation may be used.
[0033] A control system known to those skilled in the art of controls may be used to actuate the actuator 50 . The control system may receive information related to the clearance 20 to control the actuator 50 . The information may be provided by a sensor and used in a feedback control loop (referred to herein as “sensor based feedback control”). The sensor may measure at least one of the clearance 20 and parameters related to the clearance 20 . The feedback control loop will control the variable measured by the sensor to maintain a setpoint. Alternatively, the information may be derived from a model of the gas turbine 1 (referred to herein as “model based control”). Generally a detailed analysis and testing are used to provide the information related to determining an amount of the clearance 20 required for different modes of operation. With model based control, sensors are not used to measure the clearance 20 as part of a feedback control loop.
[0034] FIG. 8 presents an exemplary method 80 for controlling a dimension of the shroud ring 8 . The clearance 20 may be controlled by controlling the dimension, such as a diameter, of the shroud ring 8 . The method 80 calls for receiving 81 information from a control system. Further, the method 80 calls for moving 82 one or more of the segments 24 of the inner turbine shell 10 using the information. Further, the method 80 calls for deforming 83 the shroud ring 8 with the one or more of the segments 24 .
[0035] The method 80 may be implemented by a computer program product included in the control system. The computer program product is generally stored on machine-readable media and includes machine executable instructions for controlling a dimension of the shroud ring 8 in the gas turbine 1 . The technical effect of the computer program product is to increase the efficiency of and prevent damage to the gas turbine 1 by controlling the clearance 20 .
[0036] The use of an assembly of the sections 21 provides advantages in maintenance of the gas turbine 1 . Service and maintenance of the gas turbine 1 may include disassembling the hoop 22 and rotating the inner turbine shell 10 about the longitudinal axis 11 to gain access to any section 21 . When the top half of the casing 9 is removed, a selected section 21 may be removed and replaced individually without removing the shaft 5 . Further, service and maintenance may include removing and replacing the entire inner turbine shell 10 without removing the shaft 5 by removing and replacing the sections 21 individually. Along with removing the inner turbine shell 10 , nozzles, such as the nozzle 70 , and the shroud ring 8 may also be removed. By not removing the shaft 5 , realigning the shaft 5 and associated bearings and bearing housings can be eliminated.
[0037] Gas turbines 1 are often built to be disassembled using a bolted flange at the horizontal midplane. The inclusion of the flange along with circular discontinuity associated with the flange may cause the casing 9 to become out-of-round during engine operation due to thermal gradients. In terms of Fourier coefficients, the casing 9 with two halves is termed to have N=2 out-of-roundness. By dividing the inner turbine shell 10 into the sections 21 and assembling the sections 21 by at least one hoop 22 , circularity is improved over the use of flanges. For the same thermal gradient, the out-of-roundness of the inner turbine shell 10 is decreased as the number of sections 21 used to build the inner turbine shell 10 is increased. For example, the inner turbine shell 10 with four sections 21 (N=4) has less out-of-roundness then the inner turbine shell 10 with two sections 21 (N=2). Numerous sections 21 held together with at least one hoop 22 provides a way of reducing out-of-roundness of the inner turbine shell 10 .
[0038] Various components may be included and called upon for providing for aspects of the teachings herein. For example, the control system may include at least one of an analog system and a digital system. The digital system may include at least one of a processor, memory, storage, input/output interface, input/output devices, and a communication interface. In general, the computer program product stored on machine-readable media can be input to the digital system. The computer program product includes instructions that can be executed by the processor for controlling the clearance 20 . The various components may be included in support of the various aspects discussed herein or in support of other functions beyond this disclosure.
[0039] It will be recognized that the various components or technologies may provide certain necessary or beneficial functionality or features. Accordingly, these functions and features as may be needed in support of the appended claims and variations thereof, are recognized as being inherently included as a part of the teachings herein and a part of the invention disclosed.
[0040] While the invention has been described with reference to exemplary embodiments, it will be understood that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications will be appreciated to adapt a particular instrument, situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.
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An inner shell for a rotating machine including at least one segment; and at least one complementary segment in operable communication with the at least one segment, the segments forming a support structure for a shroud ring; wherein the at least one segment and the at least one complementary segment are individually moved to change a set of dimensions defined by the at least one segment and the at least one complementary segment. A method for controlling a dimension of the shroud ring in a rotating machine is also disclosed.
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CROSS-REFERENCE TO RELATED APPLICATION
This application claims the priority, under 35 U.S.C. §119, of German Patent Application DE 10 2009 015 080.3, filed Mar. 31, 2009; the prior application is herewith incorporated by reference in its entirety.
BACKGROUND OF THE INVENTION
Field of the Invention
The invention relates to an apparatus for transferring different media into a rotatably mounted component of a machine. Apparatuses of that type are known as rotary leadthroughs and are used to provide a connection for introduction of the media to a stator and through a rotor into the rotatably mounted component. The invention also relates to a printing press having the apparatus.
Transfer apparatuses which are configured as so-called rotary transfer apparatuses are known from the prior art. There is, for example, European Patent EP 0 435 164 B1, corresponding to U.S. Pat. No. 5,110,159, in which a rotary transfer apparatus for introducing compressed air into a rotating part of a printing press is described. The apparatus is configured in such a way that a cylinder journal of the rotating part is extended and configured at the same time as a rotor. Channels are guided out of the interior of the rotatable part to the outside into the rotor. The channels are formed by radially and axially parallel bores and then end in a chamber. In embodiments having a multiplicity of channels, the chambers are separated from one another by correspondingly sealed anti-friction bearings. A supply of compressed air is provided from outside into the chambers.
Furthermore, German Published, Non-Prosecuted Patent Application DE 10 2007 060 792 A1, corresponding to U.S. Patent Application Publication No. US 2008/0148974, is known from the prior art. That document describes an apparatus for transferring or producing electrical energy or for transferring signals into a machine which processes printing materials. A rotationally movable component of a machine is driven by an electric motor which is situated directly on the shaft of the rotationally movably mounted component. Furthermore, apparatuses for transferring electrical energy or for transferring signals are disposed in a common housing.
A disadvantage of the previously known prior art is that different media cannot be transferred jointly.
SUMMARY OF THE INVENTION
It is accordingly an object of the invention to provide a rotary transfer apparatus for transferring different media and a printing press having the apparatus, which overcome the hereinafore-mentioned disadvantages of the heretofore-known apparatuses and printing presses of this general type and with which at least one further different medium can be transferred into a rotatably mounted component.
With the foregoing and other objects in view there is provided, in accordance with the invention, a rotary transfer apparatus for transferring compressed air or hydraulic fluid into a rotatably mounted component of a machine. The rotary transfer apparatus comprises a pressure-tight housing, a stationary part, a rotor, a connection guiding the compressed air or hydraulic fluid into the stationary part and through the rotor to the rotatably mounted component, and at least one additional component disposed in the pressure-tight housing for transferring at least one further medium.
The apparatus affords the advantage that, in addition to the transfer of compressed air, further media such as electrical energy, signals or data or drive energy can also be introduced into the rotatably mounted component. The basic advantage of the invention resides in it being possible for an additional component, which is responsible for introducing the further medium, to be accommodated in a pressure-tight housing.
If a corresponding space is provided for this purpose, the transfer of electrical energy or signals/data can be provided in it through the use of transfer apparatuses which have contacts or are contactless. The transfer of compressed air, as a result of which the pressure-tight housing is under positive pressure, does not generally disturb the additional component, since the air can flow around a component of this type. It is merely to be ensured that the compressed air is dry, which is usually prevented by corresponding precautions in a compressed-air supply.
Instead of a transfer apparatus for electrical energy, etc., a drive motor which moves the rotatably mounted component could also be accommodated in the pressure-tight housing. A direct drive which is attached on one of the cylinder journals of the rotatably mounted component would be advantageous in this case. However, it is to be ensured in this case that the feed lines of the drive motor are sealed when they are led through into the pressure-tight housing, so that there is no pressure loss.
A further possibility includes a gear mechanism being accommodated within the pressure-tight housing, in which the gear mechanism can also additionally be combined with the drive motor which is mentioned in the introduction. It is possibly to be ensured that very fine particles which are detached from the gear mechanism as a result of abrasion do not pass into the pneumatic system. To this end, the feed lines and discharge lines which supply the system with compressed air can be equipped with filters.
In addition to the actual object of the rotary transfer apparatus, namely the transfer of compressed air for a pneumatic system in the rotatably mounted component, a vacuum can also be active in the pressure-tight housing. That is to say, if a vacuum is required in the rotatably mounted component, a reversal of the pressure level can take place.
Furthermore, it is also conceivable that the transfer apparatus is used for transferring fluid, such as oil, for supplying a hydraulic system in the rotatably mounted component. If the hydraulic system in the rotatably mounted component has a restricted volume, a single-channel configuration is also conceivable in this case. That is to say, the pressure which is applied from outside ensures that a hydraulically moving actuating element performs a function in the rotatably mounted component. If a restoring movement is to take place, the pressure is canceled and a mechanical spring in the hydraulic actuating element ensures that the latter assumes its initial position again. The oil is pressed back through the use of the spring. However, it would also be conceivable that the introduced oil is not provided for supplying a hydraulic system, but rather for cooling a cylinder which in this case represents the rotatably mounted component. In a configuration of this type, however, the introduced oil has to be able to flow through the cylinder and exit the cylinder again. In this case, an outlet opening on the opposite cylinder side would be conceivable.
As described in the introduction, a drive motor for the rotatably mounted component could be accommodated in the pressure-tight housing. There are motors which can be oil-cooled in the actual operating case, in order to increase performance, or in order to achieve a smaller overall size with the same performance in comparison with noncooled motors. Motors of this type could be used when the cylinder is cooled, as described above.
However, it is also conceivable that the drive motor which is situated in the pressure-tight housing is operated hydraulically. To this end, the hydraulic fluid is introduced, as is provided for the compressed air, but a return line on the housing is required, through which the hydraulic fluid which has driven the motor is guided out of the pressure-tight housing again.
With the objects of the invention in view, there is concomitantly provided a printing press comprising the apparatus according to the invention. It is possible for the rotatable component to be a cylinder or a drum. The cylinder can, in particular, be a so-called plate cylinder, on which a printing plate is clamped. The introduced compressed air can be used for controlling clamping devices, through which the printing plate is clamped. In an application of this type, the additionally introduced energy can be used for the supply of actuating motors which are situated in the plate cylinder. For an application in which different pneumatic components situated in the cylinder are to be actuated differently, there is provision for the additional component in the pressure-tight housing to be a transfer apparatus for signals/data which has contacts or is contactless. A controller which controls the actuation of the different pneumatic components can therefore be supplied in the cylinder. However, the same could also be provided on a paper-conveying drum in a printing press.
Other features which are considered as characteristic for the invention are set forth in the appended claims.
Although the invention is illustrated and described herein as embodied in a rotary transfer apparatus for transferring different media and a printing press having the apparatus, it is nevertheless not intended to be limited to the details shown, since various modifications and structural changes may be made therein without departing from the spirit of the invention and within the scope and range of equivalents of the claims.
The construction and method of operation of the invention, however, together with additional objects and advantages thereof will be best understood from the following description of specific embodiments when read in connection with the accompanying drawings.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
FIG. 1 is a fragmentary, diagrammatic, longitudinal-sectional view of a rotary leadthrough; and
FIG. 2 is a longitudinal-sectional view of a rotary leadthrough having an additional drive motor.
DETAILED DESCRIPTION OF THE INVENTION
Referring now to the figures of the drawings in detail and first, particularly, to FIG. 1 thereof, there is seen a rotatably mounted component 1 which is mounted rotatably between two bearings 2 and 3 . Each of the bearings 2 and 3 support a respective cylinder journal 4 , 5 , between which the rotatably mounted component 1 is situated. The cylinder journal 5 opens into a pressure-tight housing 6 . A bearing 7 disposed between the pressure-tight housing 6 and the cylinder journal 5 , ensures an unrestricted rotational movement of the cylinder journal 5 in the pressure-tight housing 6 and ensures a sealing action. Firstly, a bore 8 which is situated in the cylinder journal 5 guides compressed air, for example, through the bore 8 and out of the interior of the pressure-tight housing 6 to a pneumatic system 9 . One end of the bore 8 is connected to the pneumatic system 9 by a line 10 . Secondly, a rotating part or rotor 11 of a transfer apparatus 12 is situated on the cylinder journal 5 . A line 13 is guided from this rotating part 11 of the transfer apparatus 12 through the cylinder journal 5 to an electrical system 14 in the rotatably mounted component 1 . The electrical system 14 can be a controller, an actuating motor, a data processing unit or the like.
A stationary part 15 of the transfer apparatus 12 , which is connected over a line 16 to a plug element 17 that is situated on an outer side 18 of the pressure-tight housing 6 , is situated opposite the rotating part 11 of the transfer apparatus 12 . Depending on requirements, the transfer apparatus 12 can be contactless or can have contacts, with corresponding sliding contacts being required in the case where the transfer apparatus 12 has contacts. The sliding contacts are not shown, since that part is not considered to be relevant to the invention.
Furthermore, a connection 19 for the supply of compressed air is situated on the outer side 18 of the pressure-tight housing 6 . If the compressed air is guided into the pressure-tight housing 6 , the compressed air passes through the rotating bore 8 to the pneumatic system 9 . In order to ensure that the pressure-tight housing 6 is not corotated by the rotating cylinder journal 5 , the pressure-tight housing 6 is fixed through the use of screws 21 on a frame wall 20 which holds the bearing 3 .
For the case in which the pneumatic system 9 includes a plurality of components or systems 9 , 9 ′ and 9 ″, there is provision for the electrical system 14 to assume the actuation of the individual pneumatic systems 9 , 9 ′, 9 ″. In this case, the electrical system 14 is a controller, from which actuating lines 22 , 22 ′, 22 ″ are connected to the pneumatic systems 9 , 9 ′, 9 ″. In this case, the supply of compressed air is brought about through lines 10 , 10 ′, 10 ″ which are connected to a distributor 23 .
FIG. 2 shows an illustration of a rotary leadthrough, into which a drive motor 24 for the rotatably mounted component 1 is integrated. The drive motor is constructed as a brushless motor, having magnets 25 which are integrated into the cylinder journal 5 and rotate within a magnetic field which is built up by coils 26 . The coils 26 are supplied with current through lines 27 . In addition, signals which are necessary to actuate the coils 26 can be sent over the lines 27 . The cylinder journal 5 is provided with a bore 8 which opens at one end into a line 10 . The line 10 supplies a pneumatic system 9 which is fed from a connection 19 . The pressure then propagates in the interior of the pressure-tight housing 6 and passes through the bore 8 and the line 10 to the pneumatic system 9 . The pressure-tight housing 6 is mounted and sealed with respect to the cylinder journal 5 by a bearing 7 . The pressure-tight housing 6 is fixed against rotation on the frame wall 20 through the use of screws 21 .
As an alternative, hydraulic fluid can also be fed-in in the connection 19 , if the interior of the rotatably mounted component 1 is a hydraulic system 28 . The hydraulic fluid then propagates in a similar way and passes to the hydraulic system 28 . A controllable valve 29 is provided for regulating the pressure which is introduced into the hydraulic system 28 . An advantage of the introduction of hydraulic fluid is that it simultaneously damps oscillations which result in the rotatably mounted component or are transmitted by it.
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An apparatus for transferring different media into a rotatably mounted component of a machine, such as a rotary leadthrough, includes a connection for introducing the media to a stator and through a rotor into the rotatably mounted component. The invention can be used, for example, on a plate cylinder of a printing press.
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BACKGROUND OF INVENTION
[0001] This invention relates to a pelletized frozen dessert product that can be stored and consumed at regular frozen dessert temperatures while still maintaining its unique pellet structure.
BACKGROUND
[0002] Discussion of Prior Art.
FIELD OF THE INVENTION
[0003] A pelletized frozen dessert product that is similar in flavor to a bulk frozen dessert product has entered the specialty market in recent years. Unfortunately, this product requires that the storage temperature for any period of time must be below about −34 to −40 degrees Celsius for optimal taste, storage and dispensing. Consequently, the storage demands of storing the frozen pellet in the range of about −34 to about −40 degrees Celsius has limited the distribution and market of this dessert product substantially.
[0004] The pelletized frozen dessert product although generally similar in taste to its comparable bulk frozen dessert is a unique product with its own particular characteristics. This frozen pellet can be manufactured utilizing existing premixes that are utilized in the bulk products, however it results in storage demands that require extreme storage conditions in order to maintain the unique physical structure of the product.
[0005] The present invention produces the pellets and provides a premix alteration methodology such that the frozen pellet can be stored in the storage conditions utilized for storage in the bulk frozen dessert market.
[0006] These alterations in the premix result in a pelletized frozen dessert product that can be a introduced into the general retail market without the necessity for specialized storage equipment or trained staff for distribution to the public.
BACKGROUND TO THE INVENTION
[0007] In order to properly understand the uniqueness of the patent a description of existing bulk frozen dessert and pelletized frozen dessert type products and their manufacture and storage and structure of the served product is presented.
Regular Bulk Frozen Dessert Products
[0008] Bulk frozen dessert products are manufactured utilizing a liquid pre-mix. The particular pre-mixes have evolved to produce frozen products that meet the needs and demands of the market. These needs and demands are flavor and sweetness and creamy structure and the ability to be scooped and served within the temperature ranges of commercial and home freezer storage systems.
[0009] Flavors of frozen desserts range from the traditional flavors such as vanilla, chocolate and strawberry to a complex mix of different cookies and other ingredients as well as different fruit and other flavors. All flavors however, need to have the basic structure that makes them a frozen dessert.
[0010] The market basically expects a product with a familiar level of sweetness. In a bulk product the sweetness is partly a result of the need to add an ingredient to the pre-mix that alters the freezing point such that the desired structure and texture is obtained.
[0011] The structure is such that the served product must be soft enough that it is consumable with a fork or is capable of being scooped into a cone or other holder. This demands that the served product be soft enough to be eaten pleasantly at the required serving temperature.
[0012] The simplified process of manufacture is as follows. The pre-mix goes into a freezing barrel. When the pre-mix is in contact with the surface of the freezer barrel the premix starts to freeze. The freezing mix is removed from the cooling surface via a moving blade or paddle that mixes the frozen mix with the unfrozen mix. The process continues by mixing the freshly frozen pre-mix, with the remaining premix until a semi-frozen product results. The product at this point is about the consistency of soft ice cream.
[0013] A more complex description is as follows.
[0014] Inside the freezing cylinder the liquid mix, with its suspended fat globules and colloidal proteins and carbohydrates and salts, is transformed into a highly viscous “foam”
[0015] Ice crystallizes from the continuous phase, transforming it into a thick syrup. Air cells form, and hydrophilic colloids absorb to their surfaces, stabilizing them. Fat globules become increasingly crystalline, and some of them coalesce, forming structure that supports the foam. As the product exits the freezer, it has about one half of its water frozen and has expanded up to about 100% in volume. The continuous phase is a thick syrup while the disperse consists of air cells and ice crystals and fat globules and casein micelles and other hydrocolloids. This makes ice cream a three-phase system: gaseous and solid and liquid. The agglomeration is a combination of small ice crystals and concentrated small pockets of unfrozen pre-mix and air. The concentrated pockets of premix are mostly a result of the freezing process concentrating the liquid such that its freezing point is further depressed.
[0016] The product is then removed and poured into bulk containers of the desired end size. The temperature is lowered such that the bulk product evolves to the solid frozen bulk. The product is stored at a recommended commercial temperature of from about −20 to −25 degrees Celsius, however, it can be stored at temperatures below that if the equipment is available.
[0017] When a bulk product is ready to be consumed it is tempered (warmed up) such that it again becomes smooth and creamy. This enables it to be scooped for cones, on pies etc. The ideal texture of a frozen dessert is a soft and creamy product that will stick together effectively.
[0018] At serving temperature the product is actually only about 70% to 80% frozen. The frozen aspects of the dessert create sufficient stability such that the remainder of the mix is held in place. Very much like mayonnaise holding its ingredients in a mix.
[0019] The key part of this description is that the pre-mixes utilized for regular frozen desserts are about 80% frozen at recommended serving temperatures. The temperature of the dessert is from about −6 to about −10 degrees Celsius.
[0020] This is about the average temperature of a freezer connected to a fridge. Longer term storage in equipment such as a deep freezer or a commercial deep freezer results in a higher percentage of the dessert being frozen resulting in the characteristic spoon bending hardness of ice cream from the deep freeze.
[0021] The mixture also has air trapped in its texture; this can be significant with as much if not more than 50% of the volume of the finished product is air. The air will create a certain amount of product insulation such that it will inhibit heat transfer between the bulk of the frozen dessert and the ambient environment.
Frozen Dessert Pellets
[0022] The frozen dessert pellet is a unique product with its own particular characteristics, however the pre-mix historically utilized has been virtually the same as that utilized in a bulk frozen product. This has resulted in the requirement for the pellet to be stored and served at very low temperatures i.e., about −28.8 C for short term storage, about −34 C to about −40 C for general storage and about −23 C to about −28.8 C for serving/consuming.
[0023] The pre-mix is introduced into a body of liquid cryogen (such as liquid nitrogen) as a series of small volumes of liquid (droplets). As a result of the significant difference in temperature the process of freezing is extremely rapid.
[0024] Unlike ice cream that is a three-phase product a frozen dessert pellet is completely frozen virtually immediately. This results in the finished product leaving the cryogen being completely or virtually solid.
[0025] The pellet exits the process in completely or virtually one phase, solid. When it is tempered it all melts at basically the same rate, as it was never differentiated into frozen aspect and a syrup phase when processed.
[0026] The liquid pre-mix is introduced into the body of a liquid cryogen as a small droplet. Upon entering the liquid cryogen, a crust or hard outer layer is immediately formed around the droplet. Freezing of the core is very rapid resulting in very small or virtually non existent ice crystals being formed. Depending upon the management of the liquid cryogen the pre-mix droplets can be formed into pellets with the following general characteristics:
1. The pre-mix will form a percentage of hollow shells with the contents freezing as new and smaller droplets. 2. A popcorn type product, which is basically the frozen explosion of the pellet. 3. Well formed, basically spherical in nature. 4. Random shapes, with the pellets being in various sizes, mostly as a result of post introduction fusing of forming pellets.
[0031] Since the freezing process is significantly different
1. The pellets do not have any air incorporated within its solid structure in the processing. This results in a frozen product that is 100% pre-mix. 2. There aren't any pockets of concentrated liquids and syrups with different freezing points within the structure of the solidified pellet. 3. The pellet is 100% frozen. 4. The pellet is only in one phase, that phase being solid.
[0036] The frozen pellet is simply, frozen pre-mix without the effects of the freezing and mixing process associated with the freezer barrel utilized for a bulk frozen dessert. In specific it does not have the three phase agglomerated structure of a bulk frozen dessert product.
[0037] As a result of the rapid freezing the pellet maintains the original ingredient flavors to a much greater extent.
[0038] When the pellet exits the processing system, the temperature of the product is at temperatures ranging usually from about −40 to about −60 degrees Celsius to very much colder. This exit temperature is partially dependent upon the process and management and retention time in the liquid nitrogen and the average size of the pellet.
[0039] The physical appearance and structure of the product can be controlled to vary from a popcorn type product to a hollow sphere to a well formed sphere to random shapes. This is a function of the management of the Liquid Cryogen and the equipment.
[0040] After processing the finished product is sent to a storage system that is in general much warmer relative to the finished product. The pellets are usually in the range of about −60 Celsius and colder, while the standard storage temperature for bulk desserts is typically from about −25 degrees Celsius to about −40 degrees Celsius.
[0041] A finished pellet can be poured or handled as one would handle ball bearings or other generally small round solids.
[0042] The total surface area, on per volume of premix utilized, is understandably much larger in surface area than a comparable amount of pre-mix utilized in a bulk product.
[0043] The pellet is kept at the 100% solid state or very close to this single phase existence in order to maintain its structural integrity. When tempering occurs it occurs at a rather rapid rate as a result of its high surface area per unit of weight.
[0044] Once the pellet starts to melt, it immediately will stick to associated pellets resulting in fusing of the pellets into a mass or the complete loss of the pellet type structure.
[0045] Historically the required storage temperature has been required to be approximately about −34 to −40 degrees Celsius in order to prevent the fusing of pellets.
[0046] Specialized vending equipment and delivery systems have been developed in order to handle the product and hold it at these cold temperatures.
[0047] In order to prepare the product for serving tempering (warming up) is required. In spite of the fact that there aren't any regulations regarding the minimum temperatures that food can be offered to the public good practice dictates that food at about −34 to −40 Celsius cannot be given to a person to eat. If a food product is placed in a mouth at these temperatures cellular damage to the mouth can occur. The reason there is not a minimum temperature regulation is that food in general is not consumable at these cold temperatures. At these cold temperatures food is structurally very solid and cannot be scooped or bitten or chewed. So it is likely that the necessity for a regulation never existed.
[0048] The frozen dessert pellet because of its individual small size can be put in a mouth at any temperature. A pellet at about −34 to −40 Celsius or lower can be put into a mouth easily. At colder temperatures the cellular damage can just be worse.
[0049] Since there does not seem to be any guidelines as to the lowest legal temperature that food can be served, safety is left as a decision to the distribution company. The result is that trained staff is required to interact with the public.
[0050] The requirement of storing the pellets at these low temperatures limits their distribution and demands that it must be only handled for serving by trained staff.
[0051] As can be seen there are significant differences that exist between the frozen pellet and its comparable bulk frozen product.
1. The pellet has a higher density resulting from being 100% pre-mix. 2. The surface area on a per volume of premix basis is much higher in the pellet. 3. A given volume of frozen pre-mix will temper much more rapidly. 4. The pellet is in a single phase which is the solid phase. 5. Flavors will be better preserved. 6. The range of consumable temperatures is small. 7. The pellet must be tempered by trained staff. 8. The pellet must be maintained at temperatures close to about −34 to −40 degrees Celsius in order to maintain its structural integrity.
[0060] A pelletized frozen dessert is a unique product with the differences between the comparable bulk frozen dessert and a frozen pelletized dessert being significant.
[0061] Historically, a similar premix to a bulk product has been utilized for a pelletized frozen dessert type product. This demanded that in order to account for the many differences previously described the pellet had to be stored and handled at depressed temperatures.
[0062] A bulk product is in 3 phases with it being a consumable product at about −6 to −10 degrees Celsius. As the temperature of a bulk product increases percentages of the agglomeration change from a solid phase to a liquid phase. The bulk product melts in the same ratios as it was frozen.
[0063] The pellet, since it solidified immediately its frozen matrix will melt very much like a small chips of ice will melt.
[0064] What occurs with the present premixes utilized for this type of product is that the pellet must be stored at temperatures close to about −34 to −40 degrees Celsius. The pellet is served at as cold a temperature as possible without hopefully causing cellular damage in the mouth.
[0065] This cold serving temperature inhibits the flavor of the product.
[0066] The tempering that is essential in advance of serving demands trained serving staff. These restrictions on the handling and serving the product has resulted in severely inhibiting the availability of the product to the general public. Availability has only been typically at special events or via trained serving staff.
[0067] Commercial storage facilities at about −34 to −40 degrees Celsius are limited. Trucks that can move a product at about −34 to −40 degrees Celsius are also limited. In store facilities available to the public at about −34 to −40 degrees Celsius are virtually non-existent. In addition −34 to −40 degrees Celsius storage demands expensive equipment and high running costs.
[0068] In order to introduce the small individual frozen dessert pellet to the existing market infrastructure it was essential to invent a premix that allows the pellet to exist as required at the temperatures utilized in the storage of bulk frozen dessert products.
[0069] The solution is to alter the premix formulation such that a higher percentage of the pellet is in a solid phase at standard storage temperatures of the recommended serving temperatures.
SUMMARY OF THE INVENTION
[0070] The present invention is directed to an improved frozen dessert pellet that could utilize the existing storage and handling facilities presently utilized for bulk frozen dessert products. In order to achieve this, an improved premix has been developed. The frozen pellets made from the premix of the present invention have the following characteristics:
1. The pellet is preferably a solid between about −15 and about −25 degrees Celsius. 2. The pellet softens on melting and does not melt like an ice chip. 3. The melting point of the pellet is preferably approximately −6 to −10 degrees Celsius. 4. There is also inhibition of fusing of pellets once melting temperature is initiated.
[0075] The present invention is directed to a superior premix utilized in a bulk frozen dessert product. The unique premix raises the freezing point of the premix which subsequently raises the melting point of the frozen premix. In addition the additives that are included inhibit the undesirable structural breakdown of the pellet once melting or softening of the pellet is initiated.
[0076] The invention is also direct to a frozen dessert pellet made from the premix that can be stored in conventional commercial facilities at the temperature ranges utilized for bulk frozen dessert products, i.e., being approximately −20 to −25 degrees Celsius. The storage temperature of the pellets made from the present invention is significantly higher than the storage temperature of prior art pellets made in cryogenic apparatus. In addition, the invention results in a pelletized frozen dessert product that can be stored at the temperatures of a home deep freezer being from about −15 to −18 degrees Celsius and the home fridge type freezer of about −6 to −10 degrees Celsius.
[0077] The pelletized frozen dessert product will maintain its basic structural integrity and individuality at these storage temperatures.
[0078] More specifically, in order to introduce pelletized frozen dessert products into the general retail market, it is essential that the product quality and unique features be maintained within the existing storage, distribution and serving temperatures utilized for bulk frozen dessert products, that are standard to the industry. In addition the product must maintain its unique features in the frozen storage systems that exist in households.
[0079] In a preferred embodiment the present invention includes a composition that remains frozen in the following:
1. Commercial refer freezer truck temperatures ranging from about −18 to −20 degrees Celsius. 2. Commercial ice cream freezer trucks ranging from about −26 to −28 degrees Celsius. 3. Commercial freezers in warehouses utilized by commercial facilities. 4. Retail store freezers that are presently utilized to store and as point of sale freezers for bulk frozen desserts. This temperature range being generally from about −25 to −30 degrees Celsius. 5. Home deep freezers systems being in the range of about −15 to −18 degrees Celsius. 6. The home freezer associated with a fridge. This temperature range being generally from about −6 to −10 degrees Celsius.
[0086] The present invention relates generally to a unique formulation of premixes utilized in the manufacture of pelletized frozen dessert products that will be stable in the foregoing temperature ranges.
[0087] More specifically, the formulation of a premix, is such that the pellet is substantially the same flavor as its' comparable bulk frozen dessert.
[0088] In addition the frozen pellets will maintain the desired structure when taken home by the consumer and stored in a household fridge freezer system. Providing they are only exposed to the ambient environment in the same manner as regular bulk frozen desserts are exposed.
[0089] Although the term “freezing point” is utilized in the frozen dessert science with pelletized frozen dessert products the important temperature points are as follows.
[0090] There are two main temperature points in connection with the present invention.
1. The melting point of the pellet. 2. The fusing temperature of the pellet.
[0093] The melting point is the temperature at which the product begins to melt. The mix of solids in the pellet is basically homogeneous and is in a single phase. By single phase is meant being a homogeneously frozen solid in which the pre-mixed fluids are frozen very rapidly in a cryogen in small volumes and hence remain in the same homogeneous state as they were in the liquid pre-mix. The bulk product which is in three phases and is an agglomeration has multiple melting points within its structure as each agglomerate piece will have its own melting point. By three phase is meant gas, liquid and solid. Gas is the ambient air incorporated into the pre-mix as it is being frozen in a freezing barrel by the action of the paddles or blades. The liquids are those fluids that have not frozen during the slow freezing process and remain as such following said manufacturing process. The solids are those liquids that have solidified during the manufacturing/freezing process.
[0094] The temperature at which part of the single phase product initiates melting is the temperature at which virtually all of the product structure initiates melting because unlike the three phase product that melts on a gradient, the homogeneous single phase product initiates melting all at the same time because it is homogeneous and has not been differentiated or concentrated.
[0095] The fusing temperature is the temperature at which the pellet becomes sufficiently soft so that the pellet will now stick to adjacent pellets and they will stick together. The result being that the pellets start to agglomerate into a mass, thereby losing its individuality of the pellet.
[0096] Freezing point of the product is usually not a significant term in the manufacture of these frozen dessert products as the product is manufactured in a cryogen such as Liquid Nitrogen and freezing is extremely rapid with the pellet actually going into storage following the freezing process at a temperature usually much higher than when it is harvested from the freezing equipment.
[0097] Although the science refers to freezing point it is assumed that in general a freezing point is considered the same temperature as a melting point.
[0098] According to Raoult's Law, the greater the percentage of a solute in a liquid the lower the vapor pressure of the solution and the lower the freezing point of the solution. Conversely, the lower the percentage of solute in the solution the higher the vapor pressure and subsequently the higher the freezing point of the solution.
[0099] The vapor pressure of a solution is directly related to the freezing point of the product.
[0100] Thus, raising the vapor pressure of the premix subsequently raises the freezing point of the premix.
[0101] The raising of the freezing temperature of the premix subsequently raises the melting point of the pellet.
[0102] Raising the melting point of the pellet subsequently raises the fusing as well as the melting temperature point of the pellet.
[0103] The formulation of the present invention is such that the average melting temperature of the frozen product is raised as a result of raising the vapor pressure of the premix. This results in a pellet that can be stored and served at a comparable temperature to a bulk frozen product. Those comparable products being Ice Cream, Sorbet, Water ice, Ice Milk, Frozen Yogurt and similar type products.
[0104] The primary ingredient that alters the freezing point of a premix is the quantity of sugar in solution. Additional materials in solution also adjust the freezing point as well, however the primary freezing point altering ingredient is the sugars present. Within the context of this invention and the product quality desired the melting point is more important than a freezing point, however essentially these temperature are the same.
[0105] The fusing point is also a useful term in relation to this invention as the goal was to produce a frozen dessert pellet that will maintain its structural integrity when handled and served at recommended temperatures similar to those utilized for bulk frozen desserts.
[0106] Various stabilizers are added to the premix in the form of edible gums, depending upon the product being manufactured. As a result when the pellet is in the range of its melting point this causes the product to soften a little yet the pellet will continue to maintain its basic structure.
[0107] The elevation of the melting temperature and fusing point takes into account a variety of important factors.
1. The surface area of the product on a volumetric basis is substantially higher than its comparable bulk product. 2. The heat transfer within the product itself is faster as the pellet does not have the advantage of air mixed with the product to inhibit heat transfer. 3. The product although desired to be firm, must be sufficiently soft that it can be consumed as a pleasant dessert and not as a hard pellet of ice.
[0111] More specifically, to, the formulation for preparing the premix of a pellet type product, the actual formulation will differ from product to product as flavorings, juices and other ingredients are required. The reason for this is that all of these individual ingredients will have some effect upon the overall freezing point and subsequently upon the overall fusing and melting point of the product.
[0112] The premix alterations result in maintaining the individual pellet integrity of the pelletized frozen dessert product at the desired temperatures.
[0113] In order to manufacture any acceptable frozen dessert it demands that a certain sweetness be present in the product. A variety of sugars provide this desired sweetness by the consumer.
[0114] Additionally stabilizers in the form of edible gums are added to the premix such that upon initial melting the gums assist in stabilizing a structure and allowing it to soften a little near its melting point yet preventing it from losing its basic structure at that point.
[0115] The frozen pellet maintains its structural integrity and can be stored at the storage temperature of bulk frozen desserts, that storage temperature being from about −20 degrees Celsius to −25 degrees Celsius.
[0116] The pelletized frozen dessert will maintain its structural integrity in the home deep freezer temperatures of approximately about −15 to −18 degrees Celsius.
[0117] The pelletized frozen dessert will maintain sufficient structural integrity in the home fridge freezer temperatures of about −6 to −10 degrees Celsius even though it, may soften at these temperatures.
[0118] The higher melting point combined with the gum stabilizers provide a synergistic result such that the structure is enhanced providing the desired pellet that can be presented and marketed within the infrastructure that exists for marketing and distribution of bulk frozen desserts.
DETAILED DESCRIPTION OF THE INVENTION
[0119] In order to manufacture a frozen dessert type product a premix is required. Currently available premixes typically have the following composition:
[0120] At least 10% milk fat with some premium ice creams going as high as 16%, or even 18% in super-premium ice creams. In addition to the milk fat there is also about 9% to 12% non-fat milk solids as well as about 12% to 18% sweeteners. These sweeteners are usually a cost-optimized combination of sucrose and corn sweeteners. There is also about 0.2% to 0.5% stabilizers and emulsifiers. The remainder of the formulation, typically about 55% to 64% is water, contributed primarily by the milk. It will be appreciated that there are numerous different recipes for ice cream. However, to be categorized an ice cream there must be at least 10% fat contained within the composition. Other ratios typically would be 11% for non-fat milk solids, 14% for sugars, egg yolk solids 0.5% and stabilizer additives no more than 0.5% by law. Many commercial ice cream manufacturers utilize dried egg yolk, powder skim milk, cane sugar, water (for reconstituting the powdered ingredients) and very inexpensive gums to produce product. Although current low calorie, lowered sugar or no sugar added bulk pre-mixes utilize sugar replacement products to maintain desired sweetness they are formulated to create the normal freezing characteristics and lowered vapor pressure of a regular bulk frozen pre-mix that has sugar added. Bulking agents are necessary to maintain the processing and post processing characteristics that are essential to a bulk ice cream products such as for example scoopability and mouth feel. These bulking agents, such as malto dextrin (sugar derivative) for example, lowers the vapor pressure of the pre-mix and thereby lowers the freezing temperature resulting in attaining the required freezing characteristics of a bulk frozen product.
[0121] In a preferred embodiment of the present invention the premix uses fresh milk and cream and stabilizers such as agar. In addition, the composition of the present invention does not require the presence of bulking agents such as malto dextrin because the sugar content is reduced.
[0122] An existing infrastructure exists within the distribution system and the commercial and retail storage system to maintain frozen desserts.
[0123] In addition, an infrastructure of freezing storage equipment exists within the consumer market as well consisting of the home deep freezer as well as the freezer associated with a home refrigeration system.
[0124] A pelletized frozen dessert product is typically manufactured by introducing small volumes of a premix into a body of a cryogen such as liquid nitrogen. Historically the premix utilized for this type of pelletized frozen dessert product has utilized standard premixes utilized in bulk frozen dessert type products. The utilization of this premix demanded that the frozen pellet thus made be stored at temperatures in the range of about −34 to −40 degrees Celsius. This storage temperature demands specialized freezing equipment not generally available in the retail distribution infrastructure and in addition not available in the consumer environment.
[0125] The storage temperatures generally encountered in the retail distribution market are as follows:
[0126] Commercial retail storage is in the range of about −20 to −25 degrees Celsius.
[0127] Home freezer storage in a standard deep freeze being in the range of −15 to −18 degrees Celsius.
[0128] Home fridge type freezer storage in a freezer associated with a home refrigeration system being in the range of about of −6 degrees to −10 degrees Celsius.
[0129] In order to make this specialized unique product available to the general retail market it was essential to develop a premix that could be utilized in the manufacture of a pelletized frozen dessert product that could maintain its structural integrity within the existing freezer infrastructure.
[0130] The development of this invention enables the pelletized frozen dessert product to be distributed within the existing retail commercial infrastructure as well as within the standard home freezer storage systems of the consumer market.
[0131] The main object of the invention is to elevate the melting temperature of the frozen pellet. This melting temperature is higher than the comparable melting temperature of a bulk frozen dessert product. The elevation of the melting temperature is achieved by removing a significant percentage of the sugar in the normal premix while still retaining the preferred taste of the product. Alternatively all added sugars can be removed completely and replaced with artificial sweeteners if desired for a composition that is sugarless. Accordingly, that significant percentage removed can range from about 30% to about 70% of the sugar normally in a premix. In a preferred embodiment the sugar removed ranges from about 40% to about 60%. In a more preferred range the removed sugar can range from 45% to about 55%.
[0132] In the most preferred embodiment there is removal of about 50% of the sugar in a standard premix
[0133] Quantitatively, Raoult's law states that the solvent's vapor pressure in solution is equal to its mole fraction times its vapor pressure as a pure liquid, from which it follows that the freezing point depression and boiling point elevation are directly proportional to the molality of the solute, although the constants of proportion are different in each case.
[0134] Although Raoult's Law does predict a raising or lowering of the freezing point of a Solution subject to the alteration of its vapor pressure, this invention is in specific not an extension on this law. This is because the pellet is frozen extremely quickly and taken to a temperature well below the freezing point of any pre-mix, in an environment of a liquid cryogen. Subsequently the freezing point of the pre-mix is not a factor that is even considered.
[0135] The cryogen freezing process is an essential factor in the frozen pellet structurally existing at the desired elevated melting temperatures. As a result of the rapid and very cold freezing of the pellet the ice crystallization is minimized and the pellet produced is a single phase product, unlike the multiple phase product of bulk frozen deserts.
[0136] The result of the rapid freezing achieved in the cryogen is a single phase pellet that is generally homogeneous in nature. The rapid freezing also results in a pellet with minimal crystallization. It is this minimal crystallization as a result of the rapid freezing that results in a pellet that has not separated into multiple phases during the freezing process as occurs in all bulk product manufactured. It is this single phase structure of the pellet that assists in its ability to stay stable at the elevated melting point of the pellet.
[0137] The elevated melting point is a direct result of the pellet structure combined with stabilizers, typically being the food grade gums added to the pre-mix which allows for the existence of a pellet that can softened because of partial melting, yet it does not flow like melting ice chips as the stabilizers/gums act to inhibit this natural action.
[0138] The invention comprises formulation alteration including the addition of food grade gums as stabilizers added to the pre-mix and subsequently processed in a liquid cryogen, such as liquid nitrogen, results in a frozen dessert pellet that meets the requirements essential for a frozen dessert pelletized product that remains stable within the existing bulk frozen dessert infrastructure.
[0139] In order to maintain consumer preferences and desired sweetness profiles the pelletized frozen dessert of the present invention preferably requires the addition of sweetness to compensate for the significant lowering of the sugar content.
[0140] This is achieved by the utilization of artificial sweeteners.
[0141] Accordingly, these artificial sweeteners are preferably products such as Sucralose or Aspartame and the like.
[0142] In the preferred embodiment the sweetness level of the invention's pelletized frozen dessert product is maintained in the range of about 13% to 17% of the amount of sucrose typically present in a frozen dessert product.
[0143] In general, Sucralose provides about 600 times the sweetness in sucrose equivalency.
[0144] The preferred embodiment is the utilization of Sucralose.
[0145] The sucrose equivalency is about 1 unit of Sucralose is added to the premix for every 600 units of sucrose or any equivalent in sweetness that has been removed.
[0146] An additional embodiment is the addition of Aspartame which provides 200 times in sucrose equivalent.
[0147] The sucrose equivalency is about 1 unit of Aspartame is added to the premix for every 200 units of sucrose or any equivalent sweetness that has been removed.
[0148] There are other artificial sweeteners that are currently available or that will potentially be available in the future. Whatever their sucrose equivalence is or potentially would be would hence call for the appropriate replacement ratio to attain the desired sweetness. Current available artificial sweeteners include but are not limited to the following examples: Examples: Sucralose, Aspartame, Saccharin, Acesulfame K.
[0149] An additional embodiment is a combination of Sucralose and Aspartame in order to minimize any background disagreeable taste provided by the addition of an artificial sweetener to a food product.
[0150] Accordingly that depending upon the particular flavor of the frozen desert desired the sweetness level will vary. For example a frozen dessert product such as a vanilla ice cream pre-mix with a total sugar content of 15% to 17% of the pre-mix, an approximate replacement of about 50% of those sugars would require a sucralose replacement in the range of about 0.025% to about 0.075% depending upon sweetness preference, A preferred sucralose replacement range would be from about 0.03% to about 0.07% with a most preferred range being from about 0.04% to about 0.06%.
[0151] Accordingly a chocolate frozen product demands a higher level of sweetness to counteract the harshness of the Cocoa utilized in the mix compared to a vanilla type frozen dessert product. The chocolate frozen dessert pre-mix would hence call for a sucralose replacement of sugars in the range of about 0.075% to about 0.16% depending upon sweetness preference. A preferred sucralose replacement range would be from about 0.08% to about 0.15% with the most preferred being from about 0.09% to about 0.11%.
[0152] Accordingly, frozen dessert type products such as ice cream, sorbet, water ice, ice milk, frozen yogurt and similar type products all must be first formulated as pre-mixes with sugar replacement and stabilizer additions added prior to the cryogenic freezing process. This pre-mix formulation combined with the single phase structure of the pellet that results from the cryogenic freezing process results in being able to achieve the desired melting and fusing points necessary for compatibility with the existing frozen bulk food handling and storage infrastructure. Accordingly the sugar removal and the addition of sweetener will vary in relation to the flavor desired. The reason being that, various fruit flavors will provide an alteration in the freezing point and subsequently the melting point of the frozen pellet.
[0153] Accordingly the variances necessitate the removal of more sugar or less sugar and the relative balancing of sweetness with the artificial sweeteners.
[0154] The preferred embodiment of the invention is to vary the removal of sugar and then utilize artificial sweeteners to reestablish the desired sweetness of the pelletized frozen dessert product.
[0155] Accordingly the pellet can be served when it has become partly softened. In order to maintain its structure a stabilizer in the form of a food grade gum is added to the premix. Current stabilizer gums include but are not limited to the following examples. Examples: guar gum, carob bean gum, mono+diglycerides, sodium alginate, agar. Stabilizer gum ranges for a Vanilla ice cream pre-mix depending upon the preferred texture would be from about 0.25% to about 0.60% with a preferred range from about 0.35% to about 0.55% and a most preferred range being from about 0.40% to 0.50%. For a chocolate ice cream premix the range depending upon the preferred texture would be from about 0.20% to about 0.50% with a preferred range of about 0.30% to about 0.45% and a most preferred range being from about 0.35% to about 0.44%.
[0156] Accordingly the addition of a stabilizer assists in maintaining the desired individual structure of the pellet.
[0157] Accordingly the stabilizer also inhibits fusing of the pellets when the pellet is close to the range of its melting point.
[0158] A preferred embodiment of the invention is that since the pelletized frozen dessert can now be stored at an elevated temperature the necessity of trained staff to temper the pellet to a safe temperature is not longer required.
[0159] Accordingly the safety of the pellet by avoiding potential cellular damage to the consumers mouth is achieved.
[0160] This invention of raising the freezing temperature of the premix which subsequently raises the melting point of the pelletized frozen dessert product with the subsequent addition of a stabilizer to assist in maintaining the structural integrity of the pellet when at preferred serving temperatures achieves the desired results.
[0161] The desired results being able to distribute a pelletized frozen dessert product within the existing infrastructure utilized for bulk frozen desserts.
[0162] In addition the raising of the storage temperature required removes the potential of cellular damage occurring in the mouth of the consumer. This removal of a serious safety concern enables the frozen pelletized dessert product to be a generally available dessert product rather than a specialized frozen dessert with expensive and cumbersome or almost impossible distribution demands.
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The present invention is directed to formulations of the premix utilized in the production of a pellet structured frozen dessert type product. The pelletized frozen dessert product is manufactured by introducing the liquid premix into a body of a cryogen such as liquid nitrogen such that the small volume of liquid premix is frozen rapidly. The invention elevates the melting temperature as well as the fusing temperature of the finished pellets such that the storage and serving temperatures of the pellets are similar to the bulk products. The invention utilizes the basic formulas and names and flavors associated with bulk type frozen desserts such as Ice Cream, Sorbet, Water ice, Ice Milk, Frozen Yogurt and similar type products. The pellet produced utilizing the pre-mix is structurally stable at normal retail and home freezer situations.
The formulation and manufacture of the pelletized dessert product is substantially different from bulk frozen desserts: it is in itself a unique type product.
The result of this invention is a product that maintains the desired individuality of the pellets while maintaining structure, such that fusing is inhibited at the storage and serving temperature.
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TECHNICAL FIELD OF THE INVENTION
This invention relates in general to semiconductor circuits, and more particularly an insulator separated vertical CMOS structure.
BACKGROUND OF THE INVENTION
In semiconductor processing, it is sometimes easier to form vertical structures where the vertical dimensions can be accurately controlled. U.S. Pat. No. 4,740,826 to Chatterjee and U.S. Pat. No. 4,810,906 to Shah et.al., which are incorporated herein by reference, disclose integrated electronic devices wherein two vertical transistors are vertically aligned to form a CMOS inverter. Thus, a layer of P type material is formed on the surface of an N+ type substrate, followed by the formation of an N+ layer, a P+ layer, an N- layer, and a P+ layer. A trench is etched along one side of the stack and a connector is formed to the midlevel P+ and N+ layers. Another trench is formed and a gate insulator and a gate are formed therein. The gate serves as a gate for both the N-channel and P-channel transistors. The connector is used to provide an output from the connected source/drain regions of the two transistors. Thus, current flows vertically through a pair of complementary field effect transistors, which are always in series.
The concept disclosed in the above-referenced patents may be used to form CMOS inverters, and other structures, such as NOR gates, which comprise a plurality of inverters. Since the stacked transistors have connected source/drain regions, however, the formation of more complex logic elements using a similarly vertical configuration is difficult.
Therefore, a need has arisen to provide a stacked vertical transistor structure from which complex logic devices may be configured.
SUMMARY OF THE INVENTION
In accordance with the present invention, a complementary semiconductor device is provided which substantially eliminates the disadvantages and problems associated with prior vertical transistor devices.
The complementary semiconductor structure of the present invention comprises a substrate of the first conductivity type upon which a first channel layer of a second conductivity type is formed. A first source/drain layer of said first conductivity type is formed on the surface of the first channel layer. An insulating layer is formed on the surface of the first source/drain layer and a second source/drain layer of the second conductivity type is formed on the surface of the insulating layer. A second channel layer of a first conductivity type is formed on the surface of the second source/drain layer and a third source/drain layer of the second conductivity type is formed on the surface of the second channel layer. Gate circuitry is vertically disposed on an edge perpendicular to the plane and adjacent to the first and second channels layers and is insulated therefrom.
The complementary semiconductor device of the present invention provides several technical advantages. First, complex structures may be designed using the complementary structure, since the top and bottom transistors of each mesa are not connected and need not both be used. Second, the midlevel insulator provides processing control by providing an intermediate etch stop in the silicon etching steps such that the timed etch distance is cut in half. Third, in the embodiment when the N-channel transistor is provided at the surface of the device, the use of pseudo-NMOS structures in the circuit design is facilitated. Fourth, the structure is amendable to an efficient honeycomb layout which minimizes overall circuit size.
BRIEF DESCRIPTION OF THE DRAWINGS
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:
FIG. 1 illustrates a cross-sectional side view of the present invention after a first processing stage;
FIG. 2 illustrates a cross-sectional side view of the present invention after a second processing stage;
FIG. 3 illustrates a cross-sectional side view of the present invention after a third processing stage;
FIG. 4 illustrates a cross-sectional side view of the present invention after a fourth processing stage;
FIGS. 5a-c illustrate cross-sectional side views of the present invention showing various connections to the midlevel diffused regions after a fifth processing stage;
FIG. 6 illustrates a cross-sectional side view of the present invention after a sixth processing stage;
FIG. 7 illustrates a cross-sectional side view of the present invention after a seventh processing stage; and
FIG. 8 illustrates a top plan view of one embodiment of the present invention using a honeycomb layout.
DETAILED DESCRIPTION OF THE INVENTION
The preferred embodiment of the present invention is best understood by referring to FIGS. 1-8 of the drawings, like numerals being used for like and corresponding parts of the various drawings.
FIG. 1 illustrates a cross-sectional side view depicting the initial processing steps for fabricating one embodiment of the present invention. Doped layers 10 and 12 are formed on substrate 14. The doped layers 10 and 12 may be formed epitaxially (using, for example, molecular beam epitaxial techniques) or by implantation. By using these techniques, very abrupt transitions between the N and P type doping material may be fabricated. For example, P+ type layer 10 may be approximately 1,000-2,000 angstroms thick and the N type layer 12 may be 2,000-5,000 angstroms thick. Doped layers 16, 18 and 20 are separated from P+ type layer 10 by a thick oxide region 22. Layers 16 and 20 may be on the order of 1,000-2,000 angstroms and layer 18 may be on the order of 2,000-5,000 angstroms. Thinner or thicker layers may be formed as desired and are considered within the scope of the invention. The critical thickness involve layers 12 and 18, which are preferably within the ranges stated above. However, the thickness layers 12 and 18 may alternatively be selected to achieve any desired electrical gate length.
The midlevel insulator layer 22 can be formed using several methods. One such method uses oxide bonding, or other forms of wafer-to-wafer bonding, to join two slices face-to-face, followed by lapping and global etch back to an etch stop to thin the second slice such that the top semiconductor layers 16, 18 and 20 come from the second slice and the lower layers 10, 12, and 14 come from the first slice. This embodiment of the present invention provides the advantage of allowing a thick insulator layer 22, since the only cost of increased insulator thickness is increased etch and deposition times. A thick insulator layer 22 reduces parasitic capacitances and leakage through the insulator layer.
Alternatively, and less preferably, an implant and anneal process, such as the process used to make SOI structures, could be used before the formation of the layers 16, 18 and 20. This process could be performed at a much lower energy than that used for SOI structures. For example, a thick N- layer could be grown on the P+ substrate 14 (with appropriate precautions against autodoping). A second P type implant could be performed to form the midlevel P+ layer 10. An oxygen implant could then be performed at a dose of, for example, 1×10 15 cm -2 of oxygen at a stopping distance of 200 angstroms. Epitaxial growth could then resume, using implantation techniques to form the midlevel N+ layer 20 and N+ layer 16.
After forming the layers 10, 12, 16, 18 and 20, a masking layer 24 is formed over layer 16. Masking layer 24 is formed of a suitable masking material and patterned using commonly known photolithographic techniques.
In FIG. 2, masking layer 24 is used during an etching process to fabricate trenches 26. The trenches 26 extend to surround mesas 28 of semiconductor material. In the preferred embodiment, illustrated in FIG. 2, the midlevel insulator 22 provides an effective etch stop which results in greater processing control.
FIG. 3 illustrates a cross-sectional side view of the present invention after a third processing stage, in which the trenches 26 are completed. An oxide etching step which is selective to silicon is used to etch the portion of the trench through the midlevel insulator layer 22. Following the insulator etch, another silicon etch is used to etch the trench through the P+ type layer 10 and the N type layer 12, and partially into the substrate 14.
In FIG. 4, a cross-sectional side view of the present invention is illustrated after a fourth processing stage. A planarizing insulating layer 30, typically a silicon dioxide layer, is formed over the surface of the structure of FIG. 3 and into the trenches 26. The insulating layer can be formed, for example, by chemical vapor deposition.
FIGS. 5a-c illustrate alternative structures for providing connections to the mesas 28. Two primary alternatives of the present invention combine the buried layer interconnects of FIGS. 5a and b (shown in trenches 26a and 26b) and combine the interconnects of FIGS. 5a and c (shown in trenches 26a and 26c). FIG. 5a illustrates a cross-sectional side view of the present invention wherein tungsten contacts are provided to the N+ layer 20 of a mesa 28. In this embodiment, the silicon dioxide layer 30 is etched back to provide plugs 32 which fill the trench to a level intermediate to the midlevel insulator 22. A buried lateral interconnect, shown as tungsten layer 34, or other conducting layer, is formed over the plugs 32 such that an electrical connection to the N+ layer 20 is provided. Insulating layer 36 is formed over the tungsten layer 34. For example, insulating layer 36 may be formed by a silicon dioxide deposition and etch back technique. It should be noted that whereas two trenches 26a are shown in this embodiment, only one trench is needed for the contact to the N+ layer 20. The other trench will be used to contact the gate of the transistors as illustrated in FIG. 6.
FIG. 5b illustrates a structure wherein the P+ layer 10 is contacted. In this structure, the insulating layer 30 is etched back to form plugs 38 which fill the trench to a level intermediate to the P+ layer 10. A buried lateral interconnect, shown as tungsten layer 40 is formed over the plugs 38 to provide a connection to the P+ layer 10, without contacting the N+ layer 20. An insulating layer 42 is formed over the tungsten layer 40 fill the trenches 26b. Once again, only a single contact 40 is needed to contact the P+ layer 10; the other trench may be used to provide a gate contact, as illustrated in FIG. 6, or may be completely filled with insulating material.
FIG. 5c illustrates a structure which connects the N+ and P+ layers 10 and 20 of the mesa 28. In this embodiment, plugs 44 are formed to a level intermediate to the P+ layer 20. A buried lateral interconnect, shown as tungsten layer 46 is formed such that the P+ layer 10 is electrically connected to the N+ layer 20. An insulating layer 48 is used to fill the remaining portions of the trenches 26c.
FIG. 6 illustrates the formation of a common gate region for the two vertical transistors comprising a mesa 28. This aspect of the invention is discussed in U.S. Pat. Nos. 4,740,826 and 4,810,906, referenced above. For purposes of illustration, the formation of the common gate is shown in connection the structure of FIG. 5a, which provides a connection to the N+ layer 20.
Trenches 50a and 50b are formed adjacent respective trenches 26a, using masking layer 52. The structure in FIG. 6 is subjected to a thermal oxidation process to form silicon dioxide layers 54 where silicon is exposed by the trenches 50a-b. The silicon dioxide layer 54 provides the gate insulation for the vertical transistors in the mesa 28.
In FIG. 7, a cross-sectional side view of the present invention after a seventh processing stage. Conducting regions 56, typically formed from tungsten, are formed within the trench 50a-b. The tungsten conducting region 56 formed in trench 50a provides electrical contact to the adjacent plug 32 while the conducting region 56 formed in trench 50b provides the gate to the vertical transistors. Hence, the plug 32 adjacent the conducting region 56 formed in trench 50b provides a conducting path to an adjacent mesa, if desired.
Insulating regions 58 are formed over the filled trenches 26 and at the junction of the mesa 28 and the conducting region 56. Contacts 60 are formed on exposed portions of the structure. Complex structures may result in several interconnect levels providing electrical connections between the mesas 28 and conducting regions 56. Preferably, at least two layers of interconnects are used above the surface, but an alternative embodiment could vary from this requirement as necessary.
It should be noted that while the present invention shows a common gate for the two vertical transistors comprising the mesa, it is not necessary to use both transistors in the circuit path because the two interconnect types (26a and 26b or 26a and 26c) permit separate connections to each transistor.
As shown in FIG. 8, the present invention is amendable to a hex-grid (honeycomb) layout which prevents lateral shorting of contacts to the semiconductor mesa 28. In FIG. 8, the semiconductor mesa 28 is surrounded by six regions. Insulation regions 62, which comprise trenches filled with insulating material, separate conducting regions 64 of the type illustrated in FIGS. 5a-c and 7. The hexagonal layout provides an efficient structure for a mesa surrounded by three conducting regions, one gate and two buried lateral interconnects. This structure provides an efficient configuration, since the size of each isolation region 62, conducting region 64 and mesa 28 may be as small as a single layout pixel.
While the present invention has been shown with the N-channel transistor disposed above the P-channel transistor, either transistor could be disposed above the other. However, providing the N-channel transistor on top provides the advantage that the N-channel devices will be more easily accessible, thereby facilitating the use of pseudo-NMOS structures in place of full CMOS structures.
In forming the midlevel insulator 22, two approaches could be taken. A relatively thick insulator may be provided, typically through oxide bonding, which would reduce parasitic capacitance and leakage through the insulator. Alternatively, a lower quality insulator may be treated by designers as a parasitic distributed conductance from layer 10 to layer 20 and may be isolated in areas where the conductance of the insulator loads the signal path. Use of a slightly leaky insulator avoids some floating node problems and may prevent the upper portion of the semiconductor mesas from holding a charge for long periods.
The present invention provides several advantages over the prior art. First, more complex structures may be designed, since the top and bottom transistors of each mesa are not connected. Second, the midlevel insulator provides processing control by providing an intermediate etch stop in the silicon etching steps such that the timed etch distance is cut in half. Third, the embodiment where the N-channel transistor is provided at the surface of the device facilitates use of pseudo-NMOS structures in the circuit design. Fourth, the structure is amendable to an efficient honeycomb layout which minimizes overall circuit size.
Although the present invention has 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.
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A complementary semiconductor structure comprises a substrate of a first conductivity type upon which a first channel layer of a second conductivity type is formed. The first source/drain layer of the first conductivity type is formed on the surface of the first channel layer and an insulating layer is formed on the surface of the first source/drain layer. A second source/drain layer of the second conductivity type is formed on the surface of the insulating layer and a second channel layer of said first conductivity is formed on the surface of the second source/drain layer. A third source/drain layer of the second conductivity type is formed on the surface of the second channel layer. Gate circuitry is vertically disposed on an edge perpendicular to the plane and adjacent to the first and second channel layers and insulated therefrom.
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FIELD OF THE INVENTION
This invention relates to controllers for hydraulic pumping units which power subsurface pumps.
BACKGROUND OF THE INVENTION
Pumping units for deep wells, including water and oil wells, have been, for the most part, pumping units, both mechanical and hydraulic, having a counterweighted beam, or "horsehead." Rods, called sucker rods, supported by the surface pumping unit, extend from the surface to the subsurface pump, and can weigh thousands of pounds. The counterweights balance the weight of the rods and lifted fluid and attempt to smooth out the load on the prime mover for the pumping unit. The weight of such units necessitates equally massive support structure and resulting bearing or friction losses of efficiency. Certain units have counterweights associated with the axle of the gearing so that the counterweight falls during upstroke of the subsurface pump. Some hydraulic units have been constructed using heavy counterweights and others utilize pneumatic accumulators which are pressured by downstroke and energy is released and utilized during upstroke.
Although swashplate hydraulic pumps have been utilized in such applications, the control mechanisms have not been adequate to give sufficient variability of control within a single upstroke or downstroke of the subsurface pump. Such inability contributes to a lack of pumping efficiency, particularly for long stroke pumps, and can lead to premature sucker rod failure by exerting tension forces of too great a magnitude in the phase of the upstroke or downstroke when maximum tension is exerted on the rods.
SUMMARY OF THE INVENTION
The invention is a hydraulic pump controller and method for operating a hydraulic pump which minimizes sucker rod stress and provides smooth transition between upstroke and downstroke. The controller includes means for sensing the position or stage of the pumping unit piston in the pumping cycle, means mechanically linked to the sensing means for transmitting the position of the piston to a variable flow reversible hydraulic pump, means to reverse and increase flow to the hydraulic pump from zero to full flow, and means to override the reversing and increasing means for decreasing flow from the hydraulic pump from full flow to zero at a rate different from the rate of increase in flow from the pump.
The method of the invention includes pumping hydraulic fluid to a cylinder operating a subsurface pump at a constant increasing rate until a preset maximum flow rate is reached, decreasing hydraulic fluid flow to the cylinder at a rate different than the rate at which flow was increased until flow to the cylinder ceases, reversing the flow of fluid to the cylinder and increasing the reversed flow at a constant rate until maximum reverse flow rate is reached, and reducing the reversed flow rate to zero at a rate different than the increasing rate. Certain aspects of the method gather the energy of the falling mass attached to the pumping unit piston on downstroke to partially power the upstroke of the unit.
BRIEF DESCRIPTION OF THE DRAWINGS
Reference is now made to the drawings, in which:
FIG. 1 is a schematic representation of a hydraulic pumping unit, the hydraulic pump powering same and the linkage between the pumping unit piston sensor and the hydraulic pump controller.
FIG. 2 is a partially schematic view of the linkage between the pumping unit piston sensor and the controller, showing a partial side elevation cross-sectional view of the controller with parts in position to provide maximum swashplate movement.
FIG. 3 is a top plan view in partial cross-section of the controller in the same operational position as shown in FIG. 2.
FIG. 4 is the controller in partial cross-section with parts in position to put the pump swashplate in neutral position.
FIG. 5 is a top plan view of the controller in partial section with parts in the neutral position as shown in FIG. 4.
FIG. 6 is a graph showing two examples of full stroke cycles of the hydraulic pump showing cylinder travel of the pumping unit piston in terms of percent of full travel versus hydraulic pump swashplate oscillation in degrees.
FIG. 7 is a graph showing pumping unit piston travel in a complete cycle versus time.
DESCRIPTION OF THE PREFERRED EMBODIMENT
A preferred embodiment of the hydraulic pumping unit is shown in FIG. 1. An oil or water well surface installation is shown having a well head (32), in which a polished rod (33) reciprocates. Polished rod (33) supports a string of sucker rods (not shown) which are attached to the piston of a subsurface well bore pump (not shown). Such downhole sucker rod pumps are well known and used extensively in subsurface pumping applications. The piston of such subsurface pumps is operated by vertically reciprocating the sucker rod string suspended from polished rod (33) by up and down movement of the piston rod (12) of the lift cylinder generally designated by the numeral (10). The derrick (37) rests on a platform (35). Derrick (37) supports lift cylinder (10) in which the pumping unit piston (not shown) is contained. Pumping unit piston (not shown) is connected to a piston rod (12) joined at its other end by a piston rod clamp (36) to polished rod (33).
As hydraulic fluid is admitted to the fluid inlet (14) of the hydraulic lift cylinder (10), the hydraulic piston is urged upwardly and piston (10a) rod (12) attached thereto causes polished rod (33) to stroke the sucker rods suspended therefrom and the piston (10a) of the subsurface pump upwardly.
Lift cylinder (10) also includes a hydraulic drain (15) connected by a hydraulic fluid drain line (30) to tank (40). Since lift cylinder (10) is a single-acting cylinder, hydraulic drain (15) merely serves to convey to the fluid tank (40) the hydraulic fluid which has seeped past the hydraulic piston into the unpressured upper portion of lift cylinder (10). Piston (10a) rod (12) may be surrounded with an appropriate dust-tight enclosure (not shown).
Fluid inlet (14) of lift cylinder (10) is fluidly connected to the hydraulic, or hydrostatic, pump (23) which obtains hydraulic fluid from tank (40) through the supply line (54) and supplies the fluid to lift cylinder (10) during the subsurface pump upstroke. During downstroke of the subsurface pump, hydraulic fluid flows from lift cylinder (10) out fluid inlet (14) through the hydraulic power line (19), through hydrostatic pump (23) and into fluid reservoir (40) via the supply line (54). The reversal of flow through hydrostatic pump (23) permits the capture of energy of the falling mass of sucker rods (not shown) on the subsurface pump and hydraulic piston downstroke.
In FIG. 1, a mechanical arrangement for sensing the position of the pumping unit piston and piston rod (12) is shown. Following the motion and position of the pumping unit piston and piston (10a) rod (12) is a spiral timing shaft (11), joined to the lift cylinder traveling bar (34). Spiral timing shaft (11) is mounted for rotation about its long axis in derrick structure (37) by the upper and lower shaft bearings (38). The lower end of spiral timing shaft (11) is joined at a right angle to a slotted timing lever (29). Timing lever (29) has a timing lever slot (31) at a predetermined, adjustable, distance from a timing lever pivot (17) which is fixed for pivoting movement of timing lever (29) thereabout to a portion of platform (35). Thus the position and movement of polished rod (33), piston rod (12) and timing rod (11) are transmitted by a controller rod (51) to controller (50). Timing lever bearing (27) may be fixed at different positions in timing lever slot (31) to cause greater or lesser movement of controller rod (51) to provide means for sensing the position of the pumping unit piston and piston (10a) rod (12).
Spiral timing shaft (11) is rotated, for example, 180 degrees, by a guide (13) as lift cylinder traveling bar (34) is raised and lowered with piston rod (12). Timing lever (29) is fixed to a lower portion of spiral timing shaft (11) and is oscillated in the example 180 degrees by spiral timing shaft's (11) action through guide (13) which induces rotary motion of spiral timing shaft (11) as lift cylinder traveling bar (34) moves with respect to derrick frame (37). Timing lever (29) reciprocates timing rod (51). Timing rod (51) turns or rotates the controller crank (56) of the controller (50) (FIG. 2) during the latter phases of upstroke and downstroke, as will be later explained. The further from the center of rotation of spiral timing shaft (11) that timing lever bearing (27) is fixed, the greater the longitudinal movement of timing rod (51).
The power for hydraulic, or hydrostatic pump (23) is provided on the upstroke of the unit by the power train. The power train includes a power source (20) and a hydrostatic pump (23), a variable displacement, axial multipiston, reversible swashplate pump such as that available from Oilgear Company, Hydura model PVW or from Mannesmann Rexroth, model A(A)4VSGHW. Such pumps permit reversible flow variable fluid volume cycles and variable flow rates during such cycles depending upon the angle of the swashplate of the pump. Such pumps eject pressured fluid by action of the pistons powered by a power shaft (25) when flow is in a first direction, and when reversed, can extract energy from the reversed pressurized fluid by operating the pistons which transfer energy to power shaft (25). Such pumps are well known and available for use in various positive displacement and high pressure applications.
The prime mover, or power source (20), may be a conventional internal combustion engine, electric motor or other power source, such as a windmill. If a windmill is used, the inertial assist, or flywheel (21) may be incorporated into the rotating wind turbine, or be a separate mechanical element inserted into the power train. A flywheel (21) is connected to power source (20) by a flywheel clutch (22) which permits kinetic energy to be gradually added into flywheel (21) at startup of the pumping operation by engagement or disengagement with power source (20). The power from power source (20) and flywheel (21) is transmitted to hydrostatic pump (23) by power shaft (25) through the power connector (26). Power shaft (25) rotates the fluid cylinders and pistons of hydraulic pump (23) against its swashplate (23a) which produces the flow of pressured hydraulic fluid to lift cylinder (10) during subsurface pump upstroke. The swashplate (not shown) of hydrostatic pump (23) controls the rate, direction and volume of fluid through hydrostatic pump (23).
No restrictor values are present in lift cylinder (10), hydraulic power line (19) or hydrostatic pump (23). The flow of hydraulic fluid to or from lift cylinder (10) is controlled by controller (50), and is dependent in part upon the position of the piston 23a in lift cylinder (10). That position is relayed to a swashplate setting mechanism, such as a pintle control shaft (53) (FIG. 2) to set the swashplate by moving the swashplate shaft (not shown) to the proper angle for desired direction and rate of flow.
Referring now to FIGS. 2 and 3, controller (50) mechanically receives the position of timing rod (51), which indicates the latter stages of upstroke and downstroke of polished rod (33) and determines the position of the pintle control shaft (53) during such stages of stroke. In FIGS. 2 and 3, piston rod (12) in lift cylinder (10) is at mid-stroke and pintle control shaft (53) has moved to its maximum deviation from neutral. During controlling of transition, or reversal, of fluid flow in pump (23) and the early stage of upstroke and downstroke, a rotary drive source such as the adjustable speed orbital hydraulic motor (42) controls the movement of pintle control shaft (53) and therefore the position of the swashplate (23a) in hydraulic pump (23).
Pintle control shaft (53) is oscillated by the driven lever (54), fixed at a right angle thereto in the body (50a) of controller (50). Pintle control shaft (53) is mounted for reciprocating rotary motion through a limited range of swashplate (not shown) angle change about its long axis in body (50) by suitable bearings (23a). The motion of driven lever (54) is determined by the position of the drive lever (45) as it is oscillated about the drive lever pivot (46) fixed with respect to body (50a), together with the setting of the cross guide (52), a block which moves axially along the cross guide rod (47) during oscillation of pintle control shaft (53). Cross guide (52) includes an upper and lower pair of crossguide cam rollers (57) which engage the elongated openings (54a) in driven lever (54) and the cooperating elongated openings (45a) of drive lever (45).
The position of cross guide rod (47) is determined by movement toward or away from body (50a) of the controller rods (49). Each of controller rods (49) may be adjusted independently with respect to body (50a) by the adjusting nuts (48) which are affixed to threads in controller rods (49). FIG. 3 shows cross guide rod (47) in a position perpendicular to controller rods (49) which results from equal adjustment lengths for controller rods (49) with respect to body (50a) and the control piston rod (44). This position causes driven lever (54) to oscillate, and thereby pintle control shaft (53) to rotate the swashplate (23a) of hydraulic pump (23) equally in both positive and negative fluid flow directions. Such equal movement from perpendicular, or neutral, position of pintle control shaft (53) causes equal forward and reverse flow in hydraulic pump (23). Unequal adjustment of adjusting nuts (48) with respect to control piston rod (44) would produce unequal motion of driven lever (54) and pintle shaft (53) and thereby produce unequal hydraulic fluid flow to lift cylinder (10) during downstroke and upstroke in polished rod (33) (FIG. 1). The proximity of cross guide rod (47) to drive lever pivot (46) determines the degree of movement during upstroke and downstroke of driven lever (54).
Referring to FIGS. 4 and 5, as both controller rods (49) are moved into the body (50a) of controller (50) by the controller cylinder (24) acting on the control connector (44a), the center of cam rollers (57) approach coincidence with the center of rotation of drive lever pivot (46). Controller cylinder (24) is a two-way cylinder with a piston (not shown) contained therein to drive control piston rod (44) in and out with respect to body (50a). When the center of cam rollers (57) and drive lever pivot (46) are aligned, no movement of driven lever (54) and pintle control shaft (53) will occur despite reciprocation of drive lever (45). That position is neutral, or producing no flow to or from lift cylinder (10) from hydraulic pump (23).
As controller rods (49) are withdrawn from body (50a) by action of controller cylinder (24) (FIGS. 2 and 3), oscillation of drive lever (45) causes greater and greater movement in driven lever (54), which movement reaches a maximum as cross guide cam rollers (57) reach the ends of drive lever slot (45a) and driven lever slot (54a) closest to the center of rotation of pintle control shaft (53). Thus, setting controller rods (49) in and out of body (50a) equally produces different maximum flow to and from hydraulic pump (23) from and to lift cylinder (10) in a pumping cycle. The inequality of preset position between controller rods (49) by unequally adjusting nuts (48) produces unequal oscillatory movement in pintle control shaft (53) as drive lever (45) goes through a complete oscillation representing a complete upstroke and downstroke of the pumping unit piston (10a). Thus, the further controller rods (49) are withdrawn from body (50a), the greater the flow rate of hydraulic fluid to or from hydraulic pump (23).
Drive lever (45) is urged through a cyclical oscillation about drive lever pivot (46) by the controller drive crank (56), which rotates 360 degrees on each complete cycle of pumping unit piston and piston (10a) rod (12) (FIG. 1). A connecting rod (55) joins drive lever (54) and controller drive crank (56). Rotary movement of controller drive crank (56) is caused by two forces in each upstroke and each downstroke of piston rod (12) (FIG. 1). Viewing one complete 360-degree rotation of controller drive crank (56) as a complete upstroke and downstroke of piston rod (12), beginning with pintle shaft (53) in the neutral position (corresponding to the bottom of downstroke of piston rod (12)), the transition, or flow reversal movement of controller drive crank (56) is first controlled by the rotary motion of orbital hydraulic motor (42). Orbital motor (42) turns the motor pulley (42a), which is connected by v-belt or other suitable power transmission means (43) to a v-belt pulley (41) mounted on the controller drive crank axle (56a). Orbital motor (42) turns controller drive crank axle (56a) through approximately 90 degrees of rotation to the midpoint of piston rod (12) (FIG. 1) upstroke, thereby turning pintle shaft (53) to increase swashplate angle in hydraulic pump (23) at a constant rate in the first 90-degree phase to a maximum flow setting. After 90 degrees of rotation, the crank lever (60) mounted on the protrusion of crank axle (56a) through the opposite side of body (50a) drives crank axle (56a) and controller drive crank (56) by action of timing rod (51) through the second 90-degree phase of rotation which overrides the constant increasing flow rate caused by orbital hydraulic motor (42) in the first 90 degrees of rotation and decreases flow from maximum rate to zero.
The second 90 degrees of rotation of controller drive crank (56) is caused by the action of timing rod (51) having closed the gap, or longitudinal free play in the link (58) of timing rod (51). Timing rod (51) in this stage overrides the rotation of orbital motor (42). Link (58) joins two portions of timing rod (51) so that timing rod (51) only operatively links spiral timing shaft (11) with controller (50) in the second and fourth 90-degree quadrants of movement of crank axle (56a) and controller drive crank (56). Although the two phases of rotary movement of controller drive crank (56) caused by orbital motor (42) and timing rod (51) can be set to be of equal speed, it has been found with most applications a slower early phase of upstroke (corresponding to constant increasing flow from hydraulic pump 23) and faster latter stage of upstroke (corresponding to reducing the flow from such pump from maximum to zero flow) reduces stress on the sucker rods and provides them greater longevity. An important feature of the invention is the ability to decrease flow to zero through the hydraulic pump at a rate different from the increasing flow rate, thereby minimizing mechanical stress on the sucker rod string.
Referring now to FIG. 7, a schematic of a 360-degree pumping cycle according to the present invention is shown. The motion of piston rod (12) is shown corresponding to the time required to make such movement. Controller rods (49) have been set to the desired position and speed control (24) has been set to the desired speed or rate of movement for pintle shaft (53). In the lower left quadrant (I) of the graph, orbital motor (42) begins to cause movement of pintle control shaft (53) to start a constant increasing flow of hydraulic fluid to lift cylinder (10). Maximum movement of pintle control shaft (53) in the positive flow direction will be less than the full 22 degrees, so that such flow will be relatively slow, and produce a very smooth acceleration of piston rod (12) upward. In the upper left quadrant (II) of FIG. 7, movement of piston rod (12) sensed and indicated by spiral timing shaft (11) and transmitted by closure of the gap in timing rod (51) is shown. Such movement begins a diminishment of hydraulic flow to zero at a rate faster than the rate of increasing flow utilized in the lower left quadrant (I) (first 90 degrees) of the graph. As flow decreases to zero, and pintle control shaft (53) assumes the neutral position, the hydraulic pump swashplate (not shown) begins movement responsive to the constant speed set in orbital motor (42) to the reverse flow position. Pintle control shaft (53) is driven by orbital motor (42) in quadrant (III) of FIG. 7, since the gap in link (58) in timing rod (51) is now opening and prevents operative control by timing rod (51) of controller drive crank (56). Reverse flow is constant and smooth in acceleration through the midpoint of the downstroke of piston rod (12) (FIG. 1) representing full reverse flow. At such midstroke, the gap in link (58) is now fully open and timing rod (51) again operatively drives pintle control shaft (53) from full reverse flow to zero flow in the lower right quadrant (IV) of FIG. 7 at a rate different, and in this case, faster, than the increasing reverse flow of the upper right quadrant (III) of the graph. No operative force is exerted while the gap in link (58) is closing or opening. Only when the gap is fully opened or fully closed does timing rod (51) operatively override orbital motor (42). When the gap is opening and closing, pintle control shaft (53) is moved by orbital motor (42).
The time in the example above that is allocated to each of the quadrants I-IV is approximately 40%, 25%, 19% and 15%, respectively, of full cycle duration. It may also be seen that such example provides a "slower upstroke" and "faster downstroke", having allocated 66% of cycle time to upstroke, and 34% to downstroke.
Referring now to FIG. 6, the travel of piston rod (12) is plotted graphically against the angle of the swashplate (23a) in hydraulic pump (23). In the cycle designated as "A", a full stroke is illustrated with a slow upstroke and fast downstroke. In cycle "B", a half-stroke, or 1/2 maximum piston travel stroke, is illustrated, with a fast upstroke and slow downstroke. Cycle "A" could be of use in pumping a low viscosity fluid, whereas cycle "B" could be of use in pumping a high viscosity fluid.
Controller (50), after sensing the stage of stroke in lift cylinder (10), then relays the setting for the swashplate angle in hydrostatic pump (23). In the present embodiment, when the position or angle of the swashplate is perpendicular to power shaft (25), there is zero flow of hydraulic fluid between hydrostatic pump (23) and lift cylinder (10). Referring again to FIG. 6, a graphical presentation of piston rod (33) travel on the vertical axis versus flow of hydraulic fluid to and from hydrostatic pump (23) is shown. At the top of the upstroke of piston rod (33) (corresponding to apex of upstroke of the subsurface pump) and at the bottom of downstroke the swashplate of hydrostatic pump (23) has been moved by pintle control shaft (53) perpendicular to power shaft (25) and zero flow of hydraulic fluid is present. Depending upon the desired speed of upstroke and downstroke set by controller cylinder (24), the angle of the swashplate in hydrostatic pump (23) is urged away from the perpendicular relation to power shaft (25) so that at mid-upstroke or mid-downstroke of lift cylinder (10), the swashplate is at its maximum divergence (in negative and positive degrees, respectively) from perpendicularity with power shaft (25). At such position, flow is greatest between hydrostatic pump (23) and lift cylinder (10). As the piston in lift cylinder (10) approaches maximum up- or down-stroke position, the angle of swashplate stem (53) is rotated by pintle control shaft (53) to move the swashplate nearer perpendicularity to power shaft (25), thereby diminishing flow from hydraulic pump (23) and slowing the speed of piston rod (33).
Reversal of flow in hydrostatic pump (23) occurs at maximum upstroke and downstroke of the subsurface pump and the piston in lift cylinder (10). FIG. 6 shows that deviation in angle of swashplate stem (53) (and therefore the swashplate) in one direction (reflected by negative degrees on the graph) produces flow from the hydrostatic pump to lift cylinder (10) from hydrostatic pump (23). In the present embodiment, the swashplate may be deviated from perpendicularity to power shaft (25) by plus 22 degrees or minus 22 degrees. FIG. 4 shows a cycle "A" of 11 degrees negative swashplate angle for slow upstroke and 22 degrees positive angle for fast downstroke. This is the "fast up-slow down" cycle. Also note a fast-up and a slow-down half stroke is illustrated in cycle "B".
Referring again to FIG. 1, an auxiliary hydraulic pump (59) may be utilized to furnish controller (50) fine control power to controller cylinder (24) through the control valve (16) which controls flow in the control piping (18). Hydraulic fluid flows from fluid tank (40) through the control hydraulic supply line (61) to supply auxiliary hydraulic pump (59). Control valve (16) determines the speed of the pumping cycle by the degree of movement of controller rods (49). The length of stroke of the pumping unit is controlled by the setting of rod end bearing (27) in timing lever slot (31). The closer to the center of rotation of such setting, the longer the stroke of piston rod (12). Auxiliary hydraulic pump (59) also supplies hydraulic fluid to orbital motor (42) through control piping (18). Control piping (18) branches through the orbital motor control (63), a flow control valve, to furnish fluid to orbital motor (42). Hydraulic fluid which powers orbital motor (42) and controller cylinder (24) return to fluid tank (40) by the control hydraulic return line (62).
As hydraulic fluid flows from hydrostatic pump (23) to lift cylinder (10), the piston therein and piston rod (12) are forced upward on the power stroke. Flywheel (21) and power source (20) supply the energy in the power stroke to power hydrostatic pump (23). Some of the energy of flywheel (21) is expended in the power stroke, and the speed of flywheel (21) and power source (20) slow slightly. As the subsurface pump and piston rod (33) reach the apex of the stroke, controller (50) has moved the position of the swashplate in hydrostatic pump (23) from a maximum negative angle away from perpendicularity to a position approaching perpendicularity to power shaft (25).
At perpendicularity of swashplate and power shaft (25) (corresponding to zero degrees of swashplate stem oscillation) fluid flow in hydrostatic pump (23) is zero. As piston rod (33) passes the apex of stroke, the weight of the sucker rods now cause the piston in lift cylinder (10) to descend and force hydraulic fluid from lift cylinder (10) through hydraulic power line (19) and through hydrostatic pump (23). The swashplate (not shown) has moved to a slightly positive angle and that angle continues to increase until the midpoint of downstroke. The force of hydraulic fluid through hydrostatic pump (23) causes the power source and the inertial assist to speed up slightly as a result of the addition of kinetic energy from the falling sucker rods to the speed of flywheel (21) and other turning masses in the power train. Thus, kinetic energy from the downstroke of the subsurface pump has been gathered and saved in flywheel (21) for utilization, again after reversing the fluid flow in hydrostatic pump (23), to aid in powering the upstroke of the subsurface pump.
One example of sizing of such a flywheel and its power source would be a 36" diameter, 8" thick 2400-pound steel disc flywheel turned at 2400 r.p.m. with a power source of approximately 30 horsepower. When lifting a 8000-foot string of sucker rods and fluid through a 12-foot stroke, 176,000 foot pounds of power would be expended. A substantial portion of that power will be recaptured during downstroke when flow is forced by the falling rods through hydrostatic pump (23). During upstroke, the speed of the flywheel will diminish to approximately 2300 r.p.m. Approximately 156,000 foot pounds of power would come from the flywheel and approximately 20,000 foot pounds would come from the prime mover. During downstroke, approximately 138,000 foot pounds will be derived from the falling sucker rod mass and, together with approximately 20,000 foot pounds of power from the prime mover, the flywheel will gather sufficient kinetic energy to again turn at 2400 r.p.m. When run in a prototype unit, energy savings were calculated to be approximately 29% compared with such a unit not utilizing a flywheel. This savings was realized because of the even loading on the prime power source.
Thus it can be seen that a novel and efficient controller for hydraulically actuated subsurface pumping has been shown. Application of slowest linear movement of the sucker rod string during the period of greatest tension on the string reduces stress failures. Furthermore, energy can be obtained during the downstroke of the pump and utilized in the power for the upstroke.
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A reversible flow variable rate hydraulic swashplate pump furnishes hydraulic fluid to stroke a piston supporting a subsurface pump. The controller determines reversal of pump flow and timing and speed of upstroke and downstroke of the subsurface pump. No valving restricts hydraulic fluid flow, and energy from the falling mass of the beam and sucker rods is accumulated during downstroke to be utilized during upstroke. The invention also includes the method steps of pumping hydraulic fluid to a cylinder containing a piston supporting the subsurface pump piston at a constant increasing rate until a maximum preset flow is reached, decreasing the flow to zero at a rate different than the increasing rate, reversing the hydraulic fluid flow to flow from the cylinder to the hydraulic pump at a constant increasing rate until maximum preset reverse flow is reached, and reducing reversed flow to zero at a rate different than the increasing flow rate.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to catalysts based on amorphous partially dehydrated zirconium hydroxide (ZrO 2 .xcH 2 O), a process for their preparation and also their use in hydrogen transfer reactions between carbonyl compounds and alcohols, in particular the Meerwein-Ponndorf-Verley reduction and the Oppenauer oxidation. The invention further relates to a process for preparing 3-hydroxyquinuclidine of the formula: ##STR2## by reduction of quinuclidin-3-one of the formula: ##STR3##
2. Background Art
It is known that the hydrogen transfer reactions between aldehydes or ketones and primary or secondary alcohols which are usually carried out under the catalytic action of aluminum alkoxides and summarized under the names "Meerwein-Ponndorf-Verley reduction" and "Oppenauer oxidation" can also be carried out under heterogeneous catalysis [C. F. de Graauw et al., Synthesis, (1994), 1007-1017]. Owing to the easier work-up of the reaction mixture and the fact that the catalyst may possibly be reused, this variant is of great interest. As the heterogeneous catalyst, use has been made, inter alia, of partially dehydrated zirconium hydroxide (hydrous zirconium oxide) [M. Shibagaki et al., Bull. Chem. Soc. Jpn., (1988), 61, 3283-3288; Bull. Chem. Soc. Jpn., (1988), 61, 4153-4154; and Bull. Chem. Soc. Jpn., (1990), 63, 258-259; and H. Kuno et al., Bull. Chem. Soc. Jpn., (1990), 63, 1943-1946; and Bull. Chem. Soc. Jpn., (1991), 63, 312-314]. However, the activity of this catalyst is not very high, so that, particularly when using relatively unreactive carbonyl compounds and/or alcohols, only moderate or poor yields are frequently obtained.
3-Hydroxyquinuclidine is a starting material for the synthesis of various pharmaceutically active compounds such as choline mimetics (U.S. Pat. No. 2,648,667, and European Published Patent Application No. 0370415) or bronchodilators (WO-A-93/06,098). Various methods are known for preparing 3-hydroxyquinuclidine from quinuclidin-3-one (U.S. Pat. No. 2,648,667), namely, the hydrogenation of the hydrochloride using platinum oxide as the catalyst, the reduction of the hydrochloride using sodium/ethanol, the hydrogenation of the free base using platinum oxide or Raney nickel as the catalyst, and also the reduction of the free base with lithium aluminum hydride. However, none of these methods is free of disadvantages. Platinum oxide is very expensive, Raney nickel is pyrophoric and both sodium/ethanol and lithium aluminum hydride as reducing agent lead to safety and waste problems when employed on an industrial scale.
BROAD DESCRIPTION OF THE INVENTION
An object of the invention is to provide a more active heterogeneous catalyst for the Meerwein-Ponndorf-Verley reduction and the Oppenauer oxidation. Another object of the invention is to provide an alternative process for preparing 3-hydroxyquinuclidine, which process is suitable for implementation on an industrial scale, gives little waste and requires neither high pressure nor expensive or hazardous reagents. Other objects and advantages of the invention are set out herein or are obvious herefrom to one skilled in the art.
The objects and advantages of the invention are achieved by means of the catalysts of the invention and the process for preparing 3-hydroxyquinuclidine of the invention.
It has been found that the activity of amorphous, partially dehydrated zirconium hydroxide having a specific surface area by the BET method of at least 50 m 2 /g can be considerably increased by doping with from 0.01 to 20 atom percent (based on Zr) of copper and/or nickel.
The catalyst compositions according to the invention preferably correspond to the formula:
Cu.sub.a Ni.sub.b ZrO.sub.2+a+b.xH.sub.2 O III
wherein, 0≦a≦0.2, 0≦b≦0.2 and 0.2≦x≦2.0, with the proviso that a+b≧0.0001. Particularly preferred catalyst compositions are those in which a≦0.15, b≦0.1, a+b≧0.0002 and 0.3≦x≦2.0. Very particular preference is given to those catalyst compositions in which either copper or nickel is not present, i.e., in which either a=0 or b=0.
The specific surface area by the BET method of the catalyst compositions of the invention is preferably greater than 100 m 2 /g; particular preference is given to catalyst compositions having a specific surface area of more than 150 m 2 /g.
The catalyst compositions of the invention can be prepared, for example, by precipitating zirconium hydroxide from an aqueous solution of a zirconium salt by addition of a base, calcining the zirconium hydroxide at from 200° to 400° C. and subsequently impregnating it with a solution of a copper and/or nickel salt and drying it.
The zirconium salt used is preferably zirconyl chloride (ZrOCl 2 ) and the base used is preferably an aqueous solution of ammonia or an aqueous alkali metal hydroxide solution, such as, sodium hydroxide solution. As the copper and/or nickel salt, preference is given to using the corresponding nitrate.
The calcination temperature is preferably from 250° to 350° C., particularly preferably from 270° to 320° C.
The catalyst compositions of the invention are suitable as the catalyst for the reduction of aldehydes or ketones to the corresponding primary or secondary alcohols by hydrogen transfer from a secondary alcohol as the hydrogen donor (Meerwein-Ponndorf-Verley reduction). The hydrogen donor used here is preferably isopropyl alcohol.
The catalyst compositions of the invention are likewise suitable as the catalyst for the oxidation of primary or secondary alcohols to the corresponding aldehydes or ketones by hydrogen transfer to a ketone or quinone as the hydrogen acceptor (Oppenauer oxidation). As the hydrogen acceptor, preference is given to using cyclohexanone or p-benzoquinone.
The catalyst compositions of the invention can be readily used a plurality of times without any appreciable loss in activity occurring or a significant part of the doping being lost.
It has also been found that quinuclidin-3-one or a corresponding salt, such as, quinuclidin-3-one hydrochloride, can be reduced by means of a secondary alcohol as the hydrogen donor in the presence of amorphous, partially dehydrated zirconium hydroxide (ZrO 2 .xH 2 O) in the manner of a Meerwein-Ponndorf-Verley reduction to give a good yield of 3-hydroxyquinuclidine or the corresponding salt. If the reduction is carried out using a salt of quinuclidin-3-one, the resulting 3-hydroxyquinuclidine salt can, if desired, be converted into the free 3-hydroxyquinuclidine by addition of a strong base during the work-up of the reaction mixture.
The amorphous partially dehydrated zirconium hydroxide can be prepared, for example, by precipitation of zirconium hydroxide from an aqueous zirconium salt solution and subsequent calcination at low temperature. A suitable zirconium salt solution is, for example, a zirconyl chloride solution; a suitable precipitant is, for example, an alkali metal hydroxide solution. The calcination can be carried out, for example, at 270° to 320° C.
In the process of the invention, the secondary alcohol used is preferably isopropyl alcohol. This is dehydrogenated to acetone in the process. Since the reaction is an equilibrium reaction, the secondary alcohol is preferably used in excess in order to shift the equilibrium in the desired direction. The excess secondary alcohol can simultaneously serve as solvent.
The reaction is preferably carried out at a temperature of 120° to 220° C., particularly preferably at 150° to 200° C., in the liquid phase. If the secondary alcohol used has a boiling point at atmospheric pressure below the reaction temperature, the reaction is advantageously carried out at superatmospheric pressure in an autoclave or another suitable pressure vessel.
After the reaction is complete, the catalyst can be separated off very simply by filtration and (if appropriate after a washing procedure) can be reused without any great loss in activity.
DETAILED DESCRIPTION OF THE INVENTION
The following examples illustrate the invention without constituting a restriction.
EXAMPLE 1
Preparation of ZrO 2 .xH 2 O
In a flow-through reactor equipped with a high-speed stirrer (Ultra-Turrax®, 9000 min -1 ), zirconyl chloride solution (265 g/l, calculated as ZrO 2 ) was precipitated semicontinuously using sodium hydroxide solution (30 percent). The addition rate of the zirconyl chloride solution was set such that 50 kg of ZrO 2 was introduced over a period of 5 hours. The sodium hydroxide solution was added via a metering pump at such a rate that the precipitation took place at a constant pH of 8.0. Since this required less than the stoichiometric amount of NaOH, the remainder of the stoichiometric amount was added to the resulting zirconium hydroxide suspension after the precipitation. The suspension was subsequently dewatered in a chamber filter press and the filter cake was washed with deionized water until neutral and free of chloride. The washed filter cake was dried at 100° C. and then introduced into water, whereupon the pieces of filter cake broke up into small pieces. These were dried again at 100° C. and subsequently heated at 30 K/h to 300° C. and calcined at this temperature for 8 hours. The product thus obtained was X-ray-amorphous, had a specific surface area by the BET method of 196 m 2 /g and a pore volume of 0.43 cm 3 /g.
EXAMPLE 2
Preparation of ZrO 2 .xH 2 O
The procedure was as described in Example 1, but the calcination temperature was only 270° C. The product thus obtained was X-ray-amorphous, had a specific surface area by the BET method of 212 m 2 /g and a pore volume of 0.41 cm 3 /g. The water content determined by thermogravimetric analysis corresponded to the formula ZrO 2 .0.57H 2 O. At 430° C., it transformed exothermically into a crystalline form.
EXAMPLE 3
Preparation of ZrO 2 .xH 2 O
Zirconyl chloride octahydrate (ZrOCl 2 .8H 2 O) was dissolved in water. The slight turbidity was filtered off and the filtrate was adjusted to a concentration of 50 g/l (calculated as ZrO 2 ) using deionized water. 2.5 l of deionized water were placed in a reaction vessel fitted with a high-speed stirrer. While stirring vigorously (8000 min -1 ), 50 ml/min of the zirconyl chloride solution was metered in simultaneously with sufficient 10 percent strength ammonia solution to maintain a pH of 7.0±0.2 during the resulting precipitation. At the same time, deionized water was added in an amount sufficient to prevent the solids content of the suspension from exceeding about 1 percent. After the precipitation was complete, the solid was separated off by filtration and the filter cake was washed with ammonia water until the chloride content had dropped to 0.05 percent. The washed filter cake was dried at 100° C., slurried once more in water and again filtered and dried. The zirconium oxide hydrate thus obtained was calcined for 8 hours at 300° C. The product thus obtained was X-ray-amorphous and had a specific surface area by the BET method of 240 m 2 /g.
EXAMPLE 4
Cu 0 .03 ZrO 2 .03.0.61H 2 O
20 g of ZrO 2 .xH 2 O from Example 3 was treated twice with 40 ml each time of a 1.027 M copper(II) nitrate solution for 16 hours each time and after each treatment was washed ten times with water and dried for 12 hours at 120° C./30 mbar. The catalyst composition thus obtained had a copper content of 1.4 percent by weight and a loss on ignition of 8.1 percent, corresponding to the formula Cu 0 .03 ZrO 2 .03.0.61H 2 O. The specific surface area by the BET method was 247 m 2 /g and the pore volume was 0.24 cm 3 /g. Crystallization commenced at 497° C.
EXAMPLE 5
Ni 0 .013 ZrO 2 .013.0.62H 2 O
The procedure was as described in Example 4, but 200 ml of 0.5 M nickel(II) nitrate solution was used in place of the copper(II) nitrate solution and the duration of the first treatment was shortened to 2 hours. The solid was washed 15 times with water after the first treatment and seven times after the second treatment. The catalyst composition thus obtained had a nickel content of 0.6 percent by weight and a loss on ignition of 8.2 percent, corresponding to the formula Ni 0 .013 ZrO 2 .013.0.62H 2 O. The specific surface area by the BET method was 248 m 2 /g and the pore volume was 0.23 cm 3 /g. Crystallization commenced at 495° C.
EXAMPLE 6
Cu 0 .0047 ZrO 2 .0047.0.39H 2 O
In a 1000 ml flask, 100 g of ZrO 2 .xH 2 O (prepared as described in Example 1) was mixed with 400 ml of a 0.276 M copper(II) nitrate solution for 72 hours while rotating slowly (rotary evaporator). Subsequently, the catalyst suspension thus obtained was filtered on a suction filter and the filter cake was slurried with deionized water 25 times and filtered again each time. The filter cake was subsequently extracted with deionized water for 72 hours in a Soxhlet extractor and finally dried for 24 hours at 120° C./30 mbar. The catalyst composition thus obtained had a copper content of 0.23 percent by weight and a loss on ignition of 5.4 percent, corresponding to the formula Cu 0 .0047 ZrO 2 .0047.0.39H 2 O. The specific surface area by the BET method was 219 m 2 /g and the pore volume was 0.44 cm 3 /g. Crystallization commenced at 408° C.
EXAMPLE 7
Ni 0 .00022 ZrO 2 .00022.0.35H 2 O
The procedure was as described in Example 6, but a 0.256 M nickel(II) nitrate solution was used in place of the copper(II) nitrate solution. The catalyst composition thus obtained had a nickel content of 0.01 percent by weight and a loss on ignition of 4.9 percent, corresponding to the formula Ni 0 .00022 ZrO 2 .00022.0.35H 2 O. The specific surface area by the BET method was 217 m 2 /g and the pore volume was 0.44 cm 3 /g. Crystallization commenced at 404° C.
EXAMPLE 8
Cu 0 .016 ZrO 2 .016.0.5H 2 O
50 g of ZrO 2 .xH 2 O from Example 2 was treated twice with 200 ml each time of a 0.505 M copper(II) nitrate solution for 24 hours each time, washed five times with water after each treatment and finally dried for 24 hours at 120° C./30 mbar. The catalyst composition thus obtained had a copper content of 0.74 percent by weight and a loss on ignition of 6.8 percent, corresponding to the formula Cu 0 .016 ZrO 2 .016.0.5H 2 O. The specific surface area by the BET method was 214 m 2 /g and the pore volume was 0.41 cm 3 /g. Crystallization commenced at 456° C.
EXAMPLE 9
Cu 0 .053 ZrO 2 .053.1.35H 2 O
100 g of ZrO 2 .xH 2 O (type XZO 631/02 from MEL Chemicals, Manchester, UK; specific surface area by the BET method=210 m 2 /g, pore volume=0.12 cm 3 /g, crystallization from 419° C.) was treated with 200 ml of a 0.513 M copper(II) nitrate solution for 24 hours, then washed six times with water and finally dried for 24 hours at 100° C./30 mbar. The catalyst composition thus obtained had a copper content of 2.17 percent by weight and a loss on ignition of 16.0 percent, corresponding to the formula Cu 0 .053 ZrO 2 .053.1.35H 2 O. The specific surface area by the BET method was 274 m 2 /g and the pore volume was 0.12 cm 3 /g. Crystallization commenced at 508° C.
EXAMPLE 10
Cu 0 .067 ZrO 2 .067.1.40H 2 O
The procedure was as described in Example 9, but 250 g of ZrO 2 .xH 2 O and 500 ml of 0.513 M copper(II) nitrate solution were used. The number of times the solid was washed was reduced to five. The catalyst composition thus obtained had a copper content of 2.75 percent by weight. The loss on ignition of 16.4 percent corresponded to the formula Cu 0 .067 ZrO 2 .067.1.40H 2 O. The specific surface area by the BET method was 229 m 2 /g and the pore volume was 0.10 cm 3 /g. Crystallization commenced at 520° C.
EXAMPLE 11
Cu 0 .14 ZrO 2 .14.1.90H 2 O
The procedure was as described in Example 9, but 50 g of ZrO 2 .xH 2 O and 120 ml of 0.529 M copper(II) nitrate solution were used. The product was not washed. The catalyst composition thus obtained had a copper content of 5.30 percent by weight and a loss on ignition of 20.3 percent, corresponding to the formula Cu 0 .14 ZrO 2 .14.1.90H 2 O. The specific surface area by the BET method was 229 m 2 /g and the pore volume was 0.10 cm 3 /g. Crystallization commenced at 564° C.
EXAMPLES 12 AND 13
Comparative Example 1
trans-2-Hexenol (Meerwein-Ponndorf-Verley reduction)
In a round-bottomed flask provided with magnetic stirrer and reflux condenser, 0.5 g (5.1 mmol) of trans-2-hexenal, 12 g of isopropyl alcohol and 3.9 g of catalyst were heated under reflux. After the end of the reaction time, the reaction mixture was analyzed by gas chromatography and the yield was determined. The results are summarized in Table 1 below:
TABLE 1______________________________________ Reaction time Example No. Catalyst [h] Yield [%]______________________________________C1 From Example 3 (undoped) 8 77.4 12 from Example 4 7 88.0 13 from Example 5 7 79.2______________________________________
EXAMPLES 14 TO 20
Comparative Examples 2 and 3
Cinnamic alcohol (Meerwein-Ponndorf-Verley reduction)
In a three-necked flask provided with reflux condenser and magnetic stirrer, 0.5 g (3.8 mmol) of cinnamaldehyde (trans-3-phenyl-2-propanol) and 12 g of isopropyl alcohol (for a starting material/catalyst ratio=1:1) or 1.5 g (11.3 mmol) of cinnamaldehyde and 36 g of isopropyl alcohol (starting material/catalyst=3:1) were refluxed under argon with 0.5 g of catalyst and 1.5 g of dodecane (as GC standard). After the end of the reaction time, the reaction mixture was analyzed by gas chromatography and the yield was determined. The results are summarized in Table 2 below:
TABLE 2______________________________________Example Reaction Starting No. Catalyst time [h] Yield [%] material/catalyst______________________________________C2 from Example 1 24 63.8 1:1 (undoped) C3 MEL*.sup.) (undoped) 24 44.5 3:1 14 from Example 6 24 72.4 1:1 15 from Example 4 24 97.3 1:1 16 from Example 9 22.3 100.0 3:1 17 from Example 9 19.2 98.5 3:1 18 from Example 10 6.5 100.0 3:1 19 from Example 11 3.3 99.5 3:1 20 from Example 5 24 89.3 1:1______________________________________ *.sup.) Type XZO 631/02, MEL Chemicals, Manchester, UK(ZrO.sub.2 · xH.sub.2 O)
EXAMPLES 21 TO 23
Comparative Example 4
1-(p-Chlorophenyl)ethanol (Meerwein-Ponndorf-Verley reduction)
In a round-bottomed flask provided with magnetic stirrer and reflux condenser or in a 100 ml autoclave, 5.0 g (32.3 mmol) of p-chloroacetophenone, 45 g of isopropyl alcohol and 1.0 g of catalyst were heated under reflux or at 120° C. After the end of the reaction time, the reaction mixture was analyzed by gas chromatography and the yield was determined. The results are summarized in Table 3 below:
TABLE 3______________________________________ Example No. Catalyst Reaction time* .sup.) [h] Yield [%]______________________________________C4 From Example 1 24 (R) 22.5 (undoped) 21 From Example 4 24 (R) 38.9 22 From Example 9 24 (R) 69.7 23 From Example 9 16 (A) 94.2______________________________________ *.sup.) (R) = reflux; (A) = autoclave
The experiment of Example 22 was also repeated a further five times using the same catalyst sample, with the copper content of the catalyst being checked after each repetition. Neither a significant yield change nor a reduction in the copper content of the catalyst was observed.
EXAMPLES 24 AND 25
Comparative Example 5
3-Methyl-2-buten-1-ol (Meerwein-Ponndorf-Verley reduction)
In a round-bottomed flask provided with magnetic stirrer and reflux condenser or in a 100 ml autoclave, 3.0 g (35.7 mmol) of 3-methyl-2-butenal, 72 g of isopropyl alcohol and 1.0 g of catalyst were heated under reflux or at 110° C. After the end of the reaction time, the reaction mixture was analyzed by gas chromatography and the yield was determined. The results are summarized in Table 4 below:
TABLE 4______________________________________ Example No. Catalyst Reaction time* ) [h] Yield [%]______________________________________C5 From Example 2 24 (R) 3.8 (undoped) 24 From Example 10 30 (R) 86.5 25 From Example 10 18 (A) 91.5______________________________________ *.sup.) (R) = reflux; (A) = autoclave
EXAMPLES 26 AND 27
Comparative Example 6
Cinnamaldehyde (Oppenauer oxidation)
1.5 g (11.2 mmol) of cinnamyl alcohol (trans-3-phenyl-2-propen-1-ol), 36 g (367 mmol) of cyclohexanone, 0.5 g of catalyst and 1.5 g of dodecane (as GC standard) were heated under argon. After the end of the reaction time, the reaction mixture was analyzed by gas chromatography and the yield was determined. The results are summarized in Table 5 below:
TABLE 5______________________________________ Reaction Temperature Example No. Catalyst time [h] [° C.] Yield [%]______________________________________C6 MEL*.sup.) (undoped) 24 100° 37.1 26 from Example 10 24 60° 56.4 27 from Example 9 5.5 120° 67.2______________________________________ *.sup.) Type XZO 631/02, MEL Chemicals, Manchester, UK(ZrO.sub.2 · xH.sub.2 O)
EXAMPLE 28
Acetophenone (Oppenauer oxidation)
5.0 g (40.9 mmol) of 1-phenylethanol, 15.0 g (153 mmol) of cyclohexanone and 1.0 g of catalyst from Example 9 in 30 g of toluene were heated at 70° C. under argon. After a reaction time of 10 hours, the reaction mixture was analyzed by gas chromatography. The yield of product was 94.2 percent.
EXAMPLE 29
Comparative Example 7
Benzaldehyde (Oppenauer oxidation)
1.5 g (13.9 mmol) of benzyl alcohol, 3.0 g (27.8 mmol) of p-benzoquinone and 0.5 g of catalyst in 26 g of 1,4-dioxane were refluxed under argon. After a reaction time of 24 hours, the yield was determined by gas chromatography. The yield obtained using the catalyst according to the invention from Example 10 was 55.6 percent; and a yield of only 23.6 percent was obtained using the undoped catalyst from Example 2, which is not according to the invention.
EXAMPLE 30
3-Hydroxyquinuclidine
A 100 ml autoclave ("Magnedrive II", Autoclave Engineers Europe) fitted with a hollow-shaft high-speed stirrer (Dispersimax®) was charged with 5.0 g of quinuclidin-3-one (prepared from the hydrochloride by reaction with sodium methoxide and extraction with diethyl ether), 45 ml of isopropyl alcohol and 0.25 g of catalyst (from Example 1), flushed with nitrogen and placed under a nitrogen pressure of 10 bar at room temperature. While stirring (1500 min -1 ), the mixture was heated to 200° C. and held at this temperature for 8 hours. The yield was determined as 97.3 percent by means of GC. Repeating the experiment using the same catalyst still gave a yield of 92.8 percent after a reaction time of 13 hours.
EXAMPLE 31
3-Hydroxyquinuclidine
In an autoclave, 81.6 g (0.496 mol) of quinuclidin-3-one hydrochloride and 12.4 g of catalyst (from Example 1) were suspended in 800 ml of isopropyl alcohol while stirring vigorously. The autoclave was closed and the air present was displaced by argon under atmospheric pressure. The autoclave was then heated to an internal temperature of 150° C., whereupon a pressure of 6 to 8 bar was established, and held at this temperature for 7 hours. After cooling to room temperature, 89.5 g of a 30 percent strength solution of sodium methoxide in methanol was added. The mixture was stirred further for 45 minutes and then filtered. The filtrate was evaporated under reduced pressure and the residue was recrystallized hot from 640 ml of toluene. The catalyst was washed until free of salt and dried, after which it could be reused. The yield of the catalyst was 59.2 g (93 percent), and the assay (GC) of the catalyst was 99 percent.
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Catalyst compositions based on amorphous partially dehydrated zirconium hydroxide which are doped with from 0.01 to 20 atom percent of copper and/or from 0.01 to 20 atom percent of nickel, in each case based on zirconium, and have a specific surface area by the BET method of at least 50 m 2 /g. The catalyst compositions are suitable, in particular, as the catalyst in hydrogen transfer reactions, such as, the Meerwein-Ponndorf-Verley reduction or the Oppenauer oxidation. The preparation of 3-hydroxyquinuclidine of the formula: ##STR1## involves reaction of quinuclidin-3-one with a secondary alcohol in the presence of the amorphous partially dehydrated zirconium hydroxide.
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BACKGROUND OF THE INVENTION
The invention relates to the combination of a electrical motor and generator and more particularly, to a single device performs both starter motor and alternator functions in a vehicular engine system.
In general, an electromagnetic machine can be operated either as a motor or as a generator depending respectively upon whether power is delivered to the unit from an external source of electrical energy or whether the unit is mechanically driven by an external source of mechanical energy, such as an internal combustion engine.
The subject invention comprises a structure particularly adapted for automotive applications which permits the combination of the starter motor function and the generator (generic DC or AC) or alternator (AC) function in a unique package to take advantage of the motor/generator characteristics described above. The subject invention lends itself to being positioned between the internal combustion engine and the transmission in the drive train of an automobile, making use of either the fly wheel or the torque convertor as part of the system. This is in contrast to the traditional location of a separate conventional automotive starter motor which is momentarily connected to the fly wheel on the engine during the cranking or starting cycle, and the traditional location of a separate generator or alternator which is typically belt driven from the crankshaft of the engine. Since these functions of the starter and alternator are combined, the unit arranged in accordance with the principles of the invention may be located in line between the engine and transmission, thereby eliminating the need for being belt or gear driven and to take advantage of the fact that only one motor/generator unit will be used in place of two units, as in present conventional arrangements.
Various approaches in producing a dual purpose starter generator machine for use on motor vehicles have been developed since the early 1900's. For example, U.S. Pat. No. 1,250,718 to Turbanyne, issued Dec. 18, 1917, discloses a DC motor/generator having a rotating armature that is ring wound. When operated as a DC motor, DC current is supplied to the rotor through conventional commutator brushes.
Another starter generator is disclosed in U.S. Pat. No. 1,325,677 to Midgley, issued Dec. 23, 1919. In this design, a conventional DC machine having a wound rotor is fitted with four brushes on the commutator ring. One of these brushes is movable away from the commutator. Movement of the movable brush serves to engage or disengage an automatic circuit as a voltage regulation device when the machine is operated as a generator. When operated as a DC motor, the movable brush effectively disengages the automatic circuit by connecting the circuit across two brushes of the same polarity.
Another example of a starter generator machine is disclosed in U.S. Pat. No. 2,184,236 to Heintz, issued on Dec. 19, 1939. In this machine, in addition to conventional slip rings and brushes for energizing the windings on the rotor during generator and motor operation, the rotor is fitted with rotatable brushes. These rotatable brushes are in engagement with a stationary commutator which feeds low voltage direct current to the stator windings during the engine cranking operation. The rotating brushes are moved out of engagement with the commutator by centrifugal force as the engine crankshaft is accelerated. Thus, in this design, the rotatable brushes provide a rotating stator magnetic field for operation of the device as a motor. When operating as a generator, the Heintz device produces alternating current.
In a more recent starter motor alternator disclosed in U.S. Pat. No. 4,219,739 to Greenwell, issued Aug. 26, 1980, the main rotor winding is connected in series with the main stator winding. In addition, the exciter armature winding is on the rotor and the exciter field winding is on the stator. During starter motor operation, the main rotor winding is connected in series with the starter field winding through a commutator and conventional DC brushes. During alternator operation, the brushes are lifted off the commutator, and the exciter armature winding slip rings are connected to the main rotor winding.
In all of the above examples, external current is fed through a commutator to the windings on the rotor. The current carried by the conductor in the magnetic field produces a torque which causes rotation of the machine as a motor. When operated as a generator or alternator, current is once again fed through a commutator or slip rings to windings on the rotor to provide excitation. These dual purpose motor generator sets have a variety of disadvantages. In any conventional dual purpose machine, certain sacrifices must be made in order to accommodate both generator and motor functions in a single device. For example, previous conventional motor generator designs for use in a motor vehicle such as an automobile or an aircraft have a low power to size ratio, are relatively expensive, and have a high length to diameter ratio. It has therefore been impractical to develop a combined motor generator design for use in automotive engine systems.
The dual purpose machine concept has primarily been utilized in aircraft. However, these machines are extremely complex to manufacture with resultant high cost. Because of the power requirements, overall size and complexity of a conventional motor generator or dual starter motor alternator of conventional design, automotive vehicles utilize separate starter motors and alternators in past practice.
The disadvantages of conventional starter motor designs include very high noise during operation, a low electri-mechanical efficiency, relatively large size requirements, high motor weight and battery size requirements and low reliability. In addition, the necessity for providing a separate alternator increases the overall space allocation requirements for the alternator and starter motor functions.
A known approach to providing a combined starter motor/alternator system is set forth in U.S. Pat. No. 4,862,009 to King. The King patent discloses a combined starter/alternator which may be coupled directly to the vehicle drive train and which may take the form of a permanent magnet motor/alternator machine. The King system utilizes a three phase invertor in the starter mode with an electronic commutation system which uses Hall-effect sensors. Torque multiplication is achieved via a modified planetary gear assembly.
One prior approach to providing motor/generator units having a flat, non-magnetic ironless stator which could be mounted to the drive train of the vehicle is disclosed in U.S. Pat. No. 5,001,412 to Crall et al., issued Mar. 19, 1991, and assigned to the same assignee as the instant invention. However, it has been found that under high speed engine operating conditions, eddy current losses significantly increase in the flat planar windings utilized in the stator of the Crall et al. prior invention.
There also is seen to be a need for a drive circuit in the motor operating mode providing improved protection for the switching devices used therein when subjected to high reverse bias voltages resulting from high speed engine operation with the electrical machine operating in the alternator mode.
SUMMARY OF THE INVENTION
Accordingly, in a first aspect of the invention, apparatus for producing alternating current flow in the stator winding of a motor from a direct current energy source includes a first switch capable of withstanding high reverse bias voltage, such as a silicon controlled rectifier, coupled between the direct current energy source and a first end of the stator winding, a second switch capable of withstanding high reverse bias voltage, such as a silicon controlled rectifier, coupled between the direct current energy source and a second end of the stator winding, a thirth switch coupled between ground potential and a the first end of the stator winding, a fourth switch coupled between ground potential and a second end of the stator winding, and a controller for alternately (a) rendering the first and fourth switch conducting so as to establish current flow through the stator winding in a first direction, and (b) rendering the second and third switches conductive so as to establish current flow through the stator winding in a second direction.
In another aspect of the invention, a combined starter motor and alternator for a vehicular engine system having a rotatable power shaft and a source of direct current energy includes a support plate coupled to and rotatable by the power shaft and carrying a plurality of permanent magnets lying in a plane substantially perpendicular to a longitudinal axis of the power shaft, a magnetic flux return plate spaced from the support plate axially along the power shaft axis and coupled to the power shaft for rotation therewith, a stator assembly surrounding the power shaft and positioned between the support plate and the magnetic flux return plate, the stator assembly including at least one phase winding comprised of stranded conductive wire, at least a portion of the turns of the stranded winding lying in planes substantially perpendicular to the power shaft axis, the stranded winding undulating radially inwardly and outwardly of the axis of the shaft. Additionally, the combined starter motor and alternator includes apparatus for directing electrical current from the direct current energy source through the phase windings so as to produce mechanical torque on the shaft in a starter motor mode of operation and a conduction controller for regulating alternator output current from the phase winding when the machine is in an alternator mode of operation.
The construction of the ironless stator assembly housing using non-magnetic materials keeps the axial thickness of the stator assembly as small as possible. The use of non-magnetic materials along with the absence of iron losses and bearing losses and the absence of a need for a separate enclosure due to the utilization of the enclosure provided by the engine and transmission provides a much higher efficiency and output per unit weight ratio compared to conventional starters and alternators. Because there is no iron in the stator assembly body, iron losses developed in the alternator starter are extremely low.
When operated as a starter motor, a sensing mechanism dictates which of the three phase stator windings should be energized and in what sequence in order to produce a constant torque on the power shaft of the vehicle as the support plate containing the permanent magnets rotates with the shaft. The magnetic flux path and direction of the magnetic field from the permanent magnets through an air gap positioned between the magnet support and flux return plates and through the return plate and back to the opposite side of the magnets via the support plate, remains constant and does not change direction as with conventional motors and generators. Consequently, hysteresis and eddy current losses are minimized, and heating in the plates is minimized.
A variety of sensing mechanisms may be utilized. For example, an optical sensor could be utilized to sense position of appropriate marks on the magnet support plate as it rotates. Any suitable mechanism that is correlated to the position of each permanent magnet segment during the magnet plate rotation may be utilized to trigger or appropriately energize the stator windings. For example, in the disclosed embodiment, a set of Hall-effect switching devices is utilized to switch the current within each set of phase windings in the proper order.
Once the vehicle engine is started, the power to the Hall-effect switches is cut off, as the electrical machine is now in the alternator operating mode. When operated as an alternator, sensing the relative positions of the magnets is no longer required. Rotation of the permanent magnets fixed to the disc on the vehicle crankshaft causes a rotating flux which cuts the stationary stator phase windings. This relative motion produces an electromotive force (EMF) in the stator winding proportional to the number of lines of flux cut, the number of conductors (i.e. the number of winding turns), and the speed of relative motion. Since the number of conductors and the total flux is constant, the induced EMF will vary proportional to the speed of rotation of the power shaft or crankshaft of the vehicle.
The stator windings may be connected in three phase delta or wye connection or, preferably, used independently. One of the three phase windings could be utilized to produce DC output to charge the vehicle battery as well as energize appropriate DC circuits within the vehicle. The other two phase windings may remain unused or could be utilized for other purposes such as to produce a regulated AC output for various devices requiring an AC supply. Sufficient output is produced by the present invention so that a single phase may be utilized to provide all DC requirements of a motor vehicle as presently in use.
Present design requirements in automobiles are within the output production capability of a single phase winding of an alternator starter arranged in accordance with the principles of the invention. Alternatively, all three phases of the stator could be coupled via a full wave rectifier circuit into an appropriate voltage regulation circuit to provide total DC output. In such a case, the achievable DC current output far exceeds the electrical requirements of a typical automobile. It is also preferable to use all three stator phases due to the resulting decrease in output ripple.
Other embodiments of the invention are envisioned wherein the stationary components are reversed. In other words, the ironless stator may be rotated with magnets remaining stationary with respect to the rotation of the engine's crankshaft.
BRIEF DESCRIPTION OF THE DRAWINGS
The objects and features of the invention will become apparent from a reading of a detailed description, taken in conjunction with the drawings, in which:
FIG. 1 is a cross-sectional view of a combined motor starter and alternator assembly arranged in accordance with the principles of the invention;
FIGS. 2A and 2B present front and side plan views, respectively, of the magnetic flux return plate 200 of FIG. 1;
FIGS. 3A and 3B respectively set forth front and side plan views of magnet support plate 300 of FIG. 1;
FIGS. 4A and 4B respectfully depict a front plan view and a side cross-sectional view of stator assembly 400 of FIG. 1;
FIG. 4C depicts a front view of stator assembly 400 showing the arrangement of the stranded wire stator phase windings;
FIG. 5 is a diagram of an enlarged portion of a stator phase winding showing the axial and radial stacking thereof;
FIG. 6 is a functional block diagram of the electronic control circuitry utilized in both the starter motor and alternator modes of operation of an electromagnetic machine arranged in accordance with the principles of the invention;
FIG. 7 is a schematic diagram of a conventional H-switch drive circuit for a stator winding of a machine operating in a motor mode;
FIG. 8 is a waveform setting forth a typical phase winding voltage cycle when the electrical machine of the invention is operating in an alternator mode;
FIG. 9 is a schematic circuit diagram of the controller circuitry and H-driver circuits 607 for phase one winding P1 of FIG. 6;
FIG. 10 is a circuit schematic diagram of the phase angle controller 613 associated with winding P1 of FIG. 6;
FIG. 11 is a functional circuit schematic diagram of the circuitry of regulator controller 623 of FIG. 6;
FIG. 12 is a functional block diagram of the mode control circuit 621 of FIG. 6; and
FIG. 13 is a functional schematic of high frequency clock 625 of FIG. 6.
DETAILED DESCRIPTION
The mechanical arrangement of a combined starter motor and alternator following the principles of the invention is set forth in FIGS. 1-5. With reference to FIG. 1, the combined starter motor and alternator is a relatively thin disk shaped combined apparatus which encircles the power or crankshaft 100 of an automotive vehicle. The term power shaft or crankshaft refers to any type of shaft rotatable by the vehicle's engine. Mounting flange 102 of crankshaft 100 provides threaded bores for the receipt of mounting bolts 104, which couple a magnetic return plate 200 and a permanent magnet support plate 300 to the crankshaft for rotation therewith.
Plates 200 and 300 have outer annular disk portions which are spaced along longitudinal axis 106 of shaft 100 so as to provide an annular channel therebetween. In this channel is positioned a stator assembly 400 which does not rotate with rotation of crankshaft 100, and a plurality of permanent magnets 108 which are carried by plate 300 for rotation therewith.
As seen from FIGS. 2A and 2B, magnetic return plate 200 takes the form of a substantially circular disk having an annular outer stator winding cover portion 202, an inner annular stator assembly receiving cavity or depression 204, a central mounting flange portion 206, and a central bore 210 for receiving annular hub 310 of magnet mounting plate 300 (FIGS. 3A and 3B). Central mounting flange portion 206 includes a polarity of bores 208 for receipt of the mounting bolts 104 (FIG. 1).
As seen from FIGS. 3A and 3B, magnet support plate 300 is a substantially circular disk having an outer annular area 302 providing mounting positions for a plurality of permanent magnets. For example, if a 15 degree arcuate sector is provided for each permanent magnet, then 24 such magnets may be mounted in area 302. Magnet support plate 300 additionally includes an axially extending magnet retention flange portion 304 at the plate's radially outer rim, along with a central mounting annular section 306, which includes a plurality of mounting bolt receiving bores 308. Bores 308 are aligned with bores 208 (FIG. 2B) of magnetic flux return plate 200. Magnet support plate 300 additionally includes a central annular hub portion 310, the outer diametrical portion of which engages the mounting flange portion 206 of flux return plate 200 (FIGS. 2A, 2B), and the inner diameter of which abuts a hub portion 110 (FIG. 1) of crankshaft mounting flange 102. Magnet support plate 300 also includes a central crankshaft mounting flange hub receiving bore 312, which receives hub portion 110 of crankshaft 100 (FIG. 1).
FIGS. 4A and 4B set forth further details of the stator assembly 400 of FIG. 1, shown minus the stator phase coil windings embedded therein for clarity. The body of stator assembly 400 is an ironless, non-magnetic material such as a glass and resin matrix. The body includes a central annular portion 402 which encases straight portions 502 (FIG. 5) of stranded wire stator winding turns. Outer flange portion 404 of stator assembly 400 encases or encapsulates outer arcuate portions 504 of stranded wire stator turns (see FIG. 5), while inner flange portion 406 encases or encapsulates inner arcuate portions 506 of stranded wire stator winding turns. Stator 400 additionally includes a central bore 408 for receipt of mounting flange 206 of return plate 200 and mounting annulus 306 of magnet mounting plate 300. Central bore 408 provides clearance between elements 206 and 306 (see FIG. 1, for example) such that magnetic return plate 200 and magnet plate 300 will rotate with crankshaft 100, while stator 400 will remain stationary in the annular space provided therebetween.
With reference to FIG. 4C, the general positioning arrangement of stranded wire stator windings 410, which are encapsulated in the glass and resin matrix of the stator assembly is depicted. In the embodiment shown and described herein, stator assembly 400 includes three phase windings undulating radially inwardly and outwardly between portions 404 and 406 of stator assembly 400, as one traverses stator 400 circumferencially about a longitudinal axis of the crankshaft in a plane or planes substantially perpendicular thereto. 412A and 412B designate the beginning and ending ends of the winding for phase one, respectively. 414A and 414B respectively designate the beginning and ending ends of the winding for stator winding phase two, while 416A and 416B respectively designate the beginning and ending ends of the winding for stator phase 3. It is to be noted that the stranded wire stator phase windings are confined to as narrow a stator body axially extending portion as possible to achieve the goal of placing as much winding conductive material as possible into the stator. This is due to the fact that an increased stator axial length would lead to a requirement for stronger permanent magnets to achieve the same alternator output power or starter motor torque in the same machine.
Further details of how each phase winding of the stator are configured are set forth in FIG. 5. As seen from FIG. 5, each undulating turn of the phase winding as the turn proceeds around the annular ring 402 of stator 400 includes straight portions 502 which are embedded in annular portion 402, outer arcuate portions 504 embedded in flange portion 404, and inner arcuate portions 506 encapsulated or embedded in flange portion 406. The specific shape of the undulating turns is dictated by a plurality of winding guide pins 508 which extend from an inner face of a molding tool for the glass and resin matrix stator body. It is to be noted that the multiple turns of each phase winding are stacked both axially along the longitudinal axis of the crankshaft and radially in planes substantially normal to the crankshaft axis. In the specific embodiment shown in FIG. 5, four turns are provided in each phase winding housed by stator 400. It should also be noted that it is contemplated that in fabricating the encapsulated stator windings in stator assembly 400, the winding guide pins 508 of FIG. 5 are removed from the mold prior to the actual formation of the stator housing.
FIG. 5 sets forth the arrangement for the phase one stator winding, which begins at 412A. In the view of FIG. 5, only two of the four undulating windings are visible in most of the diagram. The four turns are designated 1, 2, 3 and 4. It will be understood that turn 1 lies, for the most part, directly underneath turn 2, while turn 3 lies, for the most part, directly above turn 4. As seen in FIG. 5, the beginning of the winding at 412A proceeds into the commencement of winding turn 1. Turn 1 undulates radially inwardly and outwardly of the stator body directly beneath winding 2, making a full circle about the annular housing area to back near the starting point where turn 1 then becomes turn 2, which is wound directly axially on top of turn 1. Turn 2 likewise undulates in a complete circle through the annulus until it comes to a transition area 510 where turn 3 begins in substantially the same plane as turn 2, but spaced therefrom in that plane. Turn 3 then traverses the annular area in a complete circle and returns directly underneath the transition area 510, where turn 4 begins underneath turn 3. Turn 4 then likewise undulates in a complete circle until it is brought out as a terminating end 412B. It will be appreciated that, as space permits, more turns may be axially and radially stacked in the stator body.
Electronic circuitry control aspects of the invention are set forth in FIGS. 6-13. With reference to FIG. 6, a functional block diagram of the control circuitry for the starter motor and alternator modes of operation of the inventive arrangement is set forth. For each phase winding in the stator, three in this embodiment, the starter motor mode of operation requires a polarity detection and current switch drive control per phase winding. Magnetic polarity detection is provided by Hall-effect switches 601, 603, and 605, which are respectively located adjacent phase windings P1, P2, and P3 in stator body 400 of FIG. 1. Phase 1 detector device 601 has outputs 650 and 652 coupled to H-driver and control circuit 607, which is coupled via leads 654 and 656 to opposite ends of stator phase winding P1 and to inputs of phase angle control circuit 613 for phase one winding P1.
Phase control 613 has an output 644a coupled via bus 644 to the vehicular battery or direct current energy source 619. Battery 619 is additionally coupled via bus 640 to the various loads circuits in the automotive engine system and via bus 642 to H-switches 607, 609, and 611.
The arrangement set forth above is replicated for phases 2 and 3, as shown in FIG. 6. Polarity detector 603 has outputs 660 and 662 coupled to inputs of H-switch and control circuit 609, which has its outputs coupled to opposite ends of stator phase winding P2 via leads 664 and 666, which also are coupled to inputs of conduction phase angle controller 615. Controller 615 is coupled via its output 644b to bus 644.
The polarity detector for the third stator phase winding P3 is designated 605 and has its outputs 670 and 672 coupled to inputs of H-driver and control circuitry 611, which has outputs coupled across phase winding P3 via lead 674 and 676, which are also coupled to inputs of conduction phase angle controller 617. Controller 617's output 644c is coupled to bus 644 to battery 619 and the vehicular electrical load.
Enabling power for detectors 601, 603 and 605 is furnished via bus 630 from mode controller 621 in the starter motor mode of operation of the device. The selection of the starter motor mode or the alternator mode of operation is selected from an engine control computer (not shown) which passes appropriate selection signals to controller 621 via bus 638.
The mode control signal on bus 630 is additionally passed to an input of regulator control circuit 623. Regulator control 623 is operative only during the alternator mode of operation and passes phase delay control data via bus 634 to phase angle controllers 613, 615 and 617. Additionally, in the alternator mode of operation, controllers 613, 615, and 617 are disabled via signals on bus 632 emanating from mode controller 621. The specific disabling signals are coupled to controllers 613, 615, and 617 by bus portions 632a, 632b, and 632c, respectively.
A high frequency clock circuit 625 supplies timing signals on bus 636 to conduction angle controllers 613, 615, and 617.
Before discussing further details of the functional blocks set forth in FIG. 6, reference is made to FIG. 7 which depicts a conventional switch arrangement for a stator coil in a motor operating mode. The switch arrangement is commonly referred to as an H-driver, due to the configuration of the four switches with respect to the stator winding P.
Alternating current through phase winding P is generated by the H-switch circuit by alternately closing switch SW1 and SW4 and opening SW2 and SW3 to provide for current flow from the DC energy source in a direction indicated by the arrow 702, and later in time by simultaneously closing switches SW2 and SW3 and opening SW1 and SW4 to generate current flow in a direction shown by arrow 704.
In the alternator mode of operation, all switches SW1 through SW4 are to remain open or non-conductive, and the induced voltage across and current through winding P is then controlled by the conduction phase angle controller which is also coupled to winding P. In the alternator mode of operation for a vehicular engine system, as the engines speed increases, switches SW1 and SW3 will see a very high reverse potential thereacross due to the high induced voltage at stator coil P. By "high reverse voltage" is meant on the order to ten times the normal forward bias voltage seen by such switches--i.e. ten times the potential level of the DC energy source of the vehicle represented by V BAT . Such a voltage ratio will occur as the engine speed goes above the cranking speed of the motor. Hence, for such an automotive application, it has been determined that switches SW1 and SW3 should be power switching devices exhibiting a resistance to breakdown or reverse conduction, even in the presence of such high reverse bias voltages. As will be seen in a later detailed description of the H-circuit of this invention, the reverse bias problem has been overcome by utilizing silicon controlled rectifier power switches for elements SW1 and SW3.
In the alternator mode of operation of the machine embodying the invention, each phase is given a preselected current conduction time through the respective phase winding, in accordance with a control arrangement which modifies the conduction time per half cycle of the induced voltage waveform, in accordance with the amplitude of the induced voltage with respect to the potential level of the battery or direct current energy source. As seen from FIG. 8, each phase angle conduction controller 613, 615, and 617 (FIG. 6) is given a desired delay time d designated as 804 which is utilized to inhibit current flow through the associated phase winding until the time delay d has expired. Delay d is measured from a preselected induced voltage level which is just above a zero crossing of the induced voltage. This trigger level can, in theory, lay anywhere between the zero and DC level 802 shown in FIG. 8. The conduction time c then takes place for the remaining half cycle of the induced voltage wave form, as seen in FIG. 8.
Hence, the alternator output voltage (i.e. the average value thereof) will be modified as the conduction time is modified. As the engine system electrical load increases, the induced voltage will decrease, therefore requiring a larger conduction time c, or correspondingly a smaller delay time d, such that the average value of the alternator output voltage may be increased to meet the load requirements of the system. It will therefore be seen that each phase conduction angle controller 613, 615, and 617 of FIG. 6 should include a level crossing detector, a delay element, and output power switches whose conduction states are inhibited until the expiration of the desired delay time. Additionally, a regulator controller compares the level of the alternator output voltage with a predetermined reference and either increases or decreases the delay time provided by the conduction angle controllers. Further details of a specific embodiment will be explained below.
FIG. 9 sets forth further details of the circuit arrangement of the H-switch and controller therefor, 607 of FIG. 6, which is associated with the first stator phase winding P1. It will be understood that the details for elements 609 and 611 of FIG. 6 are identical to those set forth for element 607. Additionally, identical reference numerals are used for the same leads and elements common to more than one of FIGS. 6 through 13. With the arrangement shown in FIG. 6, with replicated control circuitry for each phase winding, the system is controlled as if three separate single phase motors were present.
As mentioned previously, each stator phase winding has associated therewith a plurality of detection switches, such as switch 601 of FIG. 9. Switch 601 could, for example, comprise a commercially available Hall-effect switch type UGN3235K, marketed by Allegro Microsystems. Hall-effect switch 601 has two open-collector, independent outputs which respond to magnetic flux of a predetermined polarity. Output 650 of switch 601 goes to ground in the presence of a north pole of a magnet, while output 652 goes to ground in the presence of a south pole.
Hall-effect switch output 650 is coupled to a junction of resistor 902a and capacitor 904a, and via resistor 916a to a base electrode of switching transistor 920a. Capacitor 904a has a second terminal coupled as an input to a one-shot multivibrator comprised of resistor 906a, capacitor 908a and transistor 910a, all connected as shown in FIG. 9.
The output of the one-shot multivibrator at the collector electrode of transistor 910a is coupled to the base electrode of transistor 920a via resistor 914a, and to bias voltage V DD via resistor 912a. A collector electrode of transistor 920a is coupled to its base electrode via capacitor 918a and to bias potential via resistor 950a. The collector electrode of transistor 920a is additionally coupled via resistor 922a to a gate electrode of field effect transistor 926a.
A source electrode of field effect transistor 926a is coupled via resistor 924a to the vehicle's direct current energy source designated 48 V, and to optically coupled silicon controlled rectifier (SCR) switch 930a. A drain electrode of field effect transistor 926a is coupled to an input for enabling Darlington connected power transistor package 940a. The output of the optically coupled SCR circuit 930a is coupled to a gate electrode of SCR 938b.
As seen from FIG. 9, the circuit arrangement for output 652 of Hall-effect switch 601 is a replication of the circuitry whose structure is set forth above for output 650. Corresponding circuit elements bear the suffix b, rather than a, for the elements associated with switch output 652.
An anode electrode of SCR 938a is coupled to the vehicle's battery, while the cathode electrode of SCR 938a is coupled via path 654 to one end of stator phase winding P1. The output current conducting circuit of Darlington stage 940a is coupled between ground potential and lead 654. In a similar manner, SCR 938b has its anode to cathode conduction path coupled between the vehicle direct current energy source and lead 656, which is coupled to another end of phase winding P1. Darlington stage 940b has its output conduction path coupled between ground and the same end of winding P1 via lead 656.
The alternator control circuitry of FIG. 10 to be described below, is coupled to phase winding P1 via leads 1006, 1008, 1010, and 1012. Leads 1006 and 1012 are coupled to opposite ends of winding P1 via current limiting chokes 1002 and 1004, respectively.
In the starter motor mode of operation, the mode control circuit 621 of FIG. 6 supplies enabling power to Hall-effect switch 601 via lead 630. Under this condition, assume that switch 601 detects the presence of a north magnetic pole. Upon such detection, switch 601 will place a ground potential signal on output 650. After a preselected time delay provided by the one-shot multivibrator centered about transistor 910a, the ground signal at switch output 650 will be coupled to one side of resistor 912a thereby diverting base drive current from transistor 920a, which is normally in the conductive state thereby switching transistor 920a off. When transistor 920a becomes non-conductive, enabling current is provided via resistor 922a to the gate electrode of field effect transistor 926a, thereby rendering 926a conductive. 926a becoming conductive substantially simultaneously renders optically coupled SCR 930a and the Darlington connected power transistor switch 940a conductive. The delay provided by the one-shot multivibrator centered about transistor 910a is utilized to guard against the possibility of short circuiting the phase winding due to the turn-off delay characteristics of the silicon controlled rectifier switches in the drive circuitry to be discussed below. Such characteristics could lead to switching on one device before its counterpart at the opposite end of the phase winding can turn completely off. If more expensive power switching devices with sufficiently low turn-off times are utilized in the H-drive circuitry, the one-shot multivibrator delay may be eliminated from the control circuitry.
Optical coupled SCR 930a becoming conductive provides enabling gate current to SCR switch 938b, thereby closing a current path from the vehicle's battery supply to one end of winding P1 via lead 656. The return path for the current now flowing upwards through winding P1 as seen from FIG. 9 is provided by the output collector to emitter stage of the Darlington switch 940a to ground potential. When the ground potential signal at input 650 is removed, transistor 920a will be rendered conductive by base drive current via resistor 916a.
In a similar manner, if switch 601 detects a south pole, ground potential at switch output 652 will, after an appropriate delay, render field effect transistor 926b conductive, which in turn, via the base drive of Darlington pair 940b and the optically coupled SCR 930b will render Darlington switch 940b and SCR 938a conductive, thereby providing a current path from the vehicle's battery supply downward, as viewed in FIG. 9 through stator coil P1. It will be seen that SCR 938b corresponds to switch SW1 of FIG. 7, Darlington stage 940a corresponds to switch SW2 of FIG. 7, SCR 938a corresponds to switch SW3 of FIG. 7, and Darlington stage 940b corresponds to switch SW4 of FIG. 7.
The phase angle conduction control for the alternator mode of operation may take the form of the circuitry depicted in FIG. 10. Voltage induced in winding P1 during the alternator mode will produce current which may flow either via lead 1006 through power SCR 1050a or via lead 1012 through power SCR 1050b to the vehicle direct current energy source or battery via lead 644a and to the engine system electrical load via bus 640. The purpose of the circuitry of FIG. 10 is to determine the conduction time of either SCR 1050a or 1050b for each corresponding half cycle of the voltage induced in the stator winding P1.
As seen from FIG. 10, opposing ends of stator phase winding P1 are coupled via leads 1008 and 1010 to level detector circuitry which detects the crossing of the induced voltage wave-form of a predetermined point to begin the delay period in the conduction control angle process. This time point is designated 808 in FIG. 8. Lead 1008 is coupled via a voltage divider comprised of resistors 1014a and 1018a whose junction is coupled via diode 1016a to a bias voltage. The voltage divider determines the voltage level at which the detector is to provide an output signal. Preferably, the detector detects a level just above the zero crossing and just below the DC level 802 (FIG. 8) of the induced voltage wave form.
The voltage divider 1014a, 1018a is coupled to an input of an input buffer 1020a whose output is coupled to a one-shot multivibrator centered around transistor 1030 and capacitor 1022a. The output of buffer 1020a is also passed via lead 634b to the control regulation circuitry of FIG. 11 to be discussed below.
The output of the one-shot multivibrator centered about transistor 1030 is taken from the junction of a collector electrode of transistor 1030 and resistor 1032, which is coupled to ground potential. Transistor 1030 is normally on, thereby providing a positive logic level at the multivibrator's output. Upon detecting the desired level, the multivibrator circuit is triggered such that transistor 1030 is turned off providing the required low logic level enabling input to downcounter 1034. This enabling input allows counter 1034 to be loaded or "jam-set" with a preselected delay time value at pins J0 through J7 from the regulator controller of FIG. 11. Counter 1034 counts down for the predetermined period specified by J0-J7, and upon reaching the end of its count, generates a negative going signal at its output CO-ZD. The negative going output from the counter is inverted by invertor 1036 to set-reset flip flop 1040, which in turn renders field effect transistor 1044 non-conductive. Transistor 1044 in the off state allows either SCR 1052a or 1052b to provide amplified gate enabling current to either SCR 1050a or 1050b, respectively, depending upon which of the power SCRs 1050a or 1050b has the appropriate conduction state polarity across its anode-cathode circuit, in accordance with the state of the induced voltage across winding P1.
Hence, at a predetermined delay (804 of FIG. 8) from the desired signal point crossing (808 of FIG. 8), current will be generated towards the vehicular battery via path 644a and to the vehicle's electrical load via bus 640 via either SCR 1050a or 1050b for a chosen conduction interval (806 of FIG. 8). SCRs 1052a and 1052b are small signal SCRs utilized to trigger the power SCRs 1050a and 1050b, respectively.
Flip flop 1040 is reset upon the occurrence of the next zero or predetermined level detection crossing via invertor 1038.
On alternate half cycles of the induced voltage across stator winding P1, an identical crossing detector centered about buffer 1020b and voltage divider comprised of resistors 1014b and 1018b is utilized via lead 1010 coming from an opposite terminal of stator coil P1 to again turn off transistor 1030 and begin the down counting process at counter 1034. As with the level detector centered about buffer 1020a, the output of buffer 1020b is passed via lead 634c to the regulator control circuit of FIG. 11 to be discussed below. A high frequency clock signal at bus 636 is utilized to drive the down-count process at counter 1034 and the signals on bus 636 are developed at high frequency clock circuit 625 of FIG. 13 to be discussed further below.
The circuitry of the phase angle conduction controller 613 of FIG. 10 is disabled in the starter motor mode of operation of the machine by a ground potential signal on lead 632a emanating from the mode control circuitry 621 of FIGS. 6 and 12. Ground at lead 632a will inhibit the conduction of switching SCRs 1052a and 1052b which, in turn, will maintain power SCRs 1050a and 1050b in the non-conductive or off state.
Circuit details of the regulator controller 623 of FIG. 6 are set forth in the circuit diagram of FIG. 11. Lead 634b is coupled to a first terminal of capacitor 1101 whose opposite terminal is coupled to a junction of resistor 1105 and a cathode electrode of diode 1107. An anode electrode of diode 1107 is coupled to the CNTRL input of bilateral switch 1115. Switch 1115 is a type CD 40668, which conducts in both directions between terminals IO and OI whenever a logic high signal appears at its CNTRL input. In a similar manner, lead 634C is coupled via capacitor 1103 to a junction of resistor 1109 and a cathode electrode of diode 1111. The anode electrode of diode 1111 is coupled to the CNTRL input of bilateral switch 1115. The combination of resistive and capacitive elements as shown, along with the bilateral switch elements, forms a one-shot multivibrator triggered in accordance with the frequency of the voltage being induced in the first phase winding P1 of the stator. This is seen from the fact that leads 634b and 634c originate at the outputs of the crossing detectors in the conduction control circuitry 613 of FIG. 10.
The output of the clock circuit at switch 1115 is coupled to the CLK inputs of a D-type toggle flip flop 1155 and of an eight bit up/down counter formed by the combination of the two four-bit up/down counters 1157a and 1157b.
Operational amplifier 1131, along with resistors 1119, 1121, 1123, 1125, and capacitors 1127, 1129, and 1133, when connected as shown in FIG. 11, form an integrating circuit for integrating the difference between the desired vehicle system DC voltage and a preselected reference. The output of the integrator centered about operational amplifier 1131 is fed to a comparator comprised of operational amplifier 1149 along with resistors 1135, 1137, and 1151. The output of the comparator 1149 is used to toggle flip flop 1155. The output of flip flop 1155 is used to either request an upcount or a downcount from the counters 1157a and 1157b.
A carry-out signal at path 1160 of counter 1157b is coupled via an invertor 1141 to a first input of AND-gates 1145 and 1147. The highest order output bit D7 of counter 1157b is coupled via invertor 1139 to a second input of AND-gate 1145 and directly to a second input of AND-gate 1147. The output of AND-gate 1145 is coupled to a SET input on flip flop 1155, while the output of AND-gate 1147 is coupled to a RESET input of flip flop 1155. The toggle flip flop 1155, configured as shown with its logic circuitry coupled thereto and with the output of the basic clock circuit from switch device 1115, is used to synchronize the up/down count function with the clock signal being generated by monitoring a phase of induced voltage at the stator via leads 634b and 634c. Logic gates 1139, 1141, 1145 and 1147 are used as shown in their configuration of FIG. 11 to prevent carry-around of the up/down counter outputs to either all zeros or all ones.
Hence, regulator control 623 continuously compares a desired alternator output voltage to the actual output voltage and adjusts the delay count J0-J7 of FIG. 10, in accordance with the outputs of an eight-bit counter D0-D7 from counters 1157a and 1157b of FIG. 11. For the elements connected as shown, the gain of the circuitry is proportional to the speed of the alternator. Therefore, as the alternator voltage gets very high at high engine speeds, the gain function is correspondingly increased. When the alternator output voltage becomes too high, the logic circuitry and comparison elements of FIG. 11 determine that the conduction interval is occurring too soon, and that therefore a longer delay time d (i.e. a larger count value to be set into counters 1034 of FIG. 10) is required. Therefore, counters 1157a and 1157b are instructed to count up to yield a longer time d. This time period is then transferred via bus 634a to the inputs of the down counter 1034 of FIG. 10.
It should also be noted that the functions performed by the circuitry of FIG. 11 could be alternatively performed in a microprocessor or as part of the engine system control processor. Such a processor would be utilized to monitor the alternator output voltage, compare it to a preselected standard and to generate a desired delay count for transmission to the counting elements of the conduction angle controller 613, 615 and 617 of FIGS. 6 and 10. Use of the microprocessor alternative would have the advantage of yielding a nonlinear gain function by using, for example, a lookup table of desired gain versus the voltage being regulated.
FIG. 12 sets forth a circuit diagram for the mode control unit 621 of FIG. 6. Again, bilateral switch elements 1207, 1209, and 1211, having the same characteristics as described above with reference to the switch element 1115 of FIG. 11, are utilized to provide parallel power switches to the Hall-effect switches and to the alternator mode conduction control. When a start mode request signal is received on bus 638 from the engine control computer, output power for the Hall-effect switches 601, 603, and 605 is coupled thereto via bus 630. Additionally, the signal on bus 630 is coupled to the regulator controller 623 to inhibit the operation of the counters 1157a and 1157b (FIG. 11). Additionally, during the starter mode time period, transistor 1217 is rendered conductive to place a ground signal on leads 632a, 632b, and 632c to respectively disable the conduction phase control circuits 613, 615, and 617 of FIGS. 6 and 10, as previously described with reference to those figures.
Details of a high frequency clock circuit 625 of FIG. 6 are set forth in FIG. 13. With the bilateral switch elements 1301, 1303, and 1313 interconnected as shown along with resistive elements 1305, 1307, 1311, and 1315, and with capacitor 1309, the circuitry of FIG. 13 provides a high frequency free running multivibrator clock output for use by the downcounters of the conduction phase controllers 613, 615, and 617 of FIG. 6 and FIG. 10. The clock output is supplied at bus 636.
The invention has been described with reference to details of a preferred embodiment, for the sake of example. The scope and spirit of the invention is to be interpreted by the appended claims as interpreted in light of the specification.
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A combined starter motor and alternator for a vehicular engine system can be positioned for direct coupling to an engine power shaft between the engine and transmisson. A pair of axially offset magnetically permeable disks are bolted to the power shaft. These disks form an annular channel therebetween. A plurality of rare earth permanent magnets are mounted on the inside face of one of the disks in the channel. Positioned within the channel is a stationary, ironless stator assembly having stranded conductive wire windings embedded in an insulation matrix. These windings alternatively pass from the perimeter of the disk towards the interior of the disk as each winding forms a single pass around a longitudinal axis of the power shaft. In a starter mode of operation, a polarity sensor, such as a Hall-effect switch mounted adjacent each stator phase winding, is used to control the driver switches of a conventional H-type arrangement for providing drive current to a starter motor stator coil. The H-driver circuit features use of semiconductor switches capable of withstanding high reverse bias voltage in the H-legs extending between coil ends and the vehicle's battery or direct current energy source.
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FIELD OF THE INVENTION
[0001] The present invention generally relates to an apparatus for measuring the amount of fluid flowing in a channel, and more particularly to a fluidic oscillation flow meter for determining the flow rate of a gas.
BACKGROUND OF THE INVENTION
[0002] Fluidic oscillator flow meters are well known in the art. See for example, Horton et al., U.S. Pat. No. 3,185,166; Testerman et al., U.S. Pat. No. 3,273,377; Taplin, U.S. Pat. No. 3,373,600; Adams et al., U.S. Pat. No. 3,640,133; Villarroel et al., U.S. Pat. No. 3,756,068; Zupanick, U.S. Pat. No. 4,150,561; Bauer, U.S. Pat. No. 4,244,230; and Drzewiecki, U.S. Pat. No. 6,553,844. These conventional fluidic oscillators comprise a fluidic amplifier having two channels with the outputs fed back to the input to produce a free running oscillation wherein the fluid alternatively flows through one channel then the other by means of the fluid fed back being transversely applied to the input stream thereby forcing the input to the other channel.
[0003] Most fluidic oscillator flow meters measure some characteristic, e.g., volumetric flow, density, quality, enthalpy, and bulk modulus of a fluid. In the case of measuring volumetric flow, this is typically accomplished by measuring the frequency of the fluid shifting from one channel to the other. The frequency is linearly related to the volumetric flow because the flow transit time is related to flow velocity. Since the amplifier nozzle area is known, the product of velocity and area yields volumetric flow. In most cases, the acoustic feedback time for most fluids can be designed to be only a few percent of the total flow transit time.
[0004] In U.S. Pat. No. 6,076,392, the constituents of a gas mixture are determined by measuring both the flow of the fluid sample stream and the speed of sound in the fluid. A measure of the volumetric flow is required to determine the properties density and viscosity of the fluid sample, and a measure of the speed of sound is required to determine the property specific heat of the fluid.
[0005] In “A Fluidic-Electronic Hybrid System for Measuring the Composition of Binary Mixtures”, Anderson et al., Ind. Eng. Chem. Fundam., Vol. 11, No. 3, 1972, it has been shown that the density of a gas may be determined by use of an oscillation flow meter for gasses with temperatures ranging from −20 to +120° C. The speed of a pressure pulse traveling through a gas (sonic velocity) is proportional to the square root of the gas density. However, the disclosed system requires a separate liquid vaporizer.
[0006] Accordingly, it is desirable to provide a fluidic oscillation flow meter integrated within a fuel cell for measuring the volumetric flow rate of elevated temperature vapor. Furthermore, other desirable features and characteristics of the present invention will become apparent from the subsequent detailed description of the invention and the appended claims, taken in conjunction with the accompanying drawings and this background of the invention.
BRIEF SUMMARY OF THE INVENTION
[0007] An integrated vaporizer and flow meter is provided for determining the flow rate of a gas. The apparatus comprises a housing forming a vaporization chamber for converting a fluid into a gas vapor when subjected to heat. An oscillation flow meter is formed within the housing, thereby being integrated with the vaporization chamber, for receiving the gas vapor and providing a frequency signal indicative of the rate of flow of the gas vapor.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] The present invention will hereinafter be described in conjunction with the following drawing figures, wherein like numerals denote like elements, and
[0009] FIG. 1 is a schematic diagram of a fluidic oscillation flow meter in accordance with an exemplary embodiment of the present invention; and
[0010] FIG. 2 is a block diagram of a fuel cell system including the fluidic oscillation flow meter of FIG. 1 .
DETAILED DESCRIPTION OF THE INVENTION
[0011] The following detailed description of the invention is merely exemplary in nature and is not intended to limit the invention or the application and uses of the invention. Furthermore, there is no intention to be bound by any theory presented in the preceding background of the invention or the following detailed description of the invention.
[0012] Referring to FIG. 1 , a gas oscillation flow meter 10 in accordance with an exemplary embodiment of the present invention includes a vaporization chamber 14 and a flow meter 16 within a housing 12 . Ideally the device should be able to operate from a minimum of the boiling point temperature of the measured fluid to a maximum of the temperature of a secondary process. The housing 12 comprises a material able to withstand high temperatures, such as a metal, but would preferably comprise ceramic. The vaporization chamber 12 optionally includes a porous material 18 spaced throughout. The porous material 18 may comprise zirconia or alumina, for example. The porous material 18 improves the spreading of the fluid resulting in an improved uniform evaporation.
[0013] The flow meter 16 comprises a flow meter inlet nozzle 26 and first and second diversion channels 28 , 30 . Vents 32 , 34 , 36 , and 38 (output vias) are accessible through output channels 42 , 44 , 46 , 48 . Piezo chamber 52 is spaced between the first diversion channel 28 and a first return channel 54 , and piezo chamber 56 is spaced between the second diversion channel 30 and a second return channel 58 . A piezo device 62 is positioned within piezo chamber 52 and a piezo device 64 is positioned within piezo chamber 56 . In some embodiments, e.g., a multi-layer ceramic embodiment, the various elements may reside on different levels. For simplicity, the various components are shown in FIG. 1 as being on the same level.
[0014] In operation, a liquid is provided into the chamber 14 at the inlet 20 . The liquid may comprise, for example, a methanol and water mixture (such as may be used in a fuel cell system to be described subsequently in more detail). The liquid will saturate a portion of the porous material 18 . Heat 22 is applied to the chamber 14 , either by actively heating the chamber or by reclaiming waste heat from a thermally coupled secondary process, resulting in a gas vapor exiting the chamber 14 at outlet 24 . The desired temperature of heat is above the maximum boiling temperature of the inlet fluid and below the thermal constraints of the construction materials.
[0015] The gas vapor exiting the outlet 24 enters the flow meter inlet nozzle 26 having a certain velocity. As the gas vapor proceeds into the flow meter 16 , the majority of the gas vapor will enter either the first or second diversion channel. For example, the gas vapor might enter diversion channel 28 , and proceed around through piezo chamber 52 and first return channel 54 , passing through the first nozzle 66 . As the gas vapor passes through first nozzle 66 , it impacts the gas vapor entering at flow meter inlet nozzle 26 , deflecting the entering gas vapor and causing the majority of the entering gas vapor to now divert to the second diversion channel 30 . The gas vapor would then proceed around through piezo chamber 56 and second return channel 58 , passing through the second nozzle 68 . As the gas vapor passes through second nozzle 68 , it impacts the gas vapor entering at flow meter inlet nozzle 26 , deflecting the entering gas vapor and causing the majority of the entering gas vapor to again enter the first diversion channel 28 . This switching from one side of the flow meter 16 to the other will continue in a cyclic fashion having a certain frequency depending on the rate of flow of the gas as long as gas vapor enters the flow meter 16 .
[0016] As gas vapor fills the flow meter 16 and the pressure builds, gas vapor will enter output channels 42 , 44 , 46 , 48 and exit the flow meter 16 through vents 32 , 34 , 36 , 38 . The vents 32 , 34 , 36 , 38 may converge into a single outlet (not shown). Additionally, though four vents 32 , 34 , 36 , 38 are shown, any number of vents may be used. Typically, an equal number of vents would be positioned on both sides.
[0017] As the gas vapor passes through piezo chambers 52 , 56 , the pressure pulse is sufficient to trigger piezo devices 62 , 64 thus generating an ac electrical signal 60 indicative of the frequency of the oscillatory nature of the flow meter 16 . The frequency of the gas shifting from one channel 28 , 30 to the other is approximately linearly related to the volumetric flow.
[0018] The gas oscillation flow meter 10 may be used most effectively in any application that consumes liquid fuel and operates at temperatures above the boiling point of that fuel, e.g., internal combustion engine, microreactors, and more specifically fuel cells. Fuel cells are electrochemical cells in which a free energy change resulting from a fuel oxidation reaction is converted into electrical energy. Reformed Hydrogen Fuel Cells (RHFCs) utilize hydrogen fuel processed from liquid or gaseous hydrocarbon fuels, such as methanol, using a reactor, called a fuel reformer, for converting the fuel into hydrogen. Methanol is the preferred fuel for use in fuel reformers for portable applications because it is easier to reform into hydrogen gas at a relatively low temperature compared to other hydrocarbon fuels such as ethanol, gasoline, or butane. The reforming or converting of methanol into hydrogen usually takes place by one of three different types of reforming. These three types are steam reforming, partial oxidation reforming, and autothermal reforming. Of these types, stean reforming is the preferred process for methanol reforming because it is the easiest to control and produces a higher concentration of hydrogen output by the reformer, at a lower temperature, thus lending itself to favored use.
[0019] Utilizing multilayer laminated ceramic technology, ceramic components and systems are now being developed for use in microfluidic chemical processing and energy management systems, e.g., fuel cells. Monolithic structures formed of these laminated ceramic components are inert and stable to chemical reactions and capable of tolerating high temperatures. These structures can also provide for miniaturized components, with a high degree of electrical and electronic circuitry or components embedded or integrated into the ceramic structure for system control and functionality. Additionally, the ceramic materials used to form ceramic components or devices, including microchanneled configurations, are considered to be excellent candidates for catalyst supports and so are extraordinarily compatible for use in microreactor devices for generating hydrogen used in conjunction with miniaturized fuel cells. An example of a fuel cell formed in a ceramic material is disclosed in U.S. Pat. No. 6,569,553.
[0020] A simplified block diagram of a fuel cell system, including an exemplary embodiment of the fluidic oscillation flow meter 10 , is shown in FIG. 2 . A mixture 70 of methanol and water is supplied by a fuel pump 72 via fuel line 71 to the fluidic oscillation flow meter 10 . The mixture 70 of methanol and water is converted to a gas vapor as previously explained. Heat 22 is supplied to the gas oscillation flow meter 10 by the waste heat of a fuel cell 92 (an electric heater, not shown, may provide heat for startup). A frequency signal 60 is generated, as previously discussed, as well as a vapor temperature signal 73 , and supplied to micro-controller 74 . The micro-controller 74 forwards a control signal 76 to the fuel pump 72 for controlling the amount of fuel pumped in response to the frequency signal 60 . Each frequency relates proportionally to a specific flow rate. The pump control circuitry 74 determines the flow rate based on the frequency signal 60 and the vapor temperature signal 73 and directs the fuel pump 72 via the control signal 76 to increase, decrease, or maintain the fuel flow rate.
[0021] The gas vapor exits the fluidic oscillation flow meter 10 via line 81 and enters a reformer section 82 of a fuel processor 80 . A first air pump 84 pumps preferably air, though any oxidant could be used, to a mixer 86 , for mixing the air with fuel received from the fuel cell 92 via line 85 . The micro-controller 74 determines the speed of the flow rate of the first air pump 84 and controls the speed thereof with the combustor pump control signal 81 . The mixture of air and fuel is fed via line 87 to a combustor 88 for supplying heat to the reformer 82 . A heater control signal 79 from the micro-controller 74 to the combustor 88 controls the amount of heat generated by the combustor 88 for optimum operation of the reformer 82 . The reformer supplies hydrogen vapor via line 83 to the anode 72 of the fuel cell 92 .
[0022] The fuel cell 92 comprises a fuel electrode, or anode 94 , and an oxidant electrode, or cathode 96 , separated by an ion-conducting electrolyte 98 . The electrodes 94 , 96 are connected electrically to a load (such as an electronic circuit) by an external circuit conductor (not shown). In the circuit conductor, electric current is transported by the flow of electrons, whereas in the electrolyte 98 , it is transported by the flow of ions, such as the hydrogen ion (H + ) in acid electrolytes, or the hydroxyl ion (OH − ) in alkaline electrolytes. In theory, any substance capable of chemical oxidation that can be supplied continuously (as a gas or fluid) can be oxidized galvanically as the fuel at the anode of a fuel cell. Similarly, the oxidant, supplied via line 103 by second air pump 102 , can be any material that can be reduced at a sufficient rate. Gaseous hydrogen has become the fuel of choice for most applications, because of its high reactivity in the presence of suitable catalysts and because of its high power density. Similarly, at the fuel cell cathode 96 , the most common oxidant is gaseous oxygen, which is readily and economically available from air for fuel cells used in terrestrial applications. When gaseous hydrogen and oxygen are used as fuel and oxidant, the electrodes 94 , 96 are porous to permit the gas-electrolyte junction area to be as great as possible. The electrodes 94 , 96 must be electronic conductors, and possess the appropriate reactivity to give significant reaction rates. At the anode 94 , incoming hydrogen gas is oxidized to produce hydrogen ions (protons) and electrons. Since the electrolyte is a non-electronic conductor, the electrons flow away from the anode 94 via an external electrical circuit. At the cathode 96 , oxygen gas is reduced and reacts with the hydrogen ions migrating through the electrolyte 98 and the incoming electrons from the external circuit to produce water as a byproduct. The byproduct water is typically expelled as vapor at elevated temperatures via line 99 . The overall reaction that takes place in the fuel cell is the sum of the anode 94 and cathode 96 reactions, with part of the free energy of reaction released directly as electrical energy. The difference between this available free energy and the heat of reaction is produced as heat at the temperature of the fuel cell 92 . It can be seen that as long as hydrogen and oxygen are supplied to the fuel cell 92 , the flow of electric current will be sustained by electronic flow in the external circuit and ionic flow in the electrolyte.
[0023] In practice, a number of these unit fuel cells 92 are normally stacked or ‘ganged’ together to form a fuel cell assembly. A number of individual cells are electrically connected in series by abutting the anode current collector of one cell with the cathode current collector of its nearest neighbor in the stack.
[0024] The micro-controller 74 controls the overall operation of the system. For example, the operating point of the fuel cell 92 is controlled by a heater control signal 91 from the micro-controller 74 in response to a temperature signal 93 and a cell voltage signal 95 from the fuel cell 92 . The amount of oxidant supplied to the cathode 96 by the second air pump (or blower) 102 is controlled by the cathode blower signal 101 from the micro-controller. Exhaust from the fuel cell 92 via line 99 through dilution fan 106 is controlled by the micro-processor 74 via dilution fan signal 105 . A DC-DC converter 108 receives electrical current produced by the fuel cell 92 and provides power to the micro-controller 74 .
[0025] 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.
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An apparatus ( 10 ) is provided for determining the flow rate of a gas. The apparatus comprises a housing ( 12 ) forming a vaporization chamber ( 14 ) for converting a fluid into a gas vapor when subjected to heat ( 22 ). An oscillation flow meter is formed within the housing ( 12 ), thereby being integrated with the vaporization chamber, for receiving the gas vapor and providing a frequency signal ( 60 ) indicative of the rate of flow of the gas vapor.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. patent application Ser. No. 13/460,797 filed Apr. 30, 2012, which is a continuation of U.S. patent application Ser. No. 12/703,553 filed Feb. 10, 2012, now U.S. Pat. No. 8,412,365, which is a continuation of U.S. patent application Ser. No. 12/253,135 filed Oct. 16, 2008, now U.S. Pat. No. 7,680,552, which is a continuation of U.S. patent application Ser. No. 10/296,562 filed Jan. 6, 2004, now U.S. Pat. No. 7,483,753 which is a national-stage entry of International patent application no. PCT/SE01/01171 filed May 23, 2001, all of which are hereby incorporated by reference.
TECHNICAL FIELD
[0002] The present invention relates to a new method and apparatus for improvement of High Frequency Reconstruction (HFR) techniques, applicable to audio source coding systems. Significantly reduced computational complexity is achieved using the new method. This is accomplished by means of frequency translation or folding in the subband domain, preferably integrated with the spectral envelope adjustment process. The invention also improves the perceptual audio quality through the concept of dissonance guard-band filtering. The proposed invention offers a low-complexity, intermediate quality HFR method and relates to the PCT patent Spectral Band Replication (SBR) [WO 98/57436].
BACKGROUND OF THE INVENTION
[0003] Schemes where the original audio information above a certain frequency is replaced by gaussian noise or manipulated lowband information are collectively referred to as High Frequency Reconstruction (HFR) methods. Prior-art HFR methods are, apart from noise insertion or non-linearities such as rectification, generally utilizing so-called copy-up techniques for generation of the highband signal. These techniques mainly employ broadband linear frequency shifts, i.e. translations, or frequency inverted linear shifts, i.e. foldings. The prior-art HFR methods have primarily been intended for the improvement of speech codec performance. Recent developments in highband regeneration using perceptually accurate methods, have however made HFR methods successfully applicable also to natural audio codecs, coding music or other complex programme material, PCT patent [WO 98/57436]. Under certain conditions, simple copy-up techniques have shown to be adequate when coding complex programme material as well. These techniques have shown to produce reasonable results for intermediate quality applications and in particular for codec implementations where there are severe constraints for the computational complexity of the overall system.
[0004] The human voice and most musical instruments generate quasistationary tonal signals that emerge from oscillating systems. According to Fourier theory, any periodic signal may be expressed as a sum of sinusoids with frequencies f, 2 f, 3 f, 4 f, 5 f etc. where f is the fundamental frequency. The frequencies form a harmonic series. Tonal affinity refers to the relations between the perceived tones or harmonics. In natural sound reproduction such tonal affinity is controlled and given by the different type of voice or instrument used. The general idea with HFR techniques is to replace the original high frequency information with information created from the available lowband and subsequently apply spectral envelope adjustment to this information. Prior-art HFR methods create highband signals where tonal affinity often is uncontrolled and impaired. The methods generate non-harmonic frequency components which cause perceptual artifacts when applied to complex programme material. Such artifacts are referred to in the coding literature as “rough” sounding and are perceived by the listener as distortion.
[0005] Sensory dissonance (roughness), as opposed to consonance (pleasantness), appears when nearby tones or partials interfere. Dissonance theory has been explained by different researchers, amongst others Plomp and Levelt [“Tonal Consonance and Critical Bandwidth” R. Plomp, W. J. M. Levelt JASA , Vol 38, 1965], and states that two partials are considered dissonant if the frequency difference is within approximately 5 to 50% of the bandwidth of the critical band in which the partials are situated. The scale used for mapping frequency to critical bands is called the Bark scale. One bark is equivalent to a frequency distance of one critical band. For reference, the function
[0000]
z
(
f
)
=
26.81
1
+
1960
f
-
0.53
[
Bark
]
(
1
)
[0000] can be used to convert from frequency (f) to the bark scale (z). Plomp states that the human auditory system can not discriminate two partials if they differ in frequency by approximately less than five percent of the critical band in which they are situated, or equivalently, are separated less than 0,05 Bark in frequency. On the other hand, if the distance between the partials are more than approximately 0,5 Bark, they will be perceived as separate tones.
[0006] Dissonance theory partly explains why prior-art methods give unsatisfactory performance. A set of consonant partials translated upwards in frequency may become dissonant. Moreover, in the crossover regions between instances of translated bands and the lowband the partials can interfere, since they may not be within the limits of acceptable deviation according to the dissonance-rules.
SUMMARY OF THE INVENTION
[0007] The present invention provides a new method and device for improvements of translation or folding techniques in source coding systems. The objective includes substantial reduction of computational complexity and reduction of perceptual artifacts. The invention shows a new implementation of a subsampled digital filter bank as a frequency translating or folding device, also offering improved crossover accuracy between the lowband and the translated or folded bands. Further, the invention teaches that crossover regions, to avoid sensory dissonance, benefits from being filtered. The filtered regions are called dissonance guard-bands, and the invention offers the possibility to reduce dissonant partials in an uncomplicated and accurate manner using the subsampled filterbank.
[0008] The new filterbank based translation or folding process may advantageously be integrated with the spectral envelope adjustment process. The filterbank used for envelope adjustment is then used for the frequency translation or folding process as well, in that way eliminating the need to use a separate filterbank or process for spectral envelope adjustment. The proposed invention offers a unique and flexible filterbank design at a low computational cost, thus creating a very effective translation/folding/envelope-adjusting system.
[0009] In addition, the proposed invention is advantageously combined with the Adaptive Noise-Floor Addition method described in PCT patent [SE00/00159]. This combination will improve the perceptual quality under difficult programme material conditions.
[0010] The proposed subband domain based translation of folding technique comprise the following steps:
filtering of a lowband signal through the analysis part of a digital filterbank to obtain a set of subband signals; repatching of a number of the subband signals from consecutive lowband channels to consecutive highband channels in the synthesis part of a digital filterbank; adjustment of the patched subband signals, in accordance to a desired spectral envelope; and filtering of the adjusted subband signals through the synthesis part of a digital filterbank, to obtain an envelope adjusted and frequency translated or folded signal in a very effective way.
[0015] Attractive applications of the proposed invention relates to the improvement of various types of intermediate quality codec applications, such as MPEG 2 Layer III, MPEG 2/4 AAC, Dolby AC-3, NTT TwinVQ, AT&T/Lucent PAC etc. where such codecs are used at low bitrates. The invention is also very useful in various speech codecs such as G. 729 MPEG-4 CELP and HVXC etc to improve perceived quality. The above codecs are widely used in multimedia, in the telephone industry, on the Internet as well as in professional multimedia applications.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] The present invention is described by way of illustrative examples, not limiting the scope or spirit of the invention, with reference to the accompanying drawings, in which:
FIG. 1 illustrates filterbank-based translation or folding integrated in a coding system according to the present invention; FIG. 2 shows a basic structure of a maximally decimated filterbank; FIG. 3 illustrates spectral translation according to the present invention; FIG. 4 illustrates spectral folding according to the present invention; FIG. 5 illustrates spectral translation using guard-bands according to the present invention.
DESCRIPTION OF PREFERRED EMBODIMENTS
[0022] Digital filterbank based translation and folding
[0023] New filter bank based translating or folding techniques will now be described. The signal under consideration is decomposed into a series of subband signals by the analysis part of the filterbank. The subband signals are then repatched, through reconnection of analysis- and synthesis subband channels, to achieve spectral translation or folding or a combination thereof.
[0024] FIG. 2 shows the basic structure of a maximally decimated filterbank analysis/synthesis system. The analysis filter bank 201 splits the input signal into several subband signals. The synthesis filter bank 202 combines the subband samples in order to recreate the original signal. Implementations using maximally decimated filter banks will drastically reduce computational costs. It should be appreciated, that the invention can be implemented using several types of filter banks or transforms, including cosine or complex exponential modulated filter banks, filter bank interpretations of the wavelet transform, other non-equal bandwidth filter banks or transforms and multi-dimensional filter banks or transforms.
[0025] In the illustrative, but not limiting, descriptions below it is assumed that an L-channel filter bank splits the input signal x(n) into L subband signals. The input signal, with sampling frequency f s , is bandlimited to frequency f c . The analysis filters of a maximally decimated filter bank ( FIG. 2 ) are denoted H k (z) 203 , where k=0, 1, . . . , L-1. The subband signals v k (n) are maximally decimated, each of sampling frequency f s /L, after passing the decimators 204 , The synthesis section, with the synthesis filters denoted F k (z), reassembles the subband signals after interpolation 205 and filtering 206 to produce {circumflex over (x)}(n) . In addition, the present invention performs a spectral reconstruction on {circumflex over (x)}(n) , giving an enhanced signal y(n).
[0026] The reconstruction range start channel, denoted M, is determined by
[0000]
M
=
floor
{
f
c
f
s
2
L
}
.
(
2
)
[0027] The number of source area channels is denoted S (1≦S≦M). Performing spectral reconstruction through translation on {circumflex over (x)}(n) according to the present invention, in combination with envelope adjustment, is accomplished by repatching the subband signals as
[0000] v M+k ( n )= e M+k ( n ) v M−S−P+k ( n ), (3)
[0000] where k∈[0, S−1], (−1) S+P =1, i.e. S+P is an even number, P is an integer offset (0≦P≦M−S) and e M+k (n) is the envelope correction. Performing spectral reconstruction through folding on {circumflex over (x)}(n) according to the present invention, is further accomplished by repatching the subband signals as
[0000] v M+k ( n )= e M+k ( n ) v* M−P−S−k ( n ), (4)
[0000] where k∈[0, S−1], (−1) S+P =−1, i.e. S+P is an odd integer number, P is an integer offset (1−S≦P≦M−2S+1) and e M+k (n) is the envelope correction. The operator [*] denotes complex conjugation. Usually, the repatching process is repeated until the intended amount of high frequency bandwidth is attained.
[0028] It should be noted that, through the use of the subband domain based translation and folding, improved crossover accuracy between the lowband and instances of translated or folded bands is achieved, since all the signals are filtered through filterbank channels that have matched frequency responses.
[0029] If the frequency f c of x(n) is too high, or equivalently f s is too low, to allow an effective spectral reconstruction, i.e. M+S>L, the number of subband channels may be increased after the analysis filtering. Filtering the subband signals with a QL-channel synthesis filter bank, where only the L lowband channels are used and the upsampling factor Q is chosen so that QL is an integer value, will result in an output signal with sampling frequency Qf s . Hence, the extended filter bank will act as if it is an L-channel filter bank followed by an upsampler. Since, in this case, the L(Q−1) highband filters are unused (fed with zeros), the audio bandwidth will not change−the filter bank will merely reconstruct an upsampled version of {circumflex over (x)}(n). If, however, the L subband signals are repatched to the highband channels, according to Eq.(3) or (4), the bandwidth of {circumflex over (x)}(n) will be increased. Using this scheme, the upsampling process is integrated in the synthesis filtering. It should be noted that any size of the synthesis filter bank may be used, resulting in different sampling rates of the output signal.
[0030] Referring to FIG. 3 , consider the subband channels from a 16-channel analysis filterbank. The input signal x(n) has frequency contents up to the Nyqvist frequency (f c =f s /2). In the first iteration, the 16 subbands are extended to 23 subbands, and frequency translation according to Eq.(3) is used with the following parameters: M=16, S=7 and P=1. This operation is illustrated by the repatching of subbands from point a to b in the figure. In the next iteration, the 23 subbands are extended to 28 subbands, and Eq.(3) is used with the new parameters: M=23, S=5 and P=3. This operation is illustrated by the repatching of subbands from point b to c. The so-produced subbands may then be synthesized using a 28-channel filterbank. This would produce a critically sampled output signal with sampling frequency 28/16f s =1.75 f s . The subband signals could also be synthesized using a 32-channel filterbank, where the four uppermost channels are fed with zeros, illustrated by the dashed lines in the figure, producing an output signal with sampling frequency 2f s .
[0031] Using the same analysis filterbank and an input signal with the same frequency contents, FIG. 4 illustrates the repatching using frequency folding according to Eq.(4) in two iterations. In the first iteration M=16, S=8 and P=−7, and the 16 subbands are extended to 24. In the second iteration M=24, S=8 and P=−7, and the number of subbands are extended from 24 to 32. The subbands are synthesized with a 32-channel filterbank. In the output signal, sampled at frequency 2f s , this repatching results in two reconstructed frequency bands—one band emerging from the repatching of subband signals to channels 16 to 23, which is a folded version of the bandpass signal extracted by channels 8 to 15, and one band emerging from the repatching to channels 24 to 31, which is a translated version of the same bandpass signal.
[0032] Guardbands in High Frequency Reconstruction
[0033] Sensory dissonance may develop in the translation or folding process due to adjacent band interference, i.e. interference between partials in the vicinity of the crossover region between instances of translated bands and the lowband. This type of dissonance is more common in harmonic rich, multiple pitched programme material. In order to reduce dissonance, guard-bands are inserted and may preferably consist of small frequency bands with zero energy, i.e. the crossover region between the lowband signal and the replicated spectral band is filtered using a bandstop or notch filter. Less perceptual degradation will be perceived if dissonance reduction using guard-bands is performed. The bandwidth of the guard-bands should preferably be around 0,5 Bark. If less, dissonance may result and if wider, comb-filter-like sound characteristics may result.
[0034] In filterbank based translation or folding, guard-bands could be inserted and may preferably consist of one or several subband channels set to zero. The use of guardbands changes Eq.(3) to
[0000] v M+D+k ( n )= e M+D+k ( n ) v M−S−P+k ( n )
[0000] (5)
and Eq.(4) to
[0035] v M+D+k ( n )= e M+D+k ( n ) v* M−P−S−k ( n ). (6)
[0000] D is a small integer and represents the number of filterbank channels used as guardband. Now P+S+D should be an even integer in Eq.(5) and an odd integer in Eq.(6). P takes the same values as before. FIG. 5 shows the repatching of a 32-channel filterbank using Eq.(5). The input signal has frequency contents up to f c = 5/16 f s , making M=20 in the first iteration. The number of source channels is chosen as S=4 and P=2. Further, D should preferably be chosen as to make the bandwidth of the guardbands 0,5 Bark. Here, D equals 2, making the guardbands f s /32 Hz wide. In the second iteration, the parameters are chosen as M=26, S=4, D=2 and P=0. In the figure, the guardbands are illustrated by the subbands with the dashed line-connections.
[0036] In order to make the spectral envelope continuous, the dissonance guard-bands may be partially reconstructed using a random white noise signal, i.e. the subbands are fed with white noise instead of being zero. The preferred method uses Adaptive Noise-floor Addition (ANA) as described in the PCT patent application [SE00/00159]. This method estimates the noise-floor of the highband of the original signal and adds synthetic noise in a well-defined way to the recreated highband in the decoder.
[0037] Practical implementations The present invention may be implemented in various kinds of systems for storage or transmission of audio signals using arbitrary codecs. FIG. 1 shows the decoder of an audio coding system. The demultiplexer 101 separates the envelope data and other HFR related control signals from the bitstream and feeds the relevant part to the arbitrary lowband decoder 102 . The lowband decoder produces a digital signal which is fed to the analysis filterbank 104 . The envelope data is decoded in the envelope decoder 103 , and the resulting spectral envelope information is fed together with the subband samples from the analysis filterbank to the integrated translation or folding and envelope adjusting filterbank unit 105 . This unit translates or folds the lowband signal, according to the present invention, to form a wideband signal and applies the transmitted spectral envelope. The processed subband samples are then fed to the synthesis filterbank 106 , which might be of a different size than the analysis filterbank. The digital wideband output signal is finally converted 107 to an analogue output signal.
[0038] The above-described embodiments are merely illustrative for the principles of the present invention for improvement of High Frequency Reconstruction (HFR) techniques using filterbank-based frequency translation or folding. It is understood that modifications and variations of the arrangements and the details described herein will be apparent to others skilled in the art. It is the intent, therefore, to be limited only by the scope of the impending patent claims and not by the specific details presented by way of description and explanation of the embodiments herein.
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The present invention relates to a new method and apparatus for improvement of High Frequency Reconstruction (HFR) techniques using frequency translation or folding or a combination thereof. The proposed invention is applicable to audio source coding systems, and offers significantly reduced computational complexity. This is accomplished by means of frequency translation or folding in the subband domain, preferably integrated with spectral envelope adjustment in the same domain. The concept of dissonance guard-band filtering is further presented. The proposed invention offers a low-complexity, intermediate quality HFR method useful in speech and natural audio coding applications.
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FIELD OF THE INVENTION
The present invention is related to the field of electronic devices and their associated driver and/or controller integrated circuits, and more particularly to the mechanical packaging of electronic devices and to the packaging of electronic devices and their associated driver and/or controller integrated circuits.
BACKGROUND OF THE INVENTION
Electronic devices respectively electronic components such as micro-electromechanical system (MEMS) devices are of increasing importance. Many type of systems use sensors to detect the value of a property of a physical system and to generate a corresponding electrical signal representing the sensed value.
Accelerometer sensors for example comprise a mechanically active component, e.g. an acceleration dependant oscillating mass and rely on electromechanical sensors, which translate particular types of acceleration, such as rotational or linear acceleration, into corresponding electrical signals.
Since such electronic devices are quite sensitive, they need to be protected by assembling them in some kind of package. For the manufacturing of electronic or other devices for micro systems many technologies have been developed, which enable precise forming of structured encapsulation or passivation layers and/or cavities.
Typical packaging or housing concepts, as for example moulding in plastics, are disadvantageous because the mechanical properties of said sensitive components are disturbed or even damaged. In case of SAW-filter-devices for instance even the material on the surface influences the characteristics of said filter devices.
To avoid such disturbance and to protect such sensitive electronic device, wafers with corresponding sensitive electronic devices are bonded with a second wafer or a lid wafer. Said second wafer comprises holes or trenches in the area or at the position of said electronic devices. These holes or trenches of said second wafer are fabricated in such a way that they form a cavity above the sensitive structures after bonding said second wafer to said first wafer.
DE 101 47 648 A1 for example discloses this concept for the fabrication of pocket-shaped structures for a glass lid used for packaging MEMS devices.
Alternatively also expensive ceramic packages are used to protect sensitive components.
DE 102 06 919 A1 discloses a method for packaging electronic devices using a process with the following steps: Putting said electronic devices on a first wafer, fabricating a frame structure around each electronic device and covering said frame structure with a lid structure placed on a victim layer. The frame structure around each electronic device and the covering form a cavity housing and protecting the electronic device. As already mentioned above, many types of systems use electronic devices such as sensors to detect the value of a property of a physical system and to generate a corresponding electrical signal representing the sensed value. These electrical signals are commonly provided to electrical integrated circuits, located off-chip or in adjacent locations on-chip, in order to enable a desired function, e.g. amplification, discrimination and/or signal conversion, to be performed.
In the case of a separate packaging of electronic device and associated driver and/or controller integrated circuit, the packaged electronic device is mounted on a printed circuit board along with the driver and/or controller integrated circuit, which is packaged in a similar manner. Collectively they perform the desired function, e.g. a sensing function.
Since the packaging of the electronic device and the packaging of the integrated circuit are generally significantly larger than the corresponding electronic device respectively the integrated circuit, the packaging contributes notably to the dimensions and also to the costs of the assembly on the printed circuit board.
Further, the mounting of the electronic device in the packaging limits, how close the electronic device can be placed with respect to the integrated circuit performing the controller and/or driver function. This can in turn unnecessarily limit the electrical performance of the electronic system or increase the susceptibility to noise.
WO 01/29529 A2 discloses a packaging of micro-mechanical sensors and associated control circuits. The micro-mechanical sensor is fabricated on a semiconductor wafer and the control circuit on a another semiconductor. A cavity is etched on the back side of the control circuit wafer, the cavity being formed such that the sensor on the other wafer fits within the cavity when the wafers are brought together in an adjoining relation.
Document U.S. 2004/0173913 A1 describes a capacitive semiconductor, a sensor chip and a circuit chip being contained in a package. Said sensor chip in mounted onto said circuit chip to provide a stack structure. Said stack structure is contained in said package. Said package is made of single ceramic substrates which are inner-hollowed. Said circuit chip is positioned onto the top side of a plate.
U.S. Pat. No. 5,701,033 relates to a semiconductor device comprising a substrate having a hollow cavity for mounting a semiconductor element therein and a lowered step surface at a periphery of the cavity for mounting a chip component thereon. Said semiconductor element is mounted within the cavity and said chip component embodied as a chip capacitor is mounted to the lowered step surface.
Document JP 2002171150 describes the structure of a package for piezoelectric vibrating devices having one side which is positioned on the top side of a carrier by means of a type of “pedestal”.
U.S. 2004/0077117 A1 relates to a feedthrough design and a method for a hermetically sealed microdevice. Among other things a glass wafer and a silicon wafer are assembled to an assembly wafer which is diced into single microdevices.
Therefore, it is the object of the present invention to provide an easy, size and cost reduced but safe concept to package or house electronic devices or electronic devices together with their associated driver and/or controller integrated circuits, in particular by using conventional integrated circuit fabrication techniques and conventional packaging technologies.
GENERAL DESCRIPTION OF THE INVENTION
The inventive solution of the object of the present invention is surprisingly achieved by each of the subject matter of the respective attached independent claims. Advantageous and/or preferred embodiments or refinements are the subject matter of the respective attached dependent claims.
Accordingly, the invention proposes a method for packaging electronic components comprising the steps of providing at least one support substrate; producing at least one recess in a top side of said support substrate comprising at least one stair, placing at least one first electronic device at least partially onto said stair, in particular to support said first electronic device and/or to space said first electronic device from a bottom of said recess and covering at least partially said top side of said support substrate with a lid.
The step of covering said top side of said support substrate with a lid results in the formation of a cavity being constituted by said recess and said lid. Accordingly, said first electronic device is housed in or within said cavity. In one embodiment beside the first electronic device at least one second electronic device is placed on said top side of said support substrate. Preferably said second electronic device is placed adjacently to said recess.
The invention further proposes a method for packaging electronic components comprising the steps of providing at least one support substrate, producing at least one recess in a top side of said support substrate, placing at least one first electronic device into said recess, arranging, in particular adjacently to said recess, at least one second electronic device on or onto said top side top side of said support substrate and covering at least partially said top side of said support substrate with a lid.
Hereby, the step of covering said top side of said support substrate with a lid or a cover also results in the formation of a cavity built up by said recess and said lid. Accordingly, said first electronic device is housed in or within said recess and said second electronic device is encapsulated simultaneously. The housing of said first electronic device and the encapsulation of said second device are performed in only one step. In one alternative of this embodiment said recess is also manufactured with at least one stair to support said first electronic device and to space said first electronic device from a bottom of said recess.
The present invention also proposes an electronic package comprising at least one support substrate having at least one recess in a top side wherein said recess comprises at least one stair, at least one first electronic device arranged at least partially onto said stair spacing said first electronic device from the bottom of said recess and a lid covering at least partially said top side of said support substrate. Above proposed electronic package is in particular producible or produced with a method according to the present invention.
Said electronic package comprises a cavity which houses said first electronic device and which is formed by covering said recess with said lid. In one embodiment the electronic package further comprises at least one second electronic device being arranged, in particular adjacently to said recess, on said top side of said support substrate.
The invention further proposes an electronic package comprising at least one support substrate having at least one recess in a top side, at least one first electronic device arranged within said recess, at least one second electronic device arranged, in particular adjacently to said recess, on said top side of said support substrate and a lid covering at least partially said top side of said support substrate. Above proposed electronic package is in particular producible or produced with a method according to the present invention.
Accordingly, said electronic package comprises both a cavity which houses said first electronic device and an encapsulation of said second electronic device, both formed by covering said support substrate with said lid. In a preferred embodiment said recess comprises at least one stair onto which said first electronic device is at least partially arranged and which spaces said first electronic device from the bottom of said recess.
Several embodiments of the electronic package are explicitly mentioned. However, since said electronic package is particularly producible or produced by the inventive method, the features of the above and below described method according to the invention correspond also to means or components of the electronic package being produced by said method features.
Said first electronic device comprises MEMS devices such as SAW filter devices, quartz device, thermo sensors, pressure sensors and/or or gyroscopes. In further embodiments said first electronic device comprises sensorial function elements, semiconductor function elements, thermo function elements, mechanical function elements and/or optical function elements. The first electronic device according to the invention has a thickness or a height in the order of 1 μm up to 1000 μm, preferably in the order of some tens μm or 50 μm up to some hundreds μm or 200 μm and a diameter in the order of 1 μm up to some tens mm, preferably in the order 10 μm up to 10 mm.
Said support substrate can be provided as a semiconductor substrate. In one embodiment a Silicon semiconductor is provided as said semiconductor substrate. In another embodiment a compound semiconductor comprising the materials GaAs, InP and/or SiGe is provided as said semiconductor substrate.
Another embodiment uses a semiconductor being characterized by a wide energy gap as said semiconductor. The energy gap is in the order of 2.5 eV up to 10.0 eV, preferably in the order of 3.0 eV up to 6.0 eV. In this case a sapphire is a preferred semiconductor substrate.
The fabrication of said recess on said top side of said support substrate is performed by a subtractive process such as etching, lapping and/or sand blasting. The dimensions of said recess are adapted to the dimensions of the first electronic device to accommodate. The dimensions of the recess need to be chosen such that said first electronic device dives, in particular in essential, completely into said recess. Accordingly, said recess has a depth in the order of 1 μm up to 1000 μm, preferably in the order of 50 μm up to 200 μm and a diameter in the order of 1 μl m up to some tens mm, preferably in the order 10 μm up to 10 mm.
Some embodiments comprise, as already described above, the feature of a recess provided with at least one stair to support and to space said first electronic device from a bottom of said recess. The dimensions of said stair are dependent on the size of the recess. Accordingly, the stair height is smaller than the recess depth and the stair length is smaller than the recess diameter. Said stair has a height in the order of 1 μm up to 400 μm, preferably in the order of 50 μm up to 200 μm and a length in the order of 1 μm up to some tens mm, preferably in the order of 10 μm up to 10 mm. The total stair height or the average stair height corresponds to about 1% to 80%, preferably 10% to 60% of the total recess height or the average recess height. In a particular preferred embodiment said stair height corresponds to about 20% to 50% of the total recess height or the average recess height. The stair length corresponds to about 1% to 80%, preferably 3% to 40% of the total recess length or the average recess length. In a particular preferred embodiment said stair length corresponds to about 5% to 30% of the total recess length or the average recess length.
Said first electronic device is mounted on said stair by gluing, soldering, low temperature glass molding and/or pasting, in particular Ag pasting. Hereby, said first electronic device can be movable mounted. In a particular embodiment this kind of mounting enables the first electronic device to oscillate. The fabrication of said recess is performed by varying the parameters of the above mentioned subtractive process to fabricate the recess.
If the recess according to the invention comprises a stair, said stair can be produced in an one-step-process or in a multi-step-process. For instance, a one-step-process can be realized by a lapping tool or a kind of lapping stamp having the shape corresponding at least essentially to the negative shape of the recess and stair. An example for a multi-step-process corresponds to the application of lapping tools of different sizes and/or shapes. The application combination of said different lapping tools enables the formation of recesses and the corresponding stair. Another example for a multi-step-process corresponds to an etching process using photo-lithographic structuring.
In one embodiment said second electronic device is provided as an integrated circuit. Said integrated circuit can be provided or produced as a solid state or monolithic integrated circuit, as a film integrated circuit and/or as a hybrid integrated circuit. In another embodiment said integrated circuit is provided as a driver or controller integrated circuit for said first electronic device. In a further embodiment said integrated circuit comprises both function, i.e. being both driver and controller integrated circuit for said first electronic device.
To avoid or reduce electronic noise, for instance during a transmission of an electrical signal from said first electronic device to said second electronic device or vice versa, said second electronic device is placed as close as possible to said first electronic device. For instance, said second electronic device directly verges on the upper edge of said recess. Preferably said first electronic device and second electronic device are electrically connected. This connection is performed by wire bonding, soldering and/or metal pasting comprising the materials Au, Al, PbSn, SnAgCu and/or Ag.
The mounting or producing method as well as the dimensions of the second electronic device or integrated circuit are dependent on its embodiment. Said second electronic device is mounted on said top side by gluing, brazing, soldering, low temperature glass molding and/or pasting, in particular Ag pasting, respectively is produced by evaporation, CVD, sputtering, epitaxial growth and/or dotation.
At least one first electrical contact pad is deposited on said top side of said support substrate, in particular adjacent to said recess containing said first electron device. Said first electrical contact pad is fabricated by photo-lithographic techniques using for instance PVD, in particular evaporation and/or sputtering, and/or CVD. The materials forming said first electrical contact pad comprise Au, Al, TiCu, AlSiCu, AlSiTi, W, Cu and/or AlCu. Said first contact pad comprises a thickness in the order of 1 nm up to some tens μm, preferably in the order of 100 nm up to 1 μm and a diameter in the order of 1 μm up to some hundreds μm, preferably in the order of 10 μm up to 500 μm. Said first electrical contact pad is in particular electrically connected with said first electronic device. This connection is performed by wire bonding, soldering and/or metal pasting comprising the materials Au, Al, PbSn, SnAgCu and/or Ag.
According to the corresponding embodiments at least one second electrical contact pad is arranged on said top side of said support substrate, in particular adjacently, to said second electron device to contact said second electronic device. Said second electrical contact pad can be fabricated by using the same techniques and materials as mentioned above for said first electrical contact pad. Preferably the first and the second electrical contact pad are fabricated simultaneously in one step. Said second electrical contact pad is electrically connected with said second electronic device. This connection can be performed according to the above described connection between said first electronic device and said first electrical contact pad.
Said support substrate is covered by said lid or cover in an adjoining relationship. This covering leads to the formation of a cavity by said recess housing the first electronic device. According another embodiment of the present invention having both said first electronic device in said recess and second electronic device on said top side of said support substrate, the covering of the support substrate by said lid forms both a cavity housing the first electronic device and an encapsulation for said second electronic device simultaneously. The inventive method eliminates the need for a separate packaging of electronic devices and their corresponding integrated circuits. The disclosed packaging method advantageously eliminates the handling of exposed sensors during packaging operations, and results in a closer placement of the electronic device and its associated integrated circuit, so that cost are reduced and greater systems performance can be achieved using common packaging technologies.
Preferable materials for said lid comprise glass, metal, ceramic, semiconductor and/or plastic and can be provided as a film. Dependent on its material said lid comprises a thickness in the order of 10 μm up to some mm, preferably in the order of 100 μm up to 1 mm. Said lid covers at least partially said support substrate. In a further embodiment the diameter of said lid corresponds essentially to the diameter of said support substrate to cover.
A contact side of said lid touching at least partially said top side of said support substrate is provided flat, i.e. non-structured, so that said contact side of said lid is entirely in touch with said top side of said support substrate. In another embodiment said contact side of said lid, which touches said top side of said support substrate, is provided structured, i.e. comprising a first recess in the area of said first electronic device. In this particular embodiment the cavity, which houses said first electronic device is formed by said recess in said support substrate and by said recess in said lid. In another embodiment said contact side of said lid is provided structured such that said contact side comprises a first recess in the area of said first electronic device or a second recess in the area of said second electronic device. In a further embodiment said contact side of said lid is provided structured such that said contact side comprises a first recess in the area of said first electronic device and a second recess in the area of said second electronic device. Accordingly, said contact side of said lid is provided structured comprising at least one recess in said lid contact side. In this particular embodiment beside the cavity, which houses said first electronic device and which is formed by said first recess, also a cavity is formed by said second recess, which houses said second electronic device.
Said top side of said support substrate and said contact side of covering said lid are bonded together. Possible techniques for bonding said top side of said support substrate and said contact side of said lid together are anodic bonding, low-temperature-bonding, brazing, gluing, soldering and/or glass melting, in particular low temperature glass melting. According to one embodiment said contact side of said lid and/or said top side of said lid is respectively are covered at least partially with at least one adhesive layer and said support substrate and said lid are bonded together via said at least one adhesive layer. Said adhesive layer comprises a thickness in the order of 100 nm up to some tens μm, preferably in the order of 1 μm up to 10 μm and a diameter corresponding in particular essentially to the diameter of said lid or said support substrate to cover. In another embodiment both sides, i.e. said contact side of said lid and said top side of said support substrate are covered with at least one adhesive layer and said support substrate and said lid are bonded via said adhesive layers. Since it is easy to deposit, in a preferred embodiment the adhesive layer covers entirely said contact side of said lid.
In another embodiment said adhesive layer comprises at least one gap or recess. In one embodiment said adhesive layer comprises at least one first gap or one first recess in the area of said first electronic device or said recess and/or a second gap or second recess in the area of said second electronic device. Accordingly, the corresponding recess, which accommodates said first electronic device, and/or said second electronic device is respectively are not covered by said adhesive layer enabling the possibility of using electronic devices sensitive to said adhesive layer. Said adhesive layer is for instance realized by gluing, blazing, soldering and/or glass layer melting. Possible materials in accordance to above mentioned methods forming said adhesive layer are resin, preferentially epoxy resin and/or acrylic resin, AuSn, PbSn, SnAgCu and/or low temperature melting glass. Said adhesive layer is deposited by spin coating, spray coating, PVD, in particular sputtering and/or evaporation, screen printing and/or filming. In a preferred embodiment of the present invention the cavity housing the first electronic device is formed such that said first electronic device and/or said second electronic device is respectively are hermetically sealed. In particular said first electronic device and/or said second electronic device is respectively are hermetically sealed in said cavity respectively in between the contact side of the lid and the top side of the support substrate.
To provide the electrical contact to the housed first electronic device at least one first via-hole is fabricated into a bottom side of said support substrate and/or a rear side of said lid allowing access to said first electrical contact pad or connecting top said and bottom side of said support substrate. Possible techniques for the fabrication of said first via-hole are etching, lapping and/or sand blasting. If suitable, photo-lithographic techniques can be applied. The via hole or said first via-hole is fabricated as deep as allowing direct access to said first electrical contact pad. Accordingly, said first via-hole has a depth according to the thickness of said support substrate and a diameter in the order of 1 μm up to some hundreds μm, preferably in the order 50 μm up to 200 μm.
For establishing an electrical connection from said bottom side of said support substrate or from said rear side of said lid trough said first via-hole to said first electrical contact pad and said first electronic device, an electrical connection, in particular at least one first electrical connection line, is fabricated. Possible techniques for the fabrication of said first electrical connection line are PVD, for instance evaporation and/or sputtering, and/or CVD comprising the materials Au, Al, Cu, AlSi and/or AlCu. If suitable, photo-lithographic techniques can be applied.
Enabling an easy further processing of the resulting electronic package e.g. its mounting on a printed circuit board at least one first solder ball is placed onto said first electrical connection line. A preferred technique for the mounting of said first solder ball is a reflow process, laser mounting, Au/Au floating process, conductive film interconnecting process and/or Ag soldering. Accordingly, preferred processes involve a melting of prefabricated solder balls on said first electrical connection line. Said first solder ball has a diameter in the order of 10 μm up to some hundreds μm, preferably in the order 100 μm up to 500 μm comprising PbSn, SnAgCu and/or ZnSn.
According to the above mentioned particular preferred embodiment of this invention at least one second via-hole is fabricated into said bottom side of said support substrate or into said rear side of said lid, allowing access to said second electrical contact pad. Said second electrical via-hole can be fabricated by using the same technique and same materials as mentioned above for said first via-hole. Preferably said first and said second via-hole are fabricated simultaneously in one step. Said second via-hole allows access to said second electrical contact pad.
According to this embodiment also an electrical connection, in particular at least one second electrical connection line, is fabricated trough said second via-hole from said second electrical contact pad to said bottom side of said support substrate or to said rear side of said lid. And also at least one second solder ball is placed onto said second electrical connection line. Said second electrical connection line and/or said second solder ball can be fabricated by using the same technique and same materials as mentioned above for the corresponding said first electrical connection line respectively said first solder ball, preferably they are mounted simultaneously.
Electrical connections or electrical connection lines between said first contact pads and said first electronic devices, between second contact pad and second electronic device and/or between first electronic device 61 and second electronic device can be fabricated by using the same technique and same materials as for the above mentioned first electrical connection line.
The above described photo-lithographic technique for deposition processes, as for instance PVD, comprises the steps of coating the support substrate with a photosensitive resist layer, photo-lithographic structuring of the applied resist layer, coating the pre-structured substrate with the corresponding layer which comprises the corresponding material and lifting off the resist layer. The photo-lithographic structuring step comprises mask exposure and subsequent developing. The step of coating can be carried out by spin coating, spraying, electrodeposition and/or by depositing of at least one photosensitive resist foil. The step of lifting off the resist layer is carried out in such a manner that at least one layer that has been applied to the resist layer is also lifted off. The fabrication of via holes or recesses by photo-lithographic techniques is correspondingly applied.
Beside the mounting of the above mentioned components to form said electronic package, i.e. the mounting of the electronic package as a single chip, the mounting can be performed in one preferred embodiment in a wafer assembly. Accordingly, a multitude of chips of the same type are fabricated simultaneously. Said wafer assembly comprising said multitude of electronic packages is diced into single chips via sawing, lapping, sand blasting, laser cutting, diamond scribing and/or snapping. In a first embodiment each chip comprises said first electronic device, said cavity, said first electrical contact pad, said first via-hole, said first electrical connection line and said first solder ball. Said electronic package comprises a thickness in the order of 10 μm up to 5 mm, preferably in the order of 100 μm up to 1 mm and a diameter in the order of 1 μm up to 200 μm, preferably in the order of 10 μm up to 100 μm. In another embodiment each chip comprises said first electronic device, said cavity, said second electronic device, said first electrical contact pad, said second electrical contact pad, said first via-hole, said second via-hole, said first electrical connection line, said second electrical connection line, said first solder ball and said second solder ball. Said electronic package comprises a thickness in the order of 50 μm up to 2 mm, preferably in the order of 100 μm up to 1 mm and a diameter in the order of 500 μm up to 20 mm, preferably in the order of 1 mm up to 10 mm.
The method according to this invention enables an efficient fabrication of packaged electronic devices and of packaged electronic devices and their associated controller and/or driver integrated circuits.
The invention is explained subsequently in more detail on the basis of preferred embodiments and with reference to the appended figures. The features of the different embodiments are able to be combined with one another. Identical reference numerals in the figures denote identical or similar parts.
DESCRIPTION OF THE FIGURES
FIG. 1 shows a schematic side view of an electronic package comprising a first electronic device being movable mounted and a second electronic device.
FIG. 2 shows a schematic side view of a further electronic package comprising a first electronic device and a second electronic device.
FIG. 3 . a to 3 . w schematically illustrate in a side view the process steps to fabricate an electronic package according to the invention involving a first electronic device.
FIG. 4 schematically shows an electronic package being produced according to the method illustrated in FIGS. 3 . a to 3 . w.
FIG. 5 . a to 5 . l schematically illustrate in a side view the process steps to fabricate an electronic package according to the invention involving a first electronic device.
FIG. 6 schematically shows an electronic package being produced according to the method illustrated in FIGS. 3 . a to 3 . w.
Subsequently, preferred but exemplar embodiments of the invention are described in more detail with regard to the figures.
DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS
The figures show the feature of a backside-contacting. The electronic components, in particular the first and the second electronic device are electrically contacted via the backside 1 b of said support substrate.
FIGS. 1 and 2 show a schematic side view of an electronic package 20 comprising a first electronic device 61 and a second electronic device 62 producible or produced with a method according to the invention. The electronic package 20 comprises a support substrate 1 , which has at least one recess 7 in its top side 1 a . Said support substrate 1 is bonded with a lid 4 , which forms simultaneously a cavity 75 housing a first electronic device 61 and an encapsulation of a second electronic device 62 placed adjacent to said recess 7 on said top side 1 a . Said first electronic device 61 is connected to a first electrical contact pad 91 . Said first electrical contact pad 91 is connected trough a first via-hole 101 and a therein placed first electrical connection line 31 to a bottom side 1 b of said support substrate 1 and is connectable by a first solder ball 21 , e.g. to a printed circuit board. Said second electronic device 62 is connected to a second electrical contact pad 92 . Said second electrical contact pad 92 is connected trough a second via-hole 102 and a therein placed second electrical connection line 32 to a bottom side 1 b of said support substrate 1 and is further connectable by a second solder ball 22 , e.g. to a printed circuit board. In FIG. 1 said first electronic device 61 is mounted on a stair 11 . In particular said first electronic device 61 is movably mounted on said stair 11 . In FIG. 2 , in contrast to FIG. 1 , said first electronic device 61 is directly mounted or placed onto the bottom 71 of the recess 7 and said first electronic device 61 can not be enabled to oscillate.
One fabrication method embodiment is subsequently explained in more detail in FIGS. 3 . a to 3 . w . The illustrated method shows the packaging of electronic components on a wafer level. The method for packaging electronic components according to FIGS. 3 . a to 3 . d comprises the first step of providing a wafer or a support substrate 1 . Said support substrate 1 is a semiconductor substrate. Said support substrate 1 comprises a thickness in the order of 50 μm up to 500 μm and a diameter in the order of 4″ up to 12″. FIG. 3 . a shows a view onto the top side 1 a of a support substrate 1 . FIG. 3 . b shows a zoom of the section Z shown in FIG. 3 . a . It is illustrated a partitioning of the wafer in sections 1 c . A fabrication or mounting of electronic components or devices, for instance of the first and/or the second electronic device 61 respectively 62 , occurs within these sections 1 c . FIG. 3 . c and 3 . d show a schematic side view or cross section of the zoom Z shown in FIG. 3 . b along intersection line S. The shown support substrate 1 has a top side 1 a and a bottom side 1 b.
FIG. 3 . d to 3 . i illustrate the fabrication of contact pads, for instance of the first and second contact pads 91 respectively 92 , by the usage of photo-lithographic techniques. It comprises the steps of coating the substrate 1 on its top side 1 a with a photosensitive resist layer 2 (FIG. 3 . e ) and forming recesses 2 a are by a photo-lithographic structuring of the applied layer 2 (FIG. 3 . f ). In a further step the top side 1 a of the substrate 1 is coated with a layer 9 of a conductive material, for instance a metal like Au, by a PVD process like electron beam evaporation or sputtering. First electrical contact pads 91 are formed on the top side 1 a of the support substrate within said recesses 2 a (FIG. 3 . g ). The resist layer 2 is lifted off in a further step (FIG. 3 . i ) and the first electrical contacts pads 91 remain fixed on the top side 1 a (FIG. 3 . i ). The distance between said first electrical contact pads 91 is determined by the dimensions of said first electronic device 61 to be mounted or by the section 1 c partitioning.
The method for packaging electronic components further comprises the step of producing of at least one recess 7 in a top side 1 a of said support substrate 1 by a subtractive process which is illustrated in FIGS. 3 . j and 3 . k . The dimensions of said recess 7 are adapted to the dimensions of said first electronic device 61 to accommodate. The dimensions of said recess 7 are chosen such that said first electronic device 61 dives completely in said recess 7 . The fabrication of said recess 7 is performed by ultrasonic-lapping. The dimensions of a lap-tool or a lap-die is determined by the dimensions of the first electronic device 61 to accommodate within the produced recess 7 . In one embodiment of the invention said recess 7 comprises one stair 11 at a bottom 71 of said recess 7 . The dimensions of said stair 11 are determined by the dimensions of said first electronic device 61 to support and to space from said bottom 71 of said recess 7 .
The fabrication of said stair 11 within said recess 7 or the fabrication of said recess 7 and said stair 11 is performed by lapping in a 2-step process using two lap-dies, in particular a first lap-die 110 and a second lap-die 111 , having different dimensions according to the dimensions of said recess 7 and the dimensions of said stair 11 to produce. In a first lapping process the first lap-die 110 is used to fabricate a first recess section 72 corresponding to the diameter of the total recess 7 reduced by the length of said stair 11 . The lapping process is performed up to the desired depth of the recess 7 or recess section 72 . In a second lapping process a second lap-die 111 is used to increase the recess 7 diameter by a second recess section 73 to the desired recess diameter 7 . Another option is based on a lapping in a 1-step process using a lap-die with a shape corresponding to the desired shape of said recess 7 and said stair 11 or the combined shape of said first lap-die 110 and said second lap-die 111 .
The method for packaging electronic components comprises as an additional step the mounting or placing of one first electronic device 61 into said recess 7 (FIG. 3 . l ). For instance said first electronic device 61 corresponds to an acceleration sensor. Accordingly, said first electronic device 61 is movably mounted on said stair 11 by gluing. Said stair 11 supports and spaces said first electronic device 61 from the bottom 71 of the recess 7 . Since said first electronic device 61 is mounted only at least on one of its sides, said stair 11 enables said first electronic device 61 to oscillate to detect an affecting acceleration.
Said first electronic device 61 is electrically connected with said first electrical contact pad 91 by wire bonding comprising the material Au (FIG. 3 . m ). The inventive method further comprises the covering of said top side 1 a of said support substrate 1 with a lid 4 (FIG. 3 . n ). Said support substrate 1 is covered by said lid 4 in an adjoining relationship by means of an adhesive layer 4 , in particular a glue layer, placed onto the bottom side 1 b of said support substrate 1 . According to this embodiment, the covering by said lid 4 results in a formation of a cavity 75 housing said first electronic device 61 . A preferred cover comprises a glass plate having a thickness in the order of 10 μm up to some mm and a diameter corresponding essentially to the diameter of said support substrate 1 to cover. Accordingly, said top side 1 a of said support substrate 1 and a contact side 4 a of said covering lid 4 are bonded together by gluing. A curing of the adhesive layer 5 can be supported by irradiation. The adhesive layer 5 can be deposited by spin coating and substantially can cover entirely said contact side 4 a of said lid 4 . Said adhesive layer 5 comprises a thickness in the order of 100 nm up to some tens μm and a diameter corresponding essentially to the diameter of said lid 4 .
The positioning of said first electronic device 61 within said cavity 75 enables a simplified handling of the electronic package 61 in the following process steps and an efficient protection of said first electronic device 61 e.g. against arising dust produced in the following process steps.
The method for packaging electronic components comprises as a subsequent step the providing of an electrical contact to the housed first electronic devices 61 (FIG. 3 . q to 3 . v ). This is achieved by the fabrication of first via-holes 101 into a bottom side 1 b of said support substrate 1 which allows an access to the first contact pads 91 to contact the first electronic devices 61 .
The shown via hole fabrication uses photo-lithographic techniques with the steps of coating the substrate 1 on its bottom side 1 b with a photosensitive resist layer 120 (FIG. 3 . p ). Recesses 120 a are formed by a photo-lithographic structuring of the applied resist layer 120 (FIG. 3 . q ). In a further step the bottom side 1 b of the substrate 1 is treated in a selective etching process producing said via holes 101 according to said recesses 120 a (FIG. 3 . r ). The corresponding via-holes 91 are fabricated as deep as allowing direct access to said first electrical contact pads 91 . The residual resist layer 120 is removed in a lift-off process (FIG. 3 . s ).
To establish the electrical connection from said bottom side 1 b of said support substrate 1 to said first contact pads 91 the via holes 101 are filled up with a conducting material 105 (FIG. 3 . t ). First electrical connection lines 31 are fabricated by an evaporation process comprising Au using photo-lithographic structuring as described above for the fabrication of the first contact pads 91 (FIG. 3 . u ).
To enable an easy further processing of the resulting electronic packages 20 , e.g. their mounting on a printed circuit board, first solder balls 21 are placed onto said first electrical connection lines 31 (FIG. 3 . u ). A preferred technique for the fabrication of said first solder ball 21 is the reflow technique. The first contact pads 91 and the first solder balls 21 are laterally shifted to each other. A vertical projection of the first contact pad 91 center and the first solder ball center 21 does not coincident. The vertical direction corresponds to a direction perpendicular to the top side 1 a of the support substrate 1 . FIG. 3 . w shows the cutting or dicing of the fabricated wafer assembly. The assembly is cut along cutting lines C. Said cutting lines are positioned between said sections 1 c . A resulting electronic package 20 is shown in FIG. 4 . The electronic package 20 comprises a thickness in the order of 50 μm up to 2 mm and a diameter in the order of 500 μm up to 20 mm. It can be mounted e.g. on a non-shown printed circuit board or on another non-shown circuit substrate that for instance provides power inputs and receives instrument outputs as required by the system in which it is to be used. Since the connecting lines 31 extend essentially parallel to the back side 1 b from the bottom side of the filling material 105 to a bottom side of a corresponding cavity 75 projection, a compact and space-saving design of the electronic package is enabled.
FIGS. 5 . a to 5 . l schematically show a further embodiment of the present inventive method to illustrate the process steps involving the mounting of a first and a second electronic device 61 and 62 . In case that the fabrication of a second component is not explicitly explained, the fabrication of a first component described in FIGS. 3 a to 3 . w can be applied also to said second component. For instance the deposition of the second electrical contact pads 92 is performed in the same manner or at least in a similar manner as the fabrication of the first electrical contact pads 91 .
FIG. 5 . a shows the support substrate 1 after the fabrication of the recesses 7 and the deposition of the first and second electrical contact pads 91 and 92 . First electronic devices 61 , for instance optical detectors, are positioned onto the bottom 71 of said recesses 7 (FIG. 5 . b ). Second electronic devices 62 are positioned, in particular adjacently to said recesses 7 , on the top side 1 a of said support substrate 1 (FIG. 5 . c ). In one embodiment of the present invention said second electronic device 62 is an integrated circuit. In particular said integrated circuit is provided as a controller integrated circuit for said first electronic device 61 .
The electrical connection of said first electronic device 61 and said second electronic device 62 is illustrated in FIG. 5 . d . The electrical connection 81 of the first electronic device 61 with the first electrical contact pad 91 is performed by wire bonding. The connection 82 between the second electronic device 62 and the second electrical contact pad 92 is realized by metal pasting 82 . The first electronic device 61 and the second electronic device 62 are electrically connected via the connecting line 83 which can be produced also by metal pasting.
One further step for packaging electronic components corresponds to a covering of said top side 1 a of said support substrate 1 with a lid 4 (FIG. 5 . e and FIG. 5 . f ). Said support substrate 1 is covered by said lid 4 in an adjoining relationship via anodic bonding. A preferred cover or lid 4 is provided as a glass plate or a plate being at least transparent for the radiation to be detected by said first electronic device 61 . Accordingly, the covering by said lid 4 results in a simultaneous formation of a cavity 75 housing said first electronic device 61 and an encapsulation of said second electronic device 62 . The position of said first electronic device 61 within said cavity 75 and the encapsulation of said second electronic device 62 enable a simplified handling and enhanced protection of the electronic package 20 to be produced in the subsequent fabrication steps.
FIGS. 5 . g and 5 . j illustrate the providing of an electrical connection to the housed first electronic devices 61 and to the encapsulated second electronic device 62 . The respective fabrication of the first and the second via holes 101 and 102 is illustrated in FIGS. 5 . g to 5 . i and corresponds to the fabrication of the first via holes 101 as shown in FIGS. 3 . q to 3 . s . The first via-holes 101 and the second via holes 102 allow access to the first respectively second electrical contact pads 91 and 92 .
To establish the electrical connection from said bottom side 1 b of said support substrate 1 to said first respectively second contact pads 91 and 92 the respective via holes 101 and 102 are provided or equipped with first respectively second electrical connecting lines 31 and 32 . Said first and second electrical connecting lines 31 and 32 can be fabricated by photo-lithographic structuring according to the above described fabrication of the first contact pads 91 . The respective solder ball deposition and wafer dicing (FIGS. 5 . k and 5 . l ) correspond to the solder ball deposition and wafer dicing shown in FIGS. 3 . v and 3 . w . The fabricated electronic package 20 after dicing is shown in FIG. 6 .
Since the first electronic device 61 and/or the second electronic devices 62 are well protected by the housing within said cavity respectively the encapsulation in between the contact side 4 a of the lid and the top side 1 a of the substrate, a disturbance or a damage of the electronic devices 61 and 62 can be reduced or even avoided.
A method of packaging electronic devices and of packaging electronic devices with their associated integrated circuits has been shown. It will be understood that the invention may be embodied in other specific forms without departing from the spirit or central characteristics thereof. The present examples and embodiments, in particular the above mentioned materials, therefore, are to be considered in all respects as illustrative and not restrictive, and the invention is not to be limited to the details given herein. Above described sequence of method steps can be exchanged in a reasonable manner.
REFERENCES
1 Support substrate
1 a Top side of the support substrate
1 b Bottom side of the support substrate
1 c Section of the top side 1 a
2 Resist layer
2 a Recess in the resist layer 2
4 Lid or cover
4 a Contact side of the lid 4
5 Adhesive layer
7 Recess
9 Conductive material layer
11 Stair
20 Electronic package or chip
21 First solder ball
22 Second solder ball
31 First electrical connection line
32 Second electrical connection line
61 First electronic device
62 Second electronic device
71 Bottom of the Recess
72 First section of recess 7
73 Second section of recess 7
75 Cavity
81 Connection between first contact pad 91 and first electronic device 61
82 Connection between second contact pad 92 and second electronic device 62
83 Connection between first electronic device 61 and second electronic device 62
91 First electrical contact pad
92 Second electrical contact pad
101 First via-hole
102 Second via-hole
105 Conductive material filling
110 First lap-die
111 Second lap-die
120 Resist layer
120 a Recess in resist layer 120
200 Lift-off-direction
Z Zoom
S Intersection line
C Cutting line
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The present invention relates to the field of electronic devices and their associated driver and/or controller integrated circuits and in particular to the mechanical packaging of electronic devices and to the packaging of electronic devices and their associated driver and/or controller integrated circuits.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a device and method for determining in situ stresses and/or strength characteristics of a subterranean formation. More particularly, the invention relates to a device for insertion in a borehole extending into a formation, which device when pressurized exerts force radially against the borehole wall in all directions except along one plane dividing the device longitudinally.
There are many situations, such as during mining of coal or other mineral from a subterranean formation, where it is desirable to know the existing in situ stresses and/or the strength characteristics of a particular formation. Such knowledge is useful in planning the developement of the formation, and particularly as to the safety of the operation.
2. Description of the Prior Art
There are many procedures of varying degrees of usefulness which have been previously utilized in attempts to analyze the stresses and strength characteristics of subterranean formations. One method of determining the strength of a formation has been to seal a portion of a borehole with packers and then pressurize the sealed section. The formation fracture pressure can be determined in this manner, but this only gives information regarding the weakest direction. It is desirable to have information regarding stresses and strength in a plurality of directions and at a plurality of locations in order to analyze a formation by non-destructive methods. Such information is useful in techniques such as finite element analysis of force distribution within a formation.
The present invention makes possible a non-destructive "microseismic" method of formation analysis because of its capability for providing information in a plurality of directions which reflects the forces acting on the formation at a given location.
SUMMARY OF THE INVENTION
According to the present invention, a device is provided which is easily inserted into a borehole extending into a subterranean formation, which device when pressurized exerts uniform radial forces agains the borehole wall in all direction except along a particular plane extending longitudinally through the device. As a result, a parting force is exerted on the formation through that particular plane which is higher than the parting force exerted on any other plane through the axis of the device. The formation typically develops stress microcracks well before failure pressure is exerted on it, and by using a sound pickup with device which detects microcrack occurrence the strength characteristics of a formation can be determined for a given plane through the formation. The formation strength through several planes at a particular location in the formation can be determined by this invention since it is not necessary to fracture the formation to obtain a measurement through a particular plane. Such information is useful for establishing a safe mining program.
The device according to the invention includes a pair of inflatable semi-cylindrical members mounted on a shaft having a fluid passage for pressurizing the inflatable members. The device is inserted while uninflated and then when in position it is inflated by fluid pressure such that it contracts the borehole wall and exerts pressure on the wall. Because of the unique structure of the device, no pressure is exerted along one particular plane, and as a result the formation strength through that plane can be determined.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side elevational view showing a preferred form of the device.
FIG. 2 is a cross-sectional view taken along the line 2--2 of FIG. 1 showing the interior of the upper portion of the device in the pressurized condition.
FIG. 3 is a view similar to FIG. 2 but showing the device in the unpressurized condition.
FIG. 4 is a top plan view, partly in cross-section, taken along the line 4--4 of FIG. 2 with the device in the pressurized condition.
FIG. 5 is a cross-sectional view of the device of FIG. 1, taken along the line 5--5 of FIG. 2 with the device in the pressurized condition.
FIG. 6 is a top plan view, partly in cross-section, taken along the line 6--6 of FIG. 3 with the device in the unpressurized condition.
FIG. 7 is a view similar to FIG. 5 but with the device in the unpressurized condition.
FIG. 8 is a perspective view of a segment forming a part of the device.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The most preferred embodiment of the invention will now be described by reference to the accompanying drawings illustrating same.
The overall device 10 is illustrated generally in FIG. 1, and as best seen in FIGS. 2 and 3 includes a central shaft member 11 having a fluid passage 12 extending from the top end of the device to an intermediate portion of the shaft. Fluid passage 12 intersects a transverse fluid passage through shaft 11 constituting a pair of outlets 13.
A pair of elastomeric semi-cylindrical members 14 are bonded to shaft 11 and plate 25 (FIGS. 5 and 7) and positioned so as to form a generally cylindrical structure. Each semi-cylindrical member 14 includes an opening in register with an outlet 13 such that fluid transmitted down fluid passage 12 flows into semi-cylindrical members 14. An insert 15 extends from the interior of each member 14 into each outlet 13 to help position the opening in member 14 over outlet 13. The member 14 may be formed of any natural synthetic tough elastomeric material. Butyl rubber is a particularly good material for these members.
The top end of device 10 includes a fixed support plate 16 attached to shaft 11 (FIG. 2). A floating support plate 17 (FIGS. 2 and 3) movable axially along shaft 11 is positioned just above the upper ends of members 14. Floating support plate 17 has an upper angled surface 18 (FIG. 3), the purpose of which will be described later. Located between fixed support plate 16 and floating support plate 17 is a segmented radially expandable disc unit constructed of a plurability of segments 20 as shown in FIGS. 1, 4 and 6.
Each segment 20 forms a part of a circle in plan view, and the inner edge of each segment 20 is shaped to fit about shaft 11 when the device is in the unpressurized condition as shown in FIG. 6. Near the inner end of each segment 20 is a spring-retaining groove 21, and a spring 22 or elastic ring in the groove 21 of a series of segments 20 operates to bias the segments against shaft 11. Each segment 20 has an angled surface 23 (FIG. 3) which matches angled surface 18 on floating support plate 17. It will be apparent that upon movement of floating support plate 17 toward the expandable disc formed of segments 20 that the angled surface 18 of plate 17 will act on angled surfaces 23 on segments 20 and move the segments 20 radially outward from shaft 11. As is clear from FIG. 2, the outward movement of segments 20 is limited. Upon movement of floating plate 17 away from the disc unit, spring 22 acts to return segments 20 to the original position shown in FIGS. 3 and 6.
A microphone 24 including an electrical lead 29 is shown mounted on upper support plate 16 for purposes to be described later.
The lower end of device 10 includes substantially indentical parts as described above for the upper end, except that no microphone is associated therewith.
Referring now to FIGS. 5 and 7, shaft 11 includes flat plate members 25 extending outwardly therefrom and constituting separating means for keeping the flat surfaces of inflatable members 14 out of contact with each other. The outer edge of each plate member 25 has a slot 26 formed therein, and a strip 27 is positioned in each slot 26 and biased outwardly by springs 28 and retained by a shoulder formed near the outer limit of slot 26.
The operation of the device 10 will now be described for a typical project of determining the strength characteristics of a subterranean formation. First, a borehole having a diameter slightly larger than that of fixed support plate 16 of the device 10 is drilled into a subterranean formation. The device 10 is then lowered into the borehole by pipe joints (not shown) connected to shaft 11, care being taken to maintain a known orientation of device 10 within the borehole.
When the device 10 is at the desired depth, fluid is introduced through passage 12 into members 14. Members 14 expand slightly in response to the fluid pressure, and contact the wall of the borehole. Continued injection to fluid into members 14 forces the ends of members 14 outwardly against floating support plates 17, which in turn move outwardly against segments 20 of the disc units, causing segments 20 to move slightly outwardly by the camming action of surface 18 against surface 23. When segments 20 have moved to the full outward position, their outer surfaces are against or very near the wall of the borehole as shown in FIGS. 2 and 4, such that upon increasing the pressure in members 14 the ends thereof cannot bulge out beyond fixed support plates 16. Thus, it will be seen that device 10 can be built with a diameter smaller than the diameter of the borehole in which it is to be used, enabling easy insertion of the device in the borehole. At the same time, expandable disc units formed of segments 20 between fixed support plates 16 and floating plates 17 can extend outwardly to fill the gap between the fixed support plates and the borehole wall upon inflation of members 14, thereby preventing bulging out and bursting of the members 14 when they are subjected to high pressures.
When the expandable disc units are in the enlarged or outermost position, fluid pressure in members 14 is increased until microcracks begin to form in the formation along the plane between the inflatable members 14. This might require a pressure in members 14 of several hundred kilograms per square centimeter. As the microcracks begin to form, typically at about half the pressure required to fracture the formation, the microphone 24 detects the sound generated and transmits it to the operator. The pressure in members 14 is then released, and springs 22 retract segments 20 away from the borehole to the position shown in FIGS. 3 and 6. The device is then rotated through a desired angle and/or moved longitudinally in the borehole, and the process is repeated until sufficient measurements have been made to enable an analysis of the strength characteristics of the formation.
To retrieve the device 10 from the borehole, the pressure in members 14 is released, allowing segments 20 to retract, and the device is then pulled out. Strips 27 do not significantly retard removal, as they are pushed back into slots 26 by the borehole wall.
The number of segments 20 required for each disc unit is determined by the amount of radial movement expected, the strength of the elastomeric member, and the symmetry of the borehole. More than six are required to provide any improvement, as with six segments the maximum dimension of the gap between segments upon expansion is the same as the dimension between the unexpanded and expanded radii. Preferably from 24 to 48 segments are used, with 36 being a particularly preferred number of segments for each disc unit.
In accordance with an alternative simplified version of the invention (not shown), the floating support plates 17 and segments 20 can be eliminated, and the inflatable members 14 can bear directly on fixed support plates 16. This version generally requires a closer fit between the device and the borehole to prevent bulging of the pressurized inflatable members past the fixed support plates. Likewise, this version can be used without the slot and strip in the separating members.
The foregoing detailed description of the construction and operation of the most preferred embodiment of the device is intended to be illustrative rather than limiting, and it will be apparent to those skilled in the art that numerous modifications and variations could be made without departing from the true scope of the invention, which is defined by the appended claims.
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A device and method for determining strength properties of a subterranean formation. The device is insertable into a borehole formed in the formation, and includes a pair of inflatable semi-cylindrical members mounted on a shaft. The inflatable members when pressurized exert radial force in all directions except along the plane between the members, with the result that a higher parting force is exerted on the formation perpendicular to the plane between the members than across any other plane through the axis of the device.
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BACKGROUND OF THE INVENTION
This application is directed to an improved embodiment of what is known in the art as a B.R.D.A. former, with which applicants are familiar. B.R.D.A. are the initials of Boxboard Research and Development Association of Kalamazoo, Mich.
It has been known to make paper on a perforated cylinder revolving in a vat. In the above mentioned B.R.D.A. former a perforated cylinder is still used, but the vat is eliminated in favor of the flow box having a pressure lid in contact with about eight inches of the cylinder mold face. The stock is collected on the face of the mold with most of the water draining through its wire face. It is most important that the fibrous component of the paper making stock be evenly dispersed with random fiber networks and no streaking or streaming or bulges in the lid. It is also important that the stock be free of local turbulence which could cause non-uniformities in the weight, thickness and appearance of the finished paper. The B.R.D.A. former utilizes a tapered flow spreader delivering stock to a set of elongated plastic tubes which enter the explosion chamber at cross angles to each other and at oblique angles to the floor of the chambr and to the face of the upstanding baffle in the chamber, all as disclosed in U.S. Pat. No. 3,565,758 of Feb. 23, 1971 and U.S. Pat. No. 3,622,450 of Nov. 23, 1971 of St. Anne's Board Mill Company Ltd., Bristol, England.
It has heretofore been proposed in U.S. Pat. No. 2,894,581 to Goumeniouk of July 14, 1959 and U.S. Pat. No. 3,328,236 to Burgess of June 27, 1967 to provide a tapered manifold of circular, or rectangular cross section which feeds stock directly to a head box by means of a bank of elongated crossed tubes. As mentioned above it has also been proposed to provide a similar tapered manifold and a bank of shorter crossed tubes to feed stock into an expansion chamber and thence into a pressure lid as in the B.R.D.A. apparatus. It has further been proposed in U.S. Pat. No. 2,929,449 to Mardon of Mar. 22, 1960 and U.S. Pat. No. 3,119,733 to Wilson of Jan. 28, 1964 to provide a tapered manifold of rectangular cross section which has an apertured plate as one wall for delivering stock through the apertures directly into a head box.
SUMMARY OF THE INVENTION
However, as far as we are aware it has not been proposed in the prior art to provide a tapered manifold with an apertured plate and to use that plate as a common wall in a unitary flow box so that the axes of the apertures are normal to the plane of an imperforate flow box baffle. Thus the tapered manifold feeds directly into the expansion, or explosion chamber of the flow box, and the complicated, costly and relatively inefficient bank of tubes is eliminated. In the flow box of this invention, the stock not only impacts the planar face of the baffle from the plate apertures in a direction normal to the plane for 360° spreading thereof but is diverted upwardly, along the imperforate baffle, and again impacts the roof, or top wall, of the expansion chamber for a second 360° spreading normal to the plane thereof before being diverted forwardly over the baffle and reaching the narrow passage of the chamber.
The pressure lid of the flow box of the invention, contrary to the teaching of the art, is usually elongated in the range of at least 12 inches and up to 18 inches or more for greater dwell time of the stock as it drains through the cylinder mold wire under pressure in the lid. The pressure lid has an integral, resilient flange hinge, and rubber cushion, connection to the flow box together with profile knob support mountings arranged to permit the increased arcuate coverage of the lid. The lid cooperates with a novel beaded rubber strip, serving as a bottom plate which slides axially outward for replacement whenever required. To correct any uneven distribution of stock through the apertures, the tapered manifold includes a top, or roof, plate insert which controls the volume within the manifold and can be easily slidably removed for remachining to vary the pressure across the apertured plate.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a schematic side elevational view of a typical cylinder mold with the former of the invention installed therein;
FIG. 2 is an enlarged, fragmentary, side elevational view, in section, on line 2--2 of FIG. 3;
FIG. 3 is a fragmentary front view of the former shown in FIG. 2; and
FIG. 4 is a plan view, on a reduced scale of the former; and
FIG. 5 is a view similar to FIG. 2 but showing the flexible, articulated pressure lid of the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
As shown in FIG. 1, a typical cylinder mold paper making machine 21 includes a cylinder mold 22, rotatable on shaft 23 in frame 24, there being suitable controls 25, a couch roll 26, a felt 27, and shower 28 all being well known in the trade. The mold surface 29 is perforated and usually consists of a fine mesh wire, supported on a course mesh wire the latter supported on suitable axially extending rods or bars.
The former 31 of the invention comprises a unitary enclosed flow box 32, devoid of any bank of cross tubes, and having a tapered manifold 33 juxtaposed to an explosion, or expansion, chamber 34 and separated therefrom by the apertured partition 47. The unitary flow box 32 is hinge pivoted at each opposite side as at 36 to the frame 24 and supported by the fluid actuated cylinder and piston mechanism 37, preferably air, there being a pivot connection at 38 and a pivot block 39 mounted on frame 24.
The manifold 33 is preferably of rectangular cross section and tapers in the cross-machine direction from the large influent end 41 to the small effluent end 42, there being a valve 43 at the small end to permit recirculation and control of pressure within the manifold. Manifold 33 has one side wall 44 obliqued to the path of incoming stock 45, to change the direction thereof into a predetermined pattern of indentical aperatures 46 in the opposite side wall 47, there being an upper wall 48 and a parallel lower wall 49. Manifold 33 preferably includes a top insert plate 50, of predetermined dimensions to establish the volume of the manifold, the insert plate 50 being slidably removable from the large end 41 for machining and replacement.
The apertured side wall 47, constitutes a common partition separating the unitary flow box 32 into a tapered manifold 33 juxtaposed to an explosion, or expansion chamber 34; the apertures 46 extending from the inner face 51 of wall 47 to the outer face 52 thereof, face 52 also being an inner face of the explosion chamber.
The explosion chamber 34 includes the floor 53, top, or roof, wall 54, the apertured rearward sidewall 47 and the forward wall 55, there being a baffle 56 upstanding centrally from floor 53 to an upper face 57, the face 57 being at a spaced distance from top wall 54 to form a flow passage 58 of predetermined reduced dimensions called a narrow diffuser section. The forward face 59 of baffle 56 is inclined to form with the corresponding face of foward wall 55 an outwardly tapered diffuser section 61. A stock outlet 62 is formed under forward wall 55 leading to the pressure chamber 63 under the pressure lid 64.
The rearward facing face 65 of baffle 56 is imperforate vertical and planar and the axes of the apertures 46 in the wall 47 are parallel to each other and each normal to the plane of face 65 so that stock 45 emitted from the apertures will impact normal to the face 65 and spread out for 360° therearound in somewhat of a mushroom pattern thereby mixing the fibers in the stock in an unusually efficient manner.
Each aperture 46 preferably includes a truncated conical bore 66 at the influent end and a cylindrical bore 67 of reduced dimensions at the effluent end and preferably each apeture is provided with rifled grooves 68 which have been found to increase the mixing of the stock. Preferably the apertured plate 47 is of "Plexiglas", or the equivalent, with the small perforations 46 spaced evenly across the machine and designed to create a large pressure drop which ensures the same flow of stock over each perforation. The perforation length, diameter, spacing, tapering geometry and velocity ratio between the manifold 33 and perforations 46 determine the angle of taper of the manifold. The spacing of the perforations across the machine is determined by the desired pressure drop across the plate, or wall, 47 which is a function of stock 45 being used.
Stock 45 enters the expansion chamber 34 at high velocites through pertures 46 and impacts face 65 of baffle 56, which is preferably also of "Plexiglas", the impact and 360° deflection creating stable eddies thereby dissipating kinetic enerby, spreading the stock and evening out stock velocity and pressure across the flow box 32. Eddying continues as the stock flows upwardly in expansion section 69 into the right angle turn 71 which is square, with a right angular corner 72 which maximizes the pressure loss and eddying caused by passing a liquid around a 90° corner and prepares the stock for its entry into the narrow diffuser section 58. The lower face 73 of top wall 54 is flat and planar to impact the stock perpendicularly for a second time prior to entering the throat 58.
Preferably the upper rearward edge 74 of the face 57 of baffle 56 is cut away to form a convex recess 75 which is a converging entrance to the diffuser section 58 for decreasing eddying and increasing pressure. Stock then flows through the narrow passage 58 in which a sharp rise in pressure is applied to the stock in what is known as a "pressure shock". The stock then passes the second right angular turn 76 into the diverging diffuser section 61, wherein some of the kinetic energy is dissipated as adjacent layers of stock 45, near the walls 55 and 59 slide by each other. Eddies are thus reformed and turbulent mixing occurs as the stock approaches throat, or outlet, 62 and the last right angular corner 78 of the expansion chamber. The speed of the stock at this time has slowed to where it approaches the speed of rotation of the cylinder mold 22, its pressure is at a maximum, mixing subsides and the stock is ready to be laid on the mold surface 29. The stock network is set only after reaching the turn at throat 62 so that there is little possibility for stock flocculation to take place in the former 31.
The stock flow is from throat 62 leads into an enclosure 63 formed by the flexible, pressure lid 64, the lid enclosure matching the radial drainage profile of the particular mold 22 and maintaining equal pressure across the entire enclosure. The lid 64 is of flexible resilient material such as metal and extends circumferentially from an intergral upturned flange 79, fixed to the former throat opening adjustment 81 with a rubber cushion 82 therebetween, to a free terminal tip 83 and preferably covers an arc of surface 29 at least 12 inches long and up to 18 inches in length.
The clearance, or lid tip opening, 84 is adjustable by a number of fine lid tip adjustment screws 85, by means of a knob 86, the screws being located about every 6 inches parallel to the cylinder mold 22 across the machine. Lid 64 is a self adjusting spring leaf which can flex and compensate for the various basis weight sheets run on the machine. The only adjustment needed for a change of weight is to change the consistency of the stock being run through the machine. The lid 64 will also flex to pass contraries without plugging. The entire lid 64 is adjustable as a unit by means of the threaded turn knob 86, pivot connections 87 and 88, linkage 89 and shaft 91.
An axially extending strip 92, of rubber or the like has a bead, or bulb, 93 at the rearward edge seated in a corresponding groove 94 in the lower forward wall of baffle 56, and its free terminal forward tip 95 in contact with surface 29, the strip being slidable endwise out of the groove for easy replacement.
While the felt 27 would conventionally be at the level of the top of cylinder mold 22, at its approach thereto, in this invention it has been found preferable to mount a smooth faced idler roll 96 with its shaft 97 well below that level and with its surface 98 in close proximity to the tip 83 of pressure lid 62. Suitable end dams, or deckles, 99 are mounted at each opposite end of pressure lid 62 and supported on the unitary former 31, rather than being mounted on the frame 24 as in the prior art.
While, as stated above, it is usually important that the fibrous component of the paper stock be evenly dispersed with random fiber networks, an exception occurs on certain grades of board and paper. In such grades, it is essential, in order to meet test usage, and final product usage, to control the fiber orientation of the sheet.
It will be understood that as the pressure lid former of the invention flows fibrous stock onto the perforated screen surface of the cylinder, at certain relative speeds the majority of the fibres may tend to be laid parallel to the path of rotation. On the other hand, if the pressure lid is capable of adjustment from a high pressure slice effect to a slower speed stagnant pool effect, the operator is able to achieve a desired ratio of fibres lying transverse to the path.
The resulting sheet characteristic is commonly referred to by paper makers as tensile ratio, the tensile ratio depending on the machine direction to cross machine direction orientation of the fibers.
It is possible to change the degree of fiber orientation by changing the relative velocity of the surface of the cylinder and the outlfow jet emerging from the throat of the pressure lid. Thus with a given surface speed of the cylinder mold, the Machine Directional Cross/Machine Direction Tensile ration can be changed and controlled by changing and controlling the curvature and clearances of the pressure lid.
The tensile ratio gives an indication of sheet stiffness properties because the stiffness characteritics of a multiply sheet are dependent on the tensile character of the outside ply, or layer, of the multi-layer structured sheet.
By means of the improved adjustable, curvature lid 101 of the invention, shown in FIG. 5, fiber orientation may be controlled so as to yield a tensile ratio in the range of approximately 1.1 to 1 to 5.1 MD/CD (Machine Direction - Cross Machine Direction). With special former designs ratios of 10 to 1 may be achieved.
The pressure lid 101, like lid 64 ranges from twelve to eighteen inches in length from the free terminal tip 83 of the cantilevered portion 102, to the upturned flange portion 79 at the stock outlet or gateway, 62. It differs from lid 64, which is unitary and of flexible, resilient metal, or equivalent material, in that it is articulated and formed of two parts 103 and 104 hingely connected at 105, by a piano hinge device or the like, the hinge 105 being connected by pivot 106, thrust screw 107 and knob 108 in a bracket 109. Similarly the rearward portion 104 is hingedly connected at 111 by a piano hinge device or the like, the hing 111 being connected to the thrust screw 112 and turn knob 113 in a bracket 114.
It will be seen that handwheels, or knobs, 113, located one at each opposite end of the former will adjust the height of the throat, or stock outlet 62. Knobs 86 and rods 85, located at spaced distances across the former, such as every twelve inches, will adjust the clearance 84 between tip 83 and surface 29 of cylinder mold 22. The hand wheels, or knobs 108, also located at spaced distances across the former, and the rods, or thrust screws 107 wil adjust the cleareance intermediate of the pressure chamber 63 at 115 to determine the pooling of the stock in the chamber.
On conventional formers the lid enclosure is of a stationary, rigid design. This rigid design usually has a determental effect on the Machine Direction shear generated in the flow under the roof of the lid by the difference in speed between the roll surface and the stationary roof causing disruption of the formed mat. The movable geometry of the lid 101 and cantilevered section at 102 constantly provides the stock suspension with a self-relieving action which automatically increases the clearance at the exit 62 of the enclosure.
This allows at times additional discharge of the undrained stock, to take place and prevents high mat stress levels from being built up under the enclosure which causes mat disruption.
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A former for cylinder mold, paper making, machines, of the type now known as B.R.D.A., and having a pressure lid, an explosion chamber with a central imperforate baffle, and a manifold feeding stock to the chamber is characterized by the flow box unitarily containing an explosion chamber separated from a tapered manifold by an apertured plate. Stock is directed from the plate apertures in a direction normal to the baffle for improved mixing. The pressure lid includes a forward cantilevered tip end with a predetermined tip clearance, and is unusually elongated to increase drainage effect. The lower plate of the slice is rubber with an inner bulb and it is slidable axially outward for replacement. The curvature and clearances of the lid are changeable during operation and the lid acts as an adjustable gate for controlling pooling under the lid.
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BACKGROUND OF THE INVENTION
[0001] The present invention relates to a method and a kit for detecting microorganisms in food and carrying out a test such as a drug susceptibility test for the purpose of selecting an optimal drug for treating a patient infected with a microorganism.
DESCRIPTION OF THE PRIOR ART
[0002] Fungi including yeast-like fungi and filamentous fungi are food spoilage pathogens and, in particular, the genus Aspergillus and the genus Penicillium, which are filamentous fungi, produce carcinogenic mycotoxins such as aflatoxin. They are also causative agents for profound mycosis, which has been an increasing problem in recent years. Detecting these fungi is therefore extremely important hygienically and medically.
[0003] Testing of these fungi is usually carried out by a culture method using an agar culture medium or a liquid culture medium, but since testing by the culture method takes 2 to 7 days, the length of time for the test is a problem. Furthermore, in the method using a liquid culture medium the degree of proliferation is mainly measured by employing a turbidity method in which the turbidity of the liquid culture is evaluated. Although this method is suitable for bacteria such as E. coli, it is not suitable for fungi and, in particular, fungi having poor dispersibility such as filamentous fungi, and the problem that precise measurement cannot be carried out has been identified.
[0004] In order to solve these problems, Matrai, et al., have directed attention toward invertase (β-D-fructofuranosidase) present in the genus Aspergillus and the genus Penicillium, and reported a method that enables a fungus to be detected in 20 to 48 hours by calorimetric analysis of glucose formed when the fungus is cultured in a culture medium containing sucrose (Matrai T., et al., Int. J. Food Microbiol., 61, 187-191, 2000). However, this method requires heating of the liquid culture during the evaluation, thereby complicating the operation.
[0005] Recently, rapid detection methods which employ various principles other than the culture method have been developed. In the food industry an ATP bioluminescence assay for environmental analysis and quality control has been employed accompanying the introduction of HACCP (Journal of the Society for Antibacterial and Antifungal Agents, Japan, 28, 601-609, 2000), and in the medical field use of a PCR assay has started (‘Genetic Diagnosis of Mycosis’, Medicalsense). However, the ATP assay has the problem that ATP derived from non-fungal material is detected and, in addition, a special image processor is required. The PCR assay has the problems of reaction inhibition due to contaminant components and the genes of dead fungi also being detected.
[0006] With regard to another method, there is a fluorescent staining method (Journal of the Society for Antibacterial and Antifungal Agents Japan, 28, 601-609, 2000), but since commercial devices are expensive, costing at least a few tens of millions of yen, the test cost becomes extremely high, which is a problem. Under such circumstances, there has been a strong desire for a low cost method that can detect microorganisms and, in particular, yeast-like fungi and filamentous fungi, specifically, quickly, and simply.
[0007] With regard to a method for testing the drug susceptibility of fungi, accompanying an increase in the onset frequency of profound mycosis and the emergence of strains exhibiting resistance to antifungal drugs, it has become essential to select an appropriate therapeutic drug for this infection, and there is therefore a desire to establish a simple and highly reliable test method based on a method for measuring the degree of fungal proliferation. In the United States, the National Committee for Clinical Laboratory Standards (NCCLS) has proposed in 1997 the ‘Reference Method for Broth Dilution Antifungal Susceptibility Testing of yeasts; Approved Standard’ (M27-A) as a method for testing the drug susceptibility of yeast-like fungi, and in 1998 the ‘Reference Method for Broth Dilution Antifungal Susceptibility Testing of Conidium-Forming Filamentous Fungi; Proposed Standard’ (hereinafter ‘M38-P’) as a method for testing the susceptibility of filamentous fungi. However, these methods require a long period of time before the test results are obtained, since the culture time may be 2 or 3 days depending on the type of fungus. Furthermore, since these methods all employ a turbidity method, they are not suitable for a fungus that proliferates in clump form, and there is a problem that it is difficult to decipher the fungal growth endpoint (80% fungal growth inhibition), particularly in the case of an azole antifungal. There is therefore a desire for a simpler and highly reproducible method for deciphering the fungal growth endpoint.
[0008] As means for solving these problems, various colorimetric methods for measuring the degree of fungal proliferation by colorimetry have been developed. Up to now, for example, a method using the tetrazolium salt 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide (MTT), (Meletiadis J., J. Clin. Microbiol., 38, 2949-2954, 2000), a method using the redox indicator AlamarBlue™ (Alamar Biosciences Inc., Sacramento, Calif.) (Jahn B., J. Clin. Microbiol., 34, 2039-2041, 1996), and a vital staining method using Neutral Red (JP, 7-107995, A) have been reported. However, in the MTT method and the Neutral Red method the assessment operation is complicated, and the method using AlamarBlue™ has the problem that, depending on the strain, there are cases in which no fluorescence is produced, and the inhibitory concentration cannot be judged.
[0009] Nakano, et al., have reported a drug susceptibility test microplate in which a drug, a tetrazolium salt, 1-methoxy-5-methylphenazinium methylsulfate (1-methoxy PMS), potassium ferricyanide, and potassium ferrocyanide are made into a solid phase, and a method for testing drug susceptibility using same (JP, 11-287796, A). However, this microplate and the test method using it could only be applied to the measurement of yeast-like fungi, and the application thereof to filamentous fungi was difficult.
SUMMARY OF THE INVENTION
[0010] The present invention has therefore been carried out in view of the above-mentioned circumstances, and the object thereof is to provide a method for objectively assessing the proliferation of a microorganism and, in particular, the proliferation of a yeast-like fungus and a filamentous fungus by a simple operation in a short period of time when carrying out, for example, the detection of microorganisms in food and a test such as a drug susceptibility test for selecting an optimal drug for treating a patient infected with a microorganism; a drug susceptibility test method employing the above-mentioned method; and a kit used therein.
[0011] As a result of an intensive investigation by the present inventors in order to achieve the above-mentioned object, it has been found that the degree of proliferation of a microorganism, in particular, that of a yeast-like fungus and a filamentous fungus can be measured by colorimetry simply and in a short period of time by combining a coloring reagent containing, for example, a water-soluble tetrazolium salt such as WST-8 (2-(2-methoxy-4-nitrophenyl)-3-(4-nitrophenyl)-5-(2,4-disulfophenyl)-2H-tetrazolium, sodium salt: water soluble disulfonated tetrazolium salt, Ishiyama M., et al., Talanta, 44, 1299-1305, 1997) that decomposes to generate a formazan and then exhibits a color sensitively under alkaline conditions, with a liquid culture medium containing a non-reducing sugar such as sucrose. The present invention has thus been accomplished.
[0012] That is, the present invention relates to a method for detecting a microorganism, comprising adding and reacting, in a liquid culture medium, an alkaline sensitizing solution and a coloring reagent comprising a redox dye, the liquid culture medium having been inoculated with a test sample, thereby detecting the microorganism by coloration in the reaction.
[0013] Furthermore, the present invention relates to the above-mentioned detection method wherein the microorganism is a yeast-like fungus and/or a filamentous fungus.
[0014] Moreover, the present invention relates to the above-mentioned detection method wherein the liquid culture medium contains a non-reducing sugar.
[0015] Furthermore, the present invention relates to a kit for detecting a microorganism, comprising a liquid culture medium, an alkaline sensitizing solution, and a coloring reagent comprising a redox dye.
[0016] Moreover, the present invention relates to the above-mentioned detection kit wherein the redox dye is a water-soluble tetrazolium salt that forms a water-soluble formazan.
[0017] Furthermore, the present invention relates to the above-mentioned detection kit wherein the tetrazolium salt that forms the water-soluble formazan is 2-(2-methoxy-4-nitrophenyl)-3-(4-nitrophenyl)-5-(2,4-disulfophenyl)-2H-tetrazolium, sodium salt.
[0018] Moreover, the present invention relates to the above-mentioned detection kit wherein the coloring reagent further comprises an electron carrier, potassium ferricyanide, and potassium ferrocyanide.
[0019] Furthermore, the present invention relates to the above-mentioned detection kit wherein the electron carrier is 1-methoxy-5-methylphenazinium methylsulfate.
[0020] Moreover, the present invention relates to the above-mentioned detection kit wherein the liquid culture medium comprises a non-reducing sugar.
[0021] Furthermore, the present invention relates to the above-mentioned detection kit wherein the non-reducing sugar is sucrose.
[0022] Moreover, the present invention relates to the above-mentioned detection kit wherein the alkaline sensitizing solution is one that makes the pH of the liquid culture medium at least 9.
[0023] Furthermore, the present invention relates to the above-mentioned detection kit wherein the alkaline sensitizing solution is an aqueous solution of sodium hydroxide.
[0024] Moreover, the present invention relates to a method for testing drug susceptibility of a microorganism, comprising adding and reacting, in a liquid culture medium, an alkaline sensitizing solution and a coloring reagent comprising a redox dye, the liquid culture medium comprising an antimicrobial drug and having been inoculated with a test sample, thereby determining a minimum inhibitory concentration by coloration in the reaction.
[0025] Furthermore, the present invention relates to the above-mentioned test method wherein the microorganism is a yeast-like fungus and/or a filamentous fungus.
[0026] Moreover, the present invention relates to the above-mentioned test method wherein the liquid culture medium comprises a non-reducing sugar.
[0027] Furthermore, the present invention relates to a kit for testing drug susceptibility of a microorganism wherein the above-mentioned detection kit further comprises an antimicrobial drug.
[0028] Moreover, the present invention relates to the above-mentioned test kit wherein the antimicrobial drug is an antifungal drug.
[0029] In the method of the present invention, since a component that exhibits a color by reacting with an alkaline sensitizing solution is used as a coloring reagent, the color reaction in a detection operation after culturing a microorganism can be effected with extreme sensitivity. The coloration at this stage can be identified visually or by a normal absorptiometer. Furthermore, by selecting as a coloring reagent component a redox dye and, in particular, a water-soluble redox dye, the need for addition of an organic solvent and stirring after the color reaction is eliminated. In accordance with the method of the present invention, therefore, detection of a microorganism is extremely simple and precise.
[0030] In addition, the kit for detecting a microorganism and the drug susceptibility test kit of the present invention are portable. The kits of the present invention can therefore accomplish their respective objects without limiting the location where they are used.
BRIEF DESCRIPTION OF THE DRAWINGS
[0031] [0031]FIG. 1 is a graph showing the change in absorbance relative to culture time in the turbidity method, and in the colorimetry method of the present invention.
[0032] [0032]FIG. 2 is a graph showing the change in absorbance relative to antifungal drug concentration when carrying out a drug susceptibility test for A. fumigatus ATCC26430.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0033] The carbon source that is used in the culture medium of the present invention is a sugar that does not show reducibility in neutral and alkaline solutions so as to avoid a blank reaction, and the metabolic product that is produced by the action of an enzyme produced by a microorganism that is to be detected shows reducibility in neutral and alkaline solutions. Examples thereof include sucrose, sorbitol, and trehalose. In the case where the filamentous fungus that is to be detected belongs to the genus Aspergillus or the genus Penicillium, since these fungi have invertase and produce a reducing sugar, it is preferable to use sucrose.
[0034] With regard to other nutrient sources, yeast extract, peptone, Yeast Nitrogen Base (manufactured by Difco), etc. can be cited. In the case where the object is to detect only a yeast-like fungus or a filamentous fungus, addition of an antibiotic such as chloramphenicol in order to suppress the growth of bacteria can also be considered.
[0035] Any coloring reagent may be used in the present invention as long as it exhibits a color under alkaline conditions, but one containing a redox dye and, in particular, a water-soluble redox dye, is preferably used. More specifically, a tetrazolium salt such as WST-1, WST-3, WST-4, WST-5 or WST-8 that forms a water-soluble formazan is preferred. In particular, WST-8 is preferably used.
[0036] With regard to other components that are contained in the coloring reagent, there can be cited an electron carrier having the function of donating an electron to the coloring reagent, and potassium ferricyanide and potassium ferrocyanide for adjusting the redox potential of the culture medium. As for the electron carriers, PMS (phenazine methosulfate), Meldola's Blue, diaphorase, 1-methoxy PMS, etc. are preferably used, and 1-methoxy PMS is particularly preferably used.
[0037] With regard to a component of the alkaline sensitizing solution used in the present invention, any component that makes the pH of the cultured liquid about 9 or above can be used, and since WST-8 formazan exhibits a blue color when the pH is about 9 or above, a component that makes the pH about 9 or above is suitably used, and one that makes the pH 10 or above is particularly preferred. Examples of preferably used components include sodium hydroxide and potassium hydroxide. Sodium hydroxide is preferable thereamong in terms of the change in the amount of liquid and the ease of addition. In this case, it is preferable to add a 1 to 2 mol/l aqueous solution of sodium hydroxide in an amount of {fraction (1/20)} to {fraction (1/10)} of the amount of cultured liquid.
[0038] Microorganisms to which the detection method of the present invention can be applied are not limited as long as they can grow in the above type of culture medium. In particular, filamentous fungi such as those of the genus Aspergillus and the genus Penicillium can be suitably detected.
[0039] Antimicrobial drugs that are used in the drug susceptibility test of the present invention are not limited as long as they are used for the treatment of an infection where the causative agent is a fungus, and examples thereof include Amphotericin B, Flucytosine, Fluconazole, Miconazole, Itraconazole, and Ketoconazole.
[0040] The kit for detecting a microorganism used in the present invention comprises a coloring reagent, a liquid culture medium, and an alkaline sensitizing solution, and the coloring reagent and the liquid culture medium may be mixed in advance.
[0041] The drug susceptibility test kit in the present invention comprises a coloring reagent, a liquid culture medium, an alkaline sensitizing solution, and an antimicrobial drug, and the coloring reagent, the liquid culture medium, and the antimicrobial drug may be mixed in advance.
[0042] In order to implement the present invention, after the coloring reagent is added to the culture medium, the culture medium is inoculated with a test sample and cultured. Alternatively, after inoculating the culture medium with a test sample and culturing, the coloring reagent is added thereto. Although the culturing conditions depend on the type of fungus that is to be detected, culturing is carried out, for example, at 35° C. to 37° C. for 24 to 48 hours. After culturing, the alkaline sensitizing solution is added, and the color of the liquid culture after 5 to 10 minutes is observed visually or measured using an absorptiometer. The wavelength used for this measurement is 620 to 660 nm. It is preferable to prepare a negative control which has not been inoculated with a test sample.
[0043] When implementing the drug susceptibility test using the method of the present invention, the coloring reagent, the liquid culture medium, and an antifungal drug such as Amphotericin B, Flucytosine, Fluconazole, Miconazole, Itraconazole, or Ketoconazole are pipetted into a microplate or a test tube, it is inoculated with a test microorganism, and the test microorganism is cultured. After culturing, the alkaline sensitizing solution is added thereto, and the minimum inhibitory concentration is determined by observing the color of the liquid culture visually or by absorbance. Alternatively, after inoculating a microplate or test tube, into which the above-mentioned antifungal drug and the liquid culture medium have been pipetted, with a test microorganism and culturing the test microorganism, the coloring reagent and then the alkaline sensitizing solution are added thereto, and the minimum inhibitory concentration is determined by observing the color of the liquid culture visually or by absorbance.
EXAMPLES
[0044] The present invention is explained in further detail below by reference to examples, but the present invention is in no way limited by these examples.
Example 1
[0045] In order to select a growth culture medium the following procedures were carried out.
[0046] A. Strain Used
[0047] [0047] Aspergillus Fumigatus KM8001 was Used.
[0048] B. Test Method
[0049] (1) Preparation of Culture Medium
[0050] 1) MOPS Buffered RPMI 1640 Culture Medium Supplemented with Added Glucose
[0051] 10.4 g of RPMI 1640 culture medium powder (containing L-glutamine, no sodium hydrogen carbonate, and no Phenol Red, manufactured by Gibco), 2.0 g of sodium hydrogen carbonate, 10.0 g of glucose, and 34.53 g of 3-morpholinopropanesulfonic acid (MOPS) were dissolved in 900 mL of purified water, and the pH was adjusted to 7.0 with a 1N aqueous solution of sodium hydroxide. The solution was made up to 1000 mL and then filtered using a 0.2 μm filter.
[0052] 2) Preparation of Glucose YN Broth
[0053] 6.7 g of YN Base (manufactured by Difco) and 5 g of glucose were dissolved in about 900 mL of purified water, and the pH was adjusted to 5.3 with a 1N aqueous solution of sodium hydroxide. The solution was made up to 1000 mL with purified water and then filter sterilized using a 0.2 μm filter.
[0054] 3) Preparation of Sucrose YN Broth
[0055] 6.7 g of YN Base (manufactured by Difco) and 20 g of sucrose were dissolved in about 900 mL of purified water, and the pH was adjusted to 7.0 with a 1N aqueous solution of sodium hydroxide. The solution was made up to 1000 mL with purified water and then filter sterilized using a 0.2 μm filter.
[0056] (2) Preparation of Inoculum and Culturing
[0057] A tester strain was cultured using Sabouraud Dextrose Agar (manufactured by OXOID) at 35° C. for 7 days. 2 mL of sterile physiological saline containing 0.1% Tween 80 was added dropwise onto the culture medium so as to float spores. The above-mentioned physiological saline that had been added dropwise onto the culture medium was recovered and allowed to stand for 3 to 5 minutes, and after removing the precipitate it was mixed using a Vortex mixer to give a spore suspension. Dilution was carried out so that the absorbance at 530 nm was 0.09 to 0.11. The spore suspension so prepared was diluted 100 times with various test culture media, 0.2 mL of each was pipetted into a well of a microplate, and 0.02 mL of a coloring reagent (containing 0.7 mmol/L WST-8, 0.0035 mmol/L 1-methoxy PMS, 0.5 mmol/L potassium ferricyanide, and 0.5 mmol/L of potassium ferrocyanide) was added thereto. As negative controls, various test culture media which had not been inoculated with a spore liquid (uninoculated with microorganisms) were prepared. Culturing was carried out at 35° C.±1° C. for 24 hours, and the absorbance at a primary wavelength of 450 nm and a secondary wavelength of 630 nm was measured. Subsequently, 0.02 mL of a 1.5 mol/L aqueous solution of sodium hydroxide was added to each of the wells, and 5 minutes after that the absorbance at 630 nm was measured.
[0058] C. Results
[0059] The results obtained by measuring the absorbance of each growth culture medium before and after addition of the aqueous solution of sodium hydroxide are summarized in Table 1. When the absorbance was measured at the primary wavelength of 450 nm and the secondary wavelength of 630 nm using the MOPS buffered RPMI 1640 culture medium supplemented with glucose, the absorbance was 0.153, which was considerably low. When the aqueous solution of sodium hydroxide was therefore added thereto in order to increase the sensitivity, and the absorbance at 630 nm was measured, a color was also observed for the uninoculated samples. The absorbance was then measured at 630 nm for the glucose YN broth and the sucrose YN broth before and after addition of the aqueous solution of sodium hydroxide. It was found that a color was exhibited for the uninoculated sample with the glucose YN broth. On the other hand, almost no coloration was observed for the uninoculated sample with the sucrose YN broth, but when the microorganisms grew they exhibited a strong color.
[0060] The present invention can therefore be carried out using a liquid culture medium containing sucrose.
TABLE 1 Table 1 Absorbance before and after addition of aqueous solution of sodium hydroxide for various culture media MOPS buffered Addition of RPMI 1640 aqueous culture solution of medium sodium Measurement supplemented Glucose YN Sucrose YN hydroxide wavelength with glucose broth Broth Uninoculated Before 630 nm 0.045 0.015 0.013 with After 630 nm 0.976 0.968 0.089 Microorganisms Inoculated Before Primary 0.153 0.024 0.017 with wavelength microorganisms 450 nm Secondary wavelength 630 nm Before 630 nm 0.206 0.132 0.262 After 630 nm 0.836 0.827 0.767
Example 2
[0061] In order to measure the degree of proliferation of a filamentous fungus the following procedures were carried out.
[0062] A. Strains Used
[0063] [0063] Aspergillus Fumigatus ATCC26430, Aspergillus Fumigatus KM8001, and Aspergillus niger ATCC16404 were used.
[0064] B. Test Method
[0065] (1) Preparation of Sucrose YN Broth
[0066] 6.7 g of YN Base (manufactured by Difco) and 20 g of sucrose were dissolved in about 900 mL of purified water, and the pH was adjusted to 7.0 with a 1N aqueous solution of sodium hydroxide. The solution was made up to 1000 mL with purified water and then filter sterilized using a 0.2 μm filter.
[0067] (2) Preparation of Inoculum and Culturing
[0068] A tester strain was cultured using Sabouraud Dextrose Agar (manufactured by OXOID) at 35° C. for 7 days. 2 mL of sterile physiological saline containing 0.1% Tween 80 was added dropwise onto the culture medium so as to float spores. The above-mentioned physiological saline that had been added dropwise onto the culture medium was recovered and allowed to stand for 3 to 5 minutes, and after removing the precipitate it was mixed using a Vortex mixer to give a spore suspension. Dilution was carried out so that the absorbance at 530 nm was 0.09 to 0.11. 0.1 mL of the spore suspension so prepared was taken using a micro pipette, added to 10 mL of the sucrose YN broth containing 0.1 mg/mL of chloramphenicol, and stirred well using a Vortex mixer to give an inoculum.
[0069] (3) Turbidity Method
[0070] 0.2 mL of the inocula prepared in (2) was pipetted into each well of a microplate. After covering the plate, it was cultured at 35° C.±1° C. The absorbance at 630 nm was measured at predetermined intervals.
[0071] (4) Colorimetry (Method of the Present Invention)
[0072] 0.02 mL of a coloring reagent (containing 0.7 mmol/L WST-8, 0.0035 mmol/L 1-methoxy PMS, 0.5 mmol/L potassium ferricyanide, and 0.5 mmol/L of potassium ferrocyanide) and 0.2 mL of the inoculum prepared in (2) were pipetted into each well of a microplate. After the plate was covered, it was cultured at 35° C.±1° C. After culturing for 12 hours, 0.02 mL of a 1.2 mol/L aqueous solution of sodium hydroxide was added in sequence every 3 hours to the wells that were being cultured, and 10 minutes after the addition the absorbance at 630 nm was measured. As a blank, sucrose YN culture medium was added instead of the inoculum.
[0073] C. Results
[0074] [0074]FIG. 1 shows the absorbance measured after culturing for 12, 15, 18, 21, and 24 hours. The ordinate of FIG. 1 denotes the absorbance at 630 nm, and the abscissa denotes the culture time. In the present invention, the absorbance increased with the culture time, and it was possible to measure the degree of proliferation. Furthermore, a color was exhibited after 18 hours when the turbidity had hardly changed, and detection in a short time was thus possible.
[0075] It therefore becomes clear that the measurement kit and the measurement method of the present invention allow the degree of proliferation of a filamentous fungus to be measured simply.
Example 3
[0076] In order to examine the applicability to antifungal drug susceptibility testing the following procedures were carried out.
[0077] A. Strain Used
[0078] [0078] Aspergillus Fumigatus ATCC26430 was Used.
[0079] B. Microplate Used for Test
[0080] Two drugs, Amphotericin B (AMPH) and Itraconazole (ITCZ) were examined. 2-fold dilution series of AMPH (0.3 to 160 μg/mL) and ITCZ (0.16 to 80 μg/mL) were prepared using dimethyl sulfoxide and purified water. The drug solutions so prepared were pipetted into a plate at 0.02 mL/well and dried to a solid under reduced pressure for 24 hours. A coloring reagent (containing 0.7 mmol/L WST-8, 0.0035 mmol/L 1-methoxy PMS, 0.5 mmol/L potassium ferricyanide, and 0.5 mmol/L of potassium ferrocyanide) was pipetted into each of the wells at 0.02 mL/well and they were again dried to a solid under reduced pressure for 24 hours.
[0081] C. Test Method
[0082] (1) Turbidity Method
[0083] A comparative example was carried out according to NCCLS M-38P (0.2 mL culture system micro broth dilution method).
[0084] (2) Microplate Method of the Present Invention
[0085] 1) Preparation of Sucrose YN Broth
[0086] 6.7 g of YN Base (manufactured by Difco) and 20 g of sucrose were dissolved in about 900 mL of purified water, and the pH was adjusted to 7.0 with a 1N aqueous solution of sodium hydroxide. The solution was made up to 1000 mL with purified water and then filter sterilized using a 0.2 μm filter.
[0087] 2) Preparation of Inoculum and Culturing
[0088] A tester strain was cultured using Sabouraud Dextrose Agar (manufactured by OXOID) at 35° C. for 7 days. 2 mL of sterile physiological saline containing 0.1% Tween 80 was added dropwise onto the culture medium so as to float spores. The above-mentioned physiological saline that had been added dropwise onto the culture medium was recovered and allowed to stand for 3 to 5 minutes, and after removing the precipitate it was mixed using a Vortex mixer to give a spore suspension. Dilution was carried out so that the absorbance at 530 nm was 0.09 to 0.11. 0.1 mL of the spore suspension so prepared was taken using a micro pipette, added to 20 mL of sucrose YN broth, and stirred using a Vortex mixer to give an inoculum. 0.2 mL of the inoculum was pipetted into each of the wells of the microplate for the test described in B, the plate was covered, and culturing was carried out at 35° C.±1° C. for 24 hours. As a blank, sucrose YN broth was added instead of the inoculum.
[0089] 3) Evaluation Method
[0090] After 24 hours 0.02 mL of a 1.5 mol/L aqueous solution of sodium hydroxide was added to each well, and 5 minutes after the addition the absorbance at 630 nm was measured.
[0091] 1. For AMPH, the minimum concentration that gave an absorbance equal to or less than that of the negative control was defined as the minimum inhibitory concentration (MIC).
[0092] 2. For ITCZ, the 80% inhibitory concentration (IC80) was determined. The drug concentration of a well that gave an absorbance equal to or less than that obtained by the following equation was defined as the MIC.
( IC 80=(positive control−negative control)×0.2+negative control)
[0093] D. Results
[0094] [0094]FIG. 2 shows the results of measuring the absorbance when evaluating the drug susceptibility in accordance with the present invention. The abscissa denotes the antifungal drug concentration, and the ordinate denotes the absorbance at 630 nm. The absorbance increased when the concentration became 0.25 μg/mL or below for AMPH and 0.06 μg/mL or below for ITCZ. Visually, AMPH exhibited a blue to dark blue color at 0.25 μg/mL or below and almost no color at 0.5 μg/mL or above, and ITCZ exhibited a blue to dark blue color at 0.06 μg/mL or below and almost no color at 0.12 μg/mL or above. The drug susceptibility test was carried out repeatedly by the NCCLS M-38P method and the method of the present invention, and the MIC values obtained thereby are summarized in Table 2. In the table, the allowable range denotes the reference values described in NCCLS M38-P. It was found that the MIC determined in the present invention coincided with the allowance range described in NCCLS M38-P. Furthermore, the MIC values determined visually were the same as those determined using absorbance. Moreover, the time for determination with the NCCLS M38-P method was 46 to 50 hours, but the present invention took about half of the above, that is, 24 hours.
[0095] The measurement reagent and the measurement method of the present invention are therefore useful for testing the antifungal drug susceptibility of a filamentous fungus.
TABLE 2 MIC (units μg/mL) of A. fumigatus ATCC 26430 Measurement method MIC Allowable range AMPH M-38P (Turbidity method) 0.5-2.0 0.5-2.0 Colorimetry 0.5-1.0 ITCZ M-38P (Turbidity method) 0.12-0.25 0.12-1.0 Colorimetry 0.12-0.25
EFFECTS OF THE INVENTION
[0096] In accordance with the detection method and the detection kit of the present invention, microorganisms and, in particular, yeast-like fungi and filamentous fungi can be easily detected. Furthermore, the drug susceptibility test method and the kit therefor of the present invention are useful for testing the antifungal drug susceptibility of a filamentous fungus by a broth dilution method.
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A method for detecting a microorganism by coloration is provided that includes adding and reacting, in a liquid culture medium, an alkaline sensitizing solution and a coloring reagent containing a redox dye, the liquid culture medium having been inoculated with a test sample, thereby detecting the microorganism by coloration in the reaction. There is also provided a method for testing drug susceptibility of a microorganism using above-mentioned method. Furthermore, kits used in these methods are provided. The invention is useful to assess readily and objectively the growth of microorganism when carrying out e.g. a detection of microorganism in foods and a test such as a drug susceptibility test.
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CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims the benefit of U.S. Provisional Application No. 60/210,895, filed Jun. 9, 2000, the entirety of which is hereby incorporated by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] This invention relates to amorphous metallic alloys, commonly referred to as metallic glasses, and more particularly to a new process for the preparation of amorphous metallic components and tools, particularly with high aspect ratio features (ratio of height to width greater than one) in the micro- and submicrometer scale.
[0004] 2. Description of the Related Art
[0005] Amorphous metallic alloys are metal alloys that can be cooled from the melt to retain an amorphous form in the solid state. These metallic alloys are formed by solidification of alloy melts by undercooling the alloy to a temperature below its glass transition temperature before appreciable homogeneous nucleation and crystallization has occurred. At ambient temperatures, these metals and alloys remain in an extremely viscous liquid or glass phase, in contrast to ordinary metals and alloys which crystallize when cooled from the liquid phase. Cooling rates on the order of 10 4 or 10 6 K/sec have typically been required, although some amorphous metals can be formed with cooling rates of about 500 K/sec or less.
[0006] Even though there is no liquid/solid crystallization transformation for an amorphous metal, a “melting temperature” T m may be defined as the temperature at which the viscosity of the metal falls below about 10 2 poise upon heating. Similarly, an effective glass transition temperature T g may be defined as the temperature below which the equilibrium viscosity of the cooled liquid is above about 10 13 poise. At temperatures below T g , the material is for all practical purposes a solid.
[0007] Amorphous parts are typically prepared by injection casting the liquid alloy into cold metallic molds or by forming the parts in the superplastic state at temperatures close to the glass transition temperature (T g ). However, micrometer scale parts with high aspect ratios cannot be prepared by these processes. The aspect ratio of a part is defined as the ratio of height to width of the part. A part with a high aspect ratio is considered to have an aspect ratio greater than one.
[0008] Casting of a high aspect ratio part requires long filling times of the liquid alloy into the mold. However, because metallic alloys generally require high cooling rates, in an injection casting method, only small amounts of material can be made as a consequence of the need to extract heat at a sufficient rate to suppress crystallization. Moreover, cold mold casting does not enable the alloy to wet the mold effectively, thereby leading to the production of imprecise parts.
[0009] U.S. Pat. No. 5,950,704 describes a method for replicating the surface features from a master model to an amorphous metallic alloy by forming the alloy at an elevated replicating temperature. In this method, a piece of bulk-solidifying amorphous metallic alloy is cast against the surface of a master model at the replication temperature, which is described as being between about 0.75 T g to about 1.2 T g , where T g is measured in ° C. However, at these temperature ranges, the alloy material is still fairly viscous. Thus, forming high aspect ratio parts is difficult because the alloy may not be fluid enough to fill the shape of the mold in a fast enough time before the onset of crystallization. Furthermore, due to the high viscosity of the alloy, high pressures are needed to press the alloy against the model.
[0010] Accordingly, what is needed is an improved method and apparatus for the formation of amorphous metallic parts, and more particularly, a method and apparatus for the formation of high aspect ratio amorphous metallic parts.
SUMMARY OF THE INVENTION
[0011] The needs discussed above are addressed by the preferred embodiments of the present invention which describe a manufacturing process that separates the filling and quenching steps of the casting process in time. Thus, in one embodiment, the mold is heated to an elevated casting temperature at which the metallic alloy has high fluidity. The alloy fills the mold at the casting temperature, thereby enabling the alloy to effectively fill the spaces of the mold. The mold and the alloy are then quenched together, the quenching occurring before the onset of crystallization in the alloy. With this process, compared to conventional techniques, amorphous metallic parts with higher aspect ratios can be prepared.
[0012] In one aspect of the present invention, a method of forming an amorphous metallic component is provided. A mold is provided having a desired pattern thereon. An alloy capable of forming an amorphous metal is placed in contact with the mold. The mold and the alloy are heated to a casting temperature above about 1.5 T g of the alloy to allow the alloy to wet the mold. The alloy is cooled to an ambient temperature to form an amorphous metallic component.
[0013] In another aspect of the present invention, the method of forming an amorphous metallic component comprises providing a mold having a desired pattern thereon. An alloy capable of forming an amorphous metal is placed in contact with the mold, and the mold and the alloy are heated to a casting temperature wherein the viscosity of the alloy is less than about 10 4 poise, preferably less than about 10 2 poise, to allow the alloy to wet the mold. The alloy is cooled to an ambient temperature to form an amorphous metallic component.
[0014] In another aspect of the present invention, the method of forming an amorphous metallic component comprises providing a mold having a desired pattern thereon. An alloy capable of forming an amorphous metal is placed in contact with the mold, and the mold and the alloy are heated to a casting temperature above the nose of the crystallization curve of the alloy to allow the alloy to wet the mold. The alloy is cooled to an ambient temperature to form an amorphous metallic component.
[0015] In another aspect of the present invention, a method of forming an amorphous metallic component having a high aspect ratio is provided. A mold is provided having a desired pattern thereon, wherein at least a portion of the mold includes a recess having a height greater than a width thereof. The mold is filled with a metallic alloy capable of forming an amorphous metal at an elevated casting temperature, wherein the metallic alloy has sufficient fluidity to substantially fill the recess before undergoing crystallization. The alloy is cooled from the casting temperature to an ambient temperature, the cooling occurring prior to crystallization of the metallic alloy, such that an amorphous metallic component is formed replicating the shape of the mold. Components formed by this method preferably have aspect ratios greater than about one, more preferably greater than about three.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] [0016]FIG. 1 is a flow chart illustrating the steps of forming an amorphous metallic alloy component according to one embodiment of the present invention.
[0017] [0017]FIG. 2 is a schematic diagram of crystallization curves for three exemplifying amorphous metallic alloys.
[0018] [0018]FIG. 3 is a schematic diagram illustrating the viscosity of an exemplifying amorphous metallic alloy as a function of temperature.
[0019] [0019]FIG. 4 is a schematic diagram of a crystallization curve illustrating preferred cooling rates of a metallic alloy into an amorphous phase.
[0020] [0020]FIG. 5 is a cross-sectional view of the surface of a mold for forming high aspect ratio components.
[0021] [0021]FIG. 6 is a schematic side view of an apparatus for forming an amorphous metallic alloy component according to the method of FIG. 1.
[0022] [0022]FIGS. 7A and 7B are SEM pictures of a first replicated structure made according to one embodiment of the present invention, showing the structure at 30× and 300× magnification.
[0023] [0023]FIGS. 8A and 8B are SEM pictures of a second replicated structure made according to one embodiment of the present invention, showing the structure at 30× and 300× magnification.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0024] [0024]FIG. 1 illustrates one preferred method for forming an amorphous metallic component. Briefly stated, in step 10 , a mold or die with low thermal mass or low thermal conductivity and having a desired pattern thereon is provided. Next, in step 12 , the mold is filled and wetted by a metallic alloy which shows glass forming ability. This step is preferably accomplished by heating both the mold and the alloy to an elevated casting temperature in which the alloy becomes extremely fluid, as described below. This enables the alloy to flow effectively into all of the crevices of the mold. In step 14 , the mold and the alloy are quenched together at a rate sufficient to prevent crystallization of the alloy and form an amorphous solid. One preferred method of quenching the materials is by bringing the mold in contact with a heat sink, such as a cold copper block. In step 16 , the alloy is separated from the mold.
[0025] Preferably, the mold used is one of two types, both of which allow the cooling of the alloy at high rates. The first type is a mold with a low thermal mass that can be cooled at high rates together with the alloy. In this case, the alloy and the mold can be cooled from both sides. Examples of suitable materials include, but are not limited to, silicon and graphite. More preferably, a suitable mold may have a thermal mass less than about b 800 J/kg·K, even more preferably less than about 400 J/kg·K.
[0026] Another way to achieve the high cooling rates for the alloy is the use of a mold with low thermal conductivity. In this case, the alloy is preferably cooled only from the alloy's side, such as with a heat sink as described below. Examples of suitable materials include, but are not limited to, quartz. More preferably, a suitable mold may have a thermal conductivity less than about 5 W/m·K, more preferably less than about 2 W/m·K.
[0027] Optionally, the mold and the alloy may be separated by a protective layer or releasing layer. This layer may be native to the mold, such as a SiO 2 native oxide layer formed on a Si mold, described below. Other protective layers may also be used, including but not limited to amorphous carbon, silicon carbide and silicon oxynitride, and other suitable materials such as diffusion barriers (e.g., Ta—Si—N). The protective layer advantageously prevents reaction between the mold and the alloy and facilitates the subsequent separation of the mold from the alloy.
[0028] In order to prevent crystallization in the alloy upon quenching, the alloy is desirably cooled at a sufficiently rapid rate. FIG. 2 illustrates schematically a diagram of temperature plotted against time on a logarithmic scale for three exemplifying amorphous metallic alloys. A melting temperature T m and a glass transition temperature T g are indicated. The illustrated curves 18 , 20 and 22 indicate the onset of crystallization as a function of time and temperature for different amorphous metallic alloys. When the alloy is heated to a temperature above the melting temperature, in order to avoid crystallization, the alloy is cooled from above the melting temperature through the glass transition temperature without intersecting the nose 24 , 26 or 28 of the crystallization curve.
[0029] Crystallization curve 18 indicates that for these types of amorphous metallic alloys, cooling rates in excess of about 10 5 -10 6 K/sec have typically been required. Examples of amorphous metallic alloys in this category include alloys in the systems Fe—B, Fe—Si—B, Ni—Si—B and Co—Si—B.
[0030] The second crystallization curve 20 in FIG. 2 indicates that for these alloys, cooling rates on the order of about 10 3 -10 4 K/sec are required. Examples of amorphous metallic alloys in this category include alloys in the system Pt—Ni—P and Pd—Si.
[0031] With the crystallization curve 22 , cooling rates of less than about 10 3 K/sec and preferably less than 10 2 K/sec can be used. Examples of amorphous metallic alloys in this category include Zr-based alloys, as described below.
[0032] [0032]FIG. 3 is a schematic diagram of temperature and viscosity on a logarithmic scale for an undercooled amorphous alloy between the melting temperature and glass transition temperature. The glass transition temperature is typically considered to be a temperature where the viscosity of the alloy is in the order of about 10 13 poise. A liquid alloy, on the other hand, is defined to have a viscosity of less than about 10 2 poise. As shown in FIG. 3, as temperature is decreased from T m , the viscosity of the alloy first increases slowly and then more rapidly as the temperature approaches T g .
[0033] Referring again to FIG. 1, in step 12 the alloy is preferably heated to a preferred casting temperature at which a highly fluid alloy is formed. In one embodiment, this casting temperature is determined by the viscosity of the alloy. For example, the casting temperature may be the temperature at which the alloy has a viscosity below about 10 4 poise, more preferably below about 10 2 poise. In another embodiment, the casting temperature may simply be determined as a function of the melting temperature or the glass transition temperature. In one preferred embodiment, the alloy is heated above its melting temperature during step 12 . However, it will be appreciated that it is not necessary to go above the melting temperature in order to obtain a highly fluid alloy. Thus, in one embodiment, temperatures greater than about 1.2 T g will be sufficient, more preferably above about 1.5 T g , where T g is in ° C. A third method of determining casting temperature is simply to choose a temperature above the nose on the crystallization curve.
[0034] The fluidity of the alloy at these elevated casting temperatures allows wetting of the mold so that replication of fine features can be obtained. The high fluidity of the alloy also enables the use of lower pressures to press the alloy into the mold, as described below.
[0035] It will be appreciated that other methods may also be used to determine a suitable casting temperature. In general, because wetting of the alloy to the mold improves replication of the amorphous metallic part, any temperature at which suitable wetting of the alloy to the mold occurs can be used to determine a desired casting temperature.
[0036] [0036]FIG. 4 illustrates preferred cooling sequences for an amorphous metallic alloy having a crystallization curve 30 , as shown. FIG. 4 illustrates that the amorphous metallic alloy is preferably selected such that when the alloy is cooled, the cooling graph 34 does not intersect the nose 32 of the curve 30 . In the formation of high aspect ratio parts, it may also be desirable to hold the alloy in its high temperature state for a period of time in order to allow the alloy to fully wet the mold. This time, for example, may range between about 5 seconds and several minutes. When the casting process begins with the casting temperature of the alloy above T m , as shown by graph 34 , the alloy can be held at this temperature for theoretically an unlimited period of time while avoiding crystallization. Thus, while graph 34 shows only the quenching step in the production of the alloy, it will be appreciated that this quenching step can be preceded by a suitable holding period above T m to ensure suitable wetting of the mold.
[0037] [0037]FIG. 4 also illustrates a cooling graph 36 using a casting temperature below T m . For the method illustrated by this graph, the time period 38 represents holding the alloy at the casting temperature. Because the alloy will crystallize if held at this temperature for too long, the alloy is held at the casting temperature for a short period of time, more preferably about 5 seconds to several minutes. As with cooling graph 34 , cooling graph 36 illustrates quenching of the alloy at a sufficiently fast rate to avoid intersecting the nose 32 of the curve 34 , thereby avoiding crystallization of the alloy.
[0038] Because the alloy described by the methods above effectively wets the mold, replication of the pattern on the mold is more precise than in cold mold casting. This is illustrated in FIG. 5, which shows an exemplifying mold having recesses formed therein for the formation of high profile parts. As illustrated, one or more of the recesses 40 on the surface 42 of the mold 44 has a height H and a width W, the height H being greater than the width W. In order to effectively wet the mold such that the entire groove is substantially filled with alloy, the fluidity of the alloy is preferably chosen such that the groove can be filled in a fast enough time without the onset of crystallization. FIG. 4 illustrates that after a period 38 of holding the alloy at the casting temperature, the alloy is quenched as shown in cooling graph 36 such that the quenching curve does not hit the nose 32 .
[0039] A successful experiment for forming an amorphous metallic part was performed as follows. A mold was provided as a micro-structured silicon wafer. More particularly, the mold was a 4″ wafer, prepared by deep reactive ion etching with test structures, 100 μm deep and 30 to 2000 μm wide. A protective layer formed on the silicon wafer was the native SiO 2 , which is about 1 nm thick. Other molds can be used, having desirable properties of low thermal mass or low thermal conductivity. Other suitable materials for the mold include amorphous carbon.
[0040] A bulk glass forming alloy had the composition Zr 52.5 Cu 17.9 Ni 14.6 Al 10 Ti 5 with a melting point of about 800° C. and a critical cooling rate for glass forming of about 10 K/s. It will be appreciated, however, that other alloys can be used. For example, other Zr-based amorphous alloys may be used, such as Zr—Ti—Ni—Cu—Be alloys. Other alloys, such as disclosed in U.S. Pat. Nos. 5,950,704 and 5,288,344, the entirety of both of which are hereby incorporated by reference, also may be used.
[0041] [0041]FIG. 6 illustrates schematically the set up in one embodiment for the preparation of amorphous metallic parts. The micro-structured silicon wafer 46 is preferably provided on a quartz support 48 , which is supported over a heat source 50 such as an RF coil. The RF coil is used because it advantageously allows the heat supply to be stopped abruptly. It will be appreciated, however, that other heat sources may also be used, such as a hot plate which may be separated from the wafer before cooling in order to stop the heat supply.
[0042] In the illustrated example, the amorphous metallic alloy 52 was placed onto the silicon wafer 46 . The sample alloy may take any desirable form, and in the example illustrated, a 5 g button of alloy was used. The experiment was performed in a vacuum chamber at 10 −5 mbar.
[0043] The alloy and the mold were heated to above its melting temperature to about 1000° C. by the RF coil 50 positioned below the quartz disc 48 . After reaching this elevated casting temperature a copper block 54 at room temperature was lowered and pressed onto the alloy. The copper block was lowered onto the alloy after about 2 to 5 seconds at the casting temperature. The copper block was preferably lowered onto the alloy at a rate between about 0.01 and 1 m/s, with better results achieved using higher speeds. Because of the high fluidity of the metallic alloy, a relatively low pressure of about 0.01 to 0.1 N was used to press the copper block.
[0044] The alloy 52 wetted the wafer 46 on a circle of about 10 mm and was spread out and cooled by the copper block to a disc of about 30 mm in a diameter and 1 mm in thickness. Cooling of the alloy 52 preferably occurred at a sufficiently rapid rate to avoid crystallization of the alloy, more preferably at a rate of up to about 100 K/sec. After cooling, the silicon was removed from the alloy by etching it about 72 hours in concentrated KOH solution.
[0045] The topology of the amorphous disc was investigated with an optical microscope. The volume of the mold features was approximately 95% filled. There was no apparent difference between regions which had wetted the silicon wafer during heating and those which had been produced when the melt flowed outward under pressure onto exposed silicon.
[0046] [0046]FIGS. 7A and 7B are SEM pictures of an amorphous metallic component formed according to the above procedure. More particularly, these figures illustrate a replicated structure having walls of about 30 μm in width, and a depth of about 100 μm. FIG. 7A shows the structure at 30× magnification, and FIG. 7B shows the structure at 300× magnification. Such a component can preferably be made using a mold having a surface structure similar to that shown in FIG. 5, where the walls have a width W which is about 30 μm and a height H which is about 100 μm. Thus, these pictures illustrate that the methods described above are capable of forming amorphous metallic parts having aspect ratios greater than about three in the micrometer scale.
[0047] [0047]FIGS. 8A and 8B are SEM pictures of another amorphous metallic component formed according to the above procedure. These figures illustrate a replicated structure having channels that are about 40 μm wide and 100 μm deep. FIG. 8A shows the structure at 30× magnification, and FIG. 8B shows the structure at 300× magnification.
[0048] As shown in the pictures described above, amorphous metallic components can be formed having extremely fine surface features. These components, by virtue of being amorphous metals, also take advantage of at least one of the following properties: mechanical properties (e.g. high elastic deformation, high hardness), chemical properties (e.g. corrosion resistivity, catalytic properties), thermal properties (e.g. continuous softening and increase of diffusivity, low melting point) or functional properties (e.g. electronic, magnetic, optic). Thus, a finely replicated part having one or more of the above desired properties is desirably formed by the above-described procedures.
[0049] One example of an application for which the formation of high aspect ratio parts may be desirable is injection molding of polymers (e.g. for disposable culture dishes in medicine). In one experiment, replicated amorphous metallic structures were tested as tools for micro polymer injection casting. About 100 replications with polycarbonate were performed, with complete replication into a polymer part being made using amorphous metallic casters. The observed parts of the metallic glass tool that were completely amorphous before casting did not show any damage after the replications.
[0050] It will be appreciated that various microstuctures may be formed using the preferred methods described above. High aspect ratio parts, for example, can be made for microfluidic and microoptic applications. One microfluidic application provides a system of channels in micrometer scale in order to handle liquids in nanoliter volumes (e.g., reactors for expensive reactants as enzymes). In addition, flat, mirror-like polished surfaces can be prepared on amorphous metallic parts using unstructured molds. Thus, thin plates with large dimensions and mirror finishes on one side can be prepared, if for example, a silicon wafer is used as hot mold. As one example, casting of an amorphous plate of 100 mm diameter and 1 mm thickness can be accomplished using the methods described above.
[0051] It should be understood that certain variations and modifications of this invention will suggest themselves to one of ordinary skill in the art. The scope of the present invention is not to be limited by the illustrations or the foregoing descriptions thereof, but rather solely by the appended claims.
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A manufacturing process for casting amorphous metallic parts separates the filling and quenching steps of the casting process in time. The mold is heated to an elevated casting temperature at which the metallic alloy has high fluidity. The alloy fills the mold at the casting temperature, thereby enabling the alloy to effectively fill the spaces of the mold. The mold and the alloy are then quenched together, the quenching occurring before the onset of crystallization in the alloy. With this process, compared to conventional techniques, amorphous metallic parts with higher aspect ratios can be prepared.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a pallet for receiving and transporting loads, having an upper platform for receiving the loads, and a substructure, which supports the upper platform and is constructed of an upper part and a lower part and several support members therebetween inserted.
2. Discussion of Related Art
A pallet is disclosed in German Patent Reference DE 36 12 647 A1. Individual ones, or all components of this pallet, on which packages to be stored or transported are received on support decks attached to a support substructure, have been produced from comminuted fiber waste material, with plastic as a binder, to obtain a budget-priced, weather-resistant pallet with a long service life. However, such pallets often do no have a sufficient shock-absorbing capability for the goods to be transported.
German Patent Reference DE 299 09 001 U1 shows pallets with a substructure of interspersed blocks, on which a receiving platform is placed. As reinforcement, the interspersed blocks have fiber mats or a bi-axially stretched thermoplastic material, if required with additives, which are also cost-effective and can be recycled. With these pallets, the absorption of shocks is often not sufficient.
SUMMARY OF THE INVENTION
One object of this invention is to provide a pallet of the type mentioned above but which has an improved shock-absorbing effect.
This object is attained by a pallet having characteristics taught in this specification and in the claims. The support members each are of a held-together bundle of spike-like individual elements, which extend between the upper part and the lower part, which can be laterally deflected with respect to each other and which have damping properties. The support members, which assure a sufficient support strength for the loads to be received, will yield if sudden shocks occur, for example when the pallets are put down. Thus it is also possible to prevent vibrations. As a bundle, the spike-like or small rod-like individual elements for one act as good supports and, because of their spreading effect toward their end sections or by bulging in their center area are sufficiently resilient, in case of excessive forces, to absorb a shock, for example resulting from the spines of a hedgehog.
Great stability, along with dependable functioning ability can be accomplished because at locations which are vertically spaced apart from each other in the position of use, the upper part has hollowed-out spaces on an underside and the lower part has hollowed-out spaces on a top, into which the end sections of the bundles are inserted.
Here an advantageous construction results if the hollowed-out spaces have a hood-shaped curvature. An advantageous support also results from the hood-shaped or convex curvature oriented outward with respect to the linear extension of the bundles of small rods.
The steps, wherein the upper part and the lower part are connected with each other at intersecting points where the support members are arranged, also contribute to a stable construction, along with dependable functioning. Also, the upper part and the lower part can be connected with each other by elastic or flexible or movably suspended elements, so that they are securely kept together.
A construction which is advantageous regarding the way of functioning of the support elements if the bundles of the spike-like individual elements are kept together by a bundling ring. In this connection, the bundling ring provides good spreading possibilities for the individual elements in the direction toward their end sections or, in case of an elastic embodiment of the bundling ring in the center area and, when elastically embodied, the bundling ring itself can assist the damping properties, or shock absorption.
In one advantageous construction the upper part and the lower part are held together by the bundling rings, wherein the bundling rings permit a vertical movement of the upper part and the lower part relative to each other. In this case, the bundling ring can itself be elastically designed and/or permit a relative movement between the upper part and the lower part, also in the vertical direction.
It is possible to achieve a stable, yet still shock-damping, embodiment if the underside of the lower part is supported on a base, and/or the top of the upper part is supported against a receiving plate by support sections which spread in the manner like tree roots. In this case, the support sections spread in a funnel shape or finger shape conically with respect to the base or toward the receiving plate.
The steps wherein the support sections are vertically positioned below or above the bundles also contribute to an advantageous construction and good functioning.
A stable construction with advantageous transport possibilities, for example by forklifts, results from the upper part having upper longitudinal struts and transverse struts, in whose connecting points the support members are installed, and the lower part has lower longitudinal struts extending under the upper longitudinal struts, with which the support members are connected.
Steps, wherein the upper and lower longitudinal struts, diagonal struts, and possibly diagonal struts on the upper part, have a lightweight construction in the form of a skeleton, contribute to stability. The skeleton principle results in great stability, along with lightweight construction and a relatively low requirement for materials.
Manufacture, retooling and possibly simple repairs are possible if the upper part has holding elements for the tool-free attachment of the upper platform.
BRIEF DESCRIPTION OF THE DRAWINGS
This invention is explained in greater detail in view of exemplary embodiments, making reference to the drawings, wherein:
FIG. 1 shows a pallet with a receiving plate and a substructure in a perspective plan view, in an assembled and an exploded state;
FIG. 2 shows a further representation of a pallet with a substructure and parts thereof, in a perspective plan view; and
FIG. 3 shows a further representation of a pallet in a perspective plan view, in an assembled and exploded state.
DETAILED DESCRIPTION OF THE INVENTION
A pallet 1 with a substructure 3 and a receiving plate 2 for packages is shown in FIG. 1 , in the assembled state and also in an exploded state. For example, the receiving plate 2 is made of a recyclable composite fiber material of natural fibers or of wood, for example as a closed plate or as a plate-like strut construction. In a view from above, the pallet 1 can be rectangular or square.
The substructure 3 is put together from an upper part 30 and a lower part 40 , with support members 50 interspersed at intersection points, inclusive of the corner areas. The upper part 30 has horizontal struts arrangements of longitudinal struts 32 and transverse struts 31 extending at right angles with them wherein, in the example shown, two lateral longitudinal struts 32 and one further longitudinal strut extending centered and parallel with respect to them, as well as two lateral transverse struts 31 and a center transverse strut extending centered and parallel with respect to them, are connected with each other at their intersection points. Furthermore, diagonal struts 38 extend between the corner points and are also connected with the transverse struts 31 and the longitudinal struts 32 . In the present case, the longitudinal struts 32 are wider and more sturdy than the transverse struts 31 and diagonal struts 38 . The longitudinal struts 32 , the transverse struts 31 and the diagonal struts 38 are made in lightweight construction in the form of a skeleton, a skeleton principle, and connected in order to obtain the greatest possible stability with the least possible use of material. At the outer edge of the lateral longitudinal struts 32 and transverse struts 31 , two holding elements are formed which, for example, are spaced apart from each other and upwardly oriented, which partially enclose the receiving plate 2 at the edge and hold it by a clamping effect, snap-in effect or by a locked-in connection without requiring tools. In a similar way, it is also possible for other holding elements to be arranged over the length of the transverse struts 31 , the longitudinal struts 32 and/or the diagonal struts 38 , which work together with counter-elements of the receiving plates 2 .
Upper support sections 34 are inserted, for example formed-on in one piece or fixed in place as separate elements, at the intersection points of the longitudinal struts 32 and the transverse struts 31 , and have hollowed-out spaces 35 for the support members 50 , which are open toward the bottom and are closed off toward the top, in a hood shape. The hollowed-out spaces 35 , which are convex toward the top, are surrounded by support elements, or support feet 36 , which open upward in a funnel shape and on which the receiving plate 2 is supported, similar to a tree root principle. This shaping of the support sections 34 results in a structure which is advantageous for shock dampening.
The lower part 40 has lower longitudinal struts 41 extending parallel underneath the upper longitudinal struts 32 , on which lower support sections 34 ′ are formed or fixed in place underneath the support sections 34 . In this way, interspaces extending in the longitudinal direction result between the lateral longitudinal struts 41 and the center longitudinal strut, between which the pickup forks of a forklift, for example, can be inserted. For example, the lower longitudinal struts 41 have the same cross-sectional profile as the upper longitudinal struts 32 . In this case, the lower support sections 34 ′ are shaped corresponding to the upper support sections 34 , but point downward with a section which widens in a funnel shape in order to be supported, in accordance with the tree root principle, on the base and to also assist in the absorption of shocks. Corresponding to the upwardly convex hollowed-out spaces 35 with their convex arching 37 , the lower support sections 34 ′ have downwardly convex, or hood-shaped hollowed-out spaces 35 .
With their end sections, the support members 50 are inserted on the one side into the hollowed-out spaces 35 of the lower support sections 34 ′ and on the other side into the hollowed-out spaces 35 of the upper support sections 34 , which can be seen more clearly in the lower representation in FIG. 2 , in particular. Each support member 50 comprises a bundle 51 of spike-like small rods, wherein the ends of the bundles are rounded, similar to the assigned hollowed-out spaces 35 . The “spike bundles” are held together by a center circumferential ring which, in the assembled state of the upper part 30 and lower part 40 , is arranged between the facing end areas of the support sections 34 , 34 ′. In this case, there is a certain amount of play in the hollowed-out spaces 35 , which makes it possible for the spike-like small rods to spread in the direction toward the end sections and in the process to be supported on the respective facing inner wall of the hollowed-out spaces 35 . Alternatively, or additionally, the design can be such that the spike-like small rods spread in the center relatively to each other, wherein the bundling ring 52 is resilient and counters the spreading by its elastic force. The small rods themselves also have a certain amount of resilience for spreading in the center. With this design and by the insertion of the support members 50 , shock damping results in case of sudden setting-down of the pallets or during transport, while on the other hand large support forces are assured.
As FIG. 2 shows, the receiving plate 2 itself can be designed as a strut structure. Also, the top of the upper part 30 can be the receiving platform. The longitudinal struts 32 , 41 , or also the further struts, can for example be formed from two parallel rods which are spaced apart from each other and which are connected as one piece in the area of or near the support sections 34 , 34 ′.
FIG. 3 also shows a pallet 1 in an assembled representation and in an exploded representation, wherein the receiving plate 2 is omitted in contrast to FIG. 1 .
As the representations in accordance with FIGS. 1 , 2 and 3 further show, the support sections 34 , 34 ′ with the support members 50 inserted are arranged evenly distributed over the surface of the pallet, wherein support sections with support members 50 are arranged at the corners, in the center of the lateral edges, as well as in the center of the pallet. Advantageously, the bundling ring 52 can be resilient and on its part contributes to shock absorption. The upper part 30 and the lower part 40 are for example connected by the bundling rings 52 and/or by intermediate elements, which for example are designed elastically or flexibly or movably with links in the manner of a chain and prevent the falling apart of the upper part 30 and the lower part 40 .
German Patent Reference 10 2007 017 151.1, the priority document corresponding to this invention, and its teachings are incorporated, by reference, into this specification.
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A pallet for receiving and transporting loads, having an upper platform for receiving the loads, and a substructure, which supports the upper platform and is constructed of an upper part and a lower part and several support members inserted between them. A good shock absorption, along with a rugged construction, is achieved because the support members each is of a held-together bundle of spike-like individual elements, which extend between the upper part and the lower part, can be laterally deflected with respect to each other and have damping properties.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to novel ferroelectric side-chain liquid crystalline copolymers, with siloxane backbone and a triaromatic mesogen as the side group. In these copolymers, a certain proportion of the repetitive units of the polymer backbone bears the mesogenic side groups. The materials exhibit ferroelectric smectic C (or SmC*) mesophase over a large range of temperatures, in some cases extending to subambient temperature. They also possess high values of spontaneous polarization and exhibit fast electro-optic switching times. In addition, these materials show pronounced electroclinic effects in the smectic A phase. Such liquid crystalline compounds are useful in the field of electro-optic devices, pyro-electric and piezo-electric detectors, non-linear optics, etc.
2. Discussion of the Background
In the last decade, the area of applications of liquid crystal displays (LCDs) has grown from wrist-watches to computer terminals and television displays. Most of the current liquid crystal displays are based on effects shown by conventional low molecular weight nematic liquid crystals. However, these materials are limited in that their response speeds are low, i.e., on the order of several tens of milliseconds. To overcome this problem, Clark and Lagerwall described a structure in which the ferroelectric character of the chiral smectic phase (SmC*) is optimally employed: the so-called Surface Stabilized Ferroelectric Liquid Crystal (SSFLC) structure. These liquid crystals have bistable states under the application of an electric field, the states being switchable on reversing the polarity of the field. Since this switching is essentially related to molecular rotation about its long axis, the response speed is faster than in the case of a nematic liquid crystal.
Still, the application of these materials for the processing of large size and curved screens remains limited. This is because, in order to make these large screens, it is important to have a uniform and defined distance (˜microns) between the two glass substrates in which the liquid crystalline compound is sandwiched. Practically, this is impossible to accomplish over large areas.
In order to solve this problem, it has been tried to use polymeric liquid crystals so as to make the materials easily processable (molding, film making, etc.). There have been some reports of the observation of the SmC* phase in side-chain liquid crystal polymers.
For example, Shibaev et al, Polymer Bull., vol. 12, p. 299 (1984) have reported a side chain liquid crystal polymer, and the exact formula: ##STR2## was reported later by Shivaev et al, Pure and Applied Chem., vol. 57, p. 1589 (1985).
Decobert et al, Polym. Bull., vol. 14, p. 179 (1985) have reported a number of polymers having the structure AX n : ##STR3## X═H, CH 3 , Cl n=2, 6, 11.
Guglielminetti et al, Polym. Bull., vol. 16, p. 411 (1986) have reported compounds of the formula BX n ##STR4## X═H, CH 3 , Cl n=2, 6, 11
Shibaev et al, Vissokomol Soedin, vol. 29, p. 1470 (1987) have also reported a side chain liquid crystal polymer of the formula: ##STR5##
Hahn and Percec, Macromolecules, vol. 20, p. 2961 (1987) have reported a polysiloxane side chain liquid crystal polymer having the formula: ##STR6##
Keller, Ferroelectrics, vol. 85, p. 813, (1988) has described another polysiloxane liquid crystal polymer of the formula ##STR7##
Zentel et al, Liquid Crystals, vol. 2, p. 83, (1987) have prepared combined liquid crystal polymers of the formula ##STR8## n=2 or 6
Bualek et al, Makromol. Chem., vol. 189, p. 797 (1988) have also prepared combined liquid crystal polymers which have the formula: ##STR9##
Kapitza et al, Makromol. Chem., vol. 189, p. 1793 (1988) have reported combined liquid crystal polymers of the formula: ##STR10##
However, these materials exhibit the SmC* phase only at high temperatures. Also, the materials reported so far have switching times of the order of a few milliseconds and hence are not suitable for the above-described applications. Thus, there remains is a need for faster switching polymers with ferroelectric phase over a large temperature range extending to room temperature. The present invention reports novel materials which satisfy these requirements.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide novel fast switching liquid crystalline polymers.
It is another object of the present invention to provide liquid crystal displays which contain such liquid crystalline polymers.
These and other objects, which will become apparent during the following detailed description, have been achieved by the inventors' discovery that copolymers which contain (a) 0.1 to 0.9 mole % of repeating units bearing at least one side-chain mesogenic group and (b) 0.1 to 0.9 mole % of repeating units which do not bear a side-chain mesogenic group and wherein the side-chain mesogenic group has the formula:
--(CH.sub.2).sub.n O--R.sub.1 --X--R.sub.2
wherein R 1 is 1,4-phenylene or 4,4'-biphenylene; X is --COO-- or --OCO--; R 2 is ##STR11## in which k is 0 or 1, * denotes an optically active center; Z is NO 2 , F, or Cl; R 3 is C l H 2l+1 , --*CH(CH 3 )C p H 2p+1 --CH 2 C q F 2q+1 , or --*CH(CH 3 )COOC t H 2t+1 (l and p are each independently an integer of from 1 to 10 and q and t are each independently an integer of from 1 to 6); and n is an integer of 4 to 12; are ferroelectric liquid crystalline copolymers which not only exhibit a wide chiral smectic phase range within room temperature, but also exhibit high response speeds to external fields.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
As noted above, the object of the present invention is to solve the above-mentioned problems and to provide new ferroelectric liquid crystalline copolymers which not only have a wide chiral smectic phase range within room temperature, but also exhibit high response speeds to external fields.
Thus, the present invention provides side-chain liquid crystal polymers which contain (a) 0.1 to 0.9 mole % of repeating units which bear at least one of a particular mesogenic side group and (b) 0.1 to 0.9 mole % of repeating units which do not bear a mesogenic side group in which the mesogenic side group has the formula
--(CH.sub.2).sub.n O--R.sub.1 --X--R.sub.2
in which n, R 1 , X, and R 2 are as described above. Suitably, the backbone of polymer may be any type of conventional polymer, such as a poly-α,β-unsaturated acid or ester, polysiloxane, polyalkene, polyether, polyester, polysulfone or polychloroacrylate. In a preferred embodiment, the liquid crystalline copolymers provided by the present invention contain a poly(alk)acrylate or a polysiloxane backbone and bear a certain ratio of mesogenic side groups. These liquid crystalline copolymers are represented by the following general formulae: ##STR12## wherein: the ratio b/(a+b) is any fraction between 0.1 and 0.9 for the copolymers of formula (I);
the ratio (b+c)/(a+b+c) is any fraction between 0.1 and 0.9 for the copolymers of formula (II);
R is H or C 1-4 -alkyl;
R' is H or C 1-4 -alkyl;
R" is C 1-4 -alkyl;
R"' is C 1-4 -alkyl;
R 1 is 1-4-phenylene or 4,4'-biphenylene;
X is --COO-- or --OCO--;
R 2 is ##STR13## wherein k is 0 or 1;
* is an optically active center;
Z is NO 2 , F, Cl;
R 3 is C l H 2l+1 , --C*H(CH 3 )C p H 2p+1 , --CH 2 C q F 2q+1 , --C*H(CH 3 )COOC t H 2t+1 (wherein l and p are each independently an integer from 1 to 10 and q and t are each independently an integer from 1 to 6); and n is an integer of from 4 to 12.
The liquid crystal polymers of the present invention are preferably random copolymers with the units a and b distributed randomly throughout the copolymer. The copolymers of formula (II) are particularly preferred. Especially preferred are those compounds of formula (II) in which the ratio c/(a+b+c) is 0.
The copolymers of formula (I) may be prepared by copolymerizing the monomers corresponding to the repeating units a and b by the reaction shown below: ##STR14##
Such polymerization reactions may be carried out in accordance with any conventional method for polymerizing α,β-unsaturated carboxylic acids. Such polymerizations may be carried out, e.g., by heating a mixture of the monomers in an inert solvent in the presence of a polymerization catalyst such as azobis(isobutyronitrile) or ultraviolet light. In such polymerizations, the ratio of a:b in the final polymer will correspond to the relative amounts of the monomers in the reaction mixture.
Alternatively, the copolymers of formula (I) may be prepared by esterifying an already existing poly(alk)acrylate polymer as shown below: ##STR15## wherein R, R', R 1 , X, and R 2 are as defined above and Y is --OH or Cl.
The copolymers of formula (III) in which Y is --OH are commercially available or may be prepared by copolymerizing monomers as shown below: ##STR16## The copolymers of formula (III) in which Y is Cl may be prepared by treating the corresponding copolymer having Y═--OH with a chlorinating agent such as thionyl chloride in an inert solvent such as an alkane (hexane or heptanes) or an aromatic solvent (benzene or toluene).
In the case of formula (I), it is preferred that R is either H or methyl, and the number average molecular weight is suitably between 4,000 and 80,000.
The liquid crystalline copolymers of the formula (II) described in this invention may prepared by reaction of a mesogenic vinyl end group derivative with a preformed copolysiloxane backbone, e.g., poly(dimethylsiloxane-co-methylhydrogenosiloxane) in presence of Platinum catalyst, via a hydrosilylation reaction.
The starting polysiloxane backbone can be prepared or may be purchased. Different kinds of statistical poly(dialkylsiloxane-co-alkylhydrosiloxane), poly(dialkylsiloxane-co-dihydroxiloxane), and poly(dialkylsiloxane-co-alkylhydrosiloxane-co-dihydrosiloxane) copolymers are commercially available or easily synthesized, varying in the molecular weight, the polydispersity index and the proportion of methylhydrogenosiloxane units and/or dihydrosiloxane units.
The number average molecular weight of the resulting liquid crystalline copolymers of formula (II) is preferably between 4,000 and 80,000 depending upon the molecular weight and the proportion of the methylhydrogenosiloxane units of the starting copolysiloxane, the nature and the purity of the mesogenic derivative, the nature of the catalyst, etc.
The synthetic method for the preparation of the liquid crystalline copolymers of the present invention is described below.
For example, the synthesis scheme of the copolysiloxane of formula (II) with
n=10; R 1 is 4,4'-biphenylene; 0=c/(a+b+c);
X is --COO--;
R 2 is ##STR17## R 3 is --C 2 H 5 may be outlined schematically as follows: ##STR18##
The mesogenic group (R)-4'-(1-ethoxycarbonyl-1-ethoxy)-phenyl-4-[4-(9-decenyloxy)-phenyl]-benzoate 1 was synthesized as follows. 4'-(9-decenyloxy)biphenyl-4 carboxylic acid 1 was prepared by reacting hydroxybiphenyl carboxylic acid methyl ester with 10-bromo-1-decene in DMF containing NaH followed by hydrolysis. Compound 2 was synthesized by coupling of ethyl-(S)-2 hydroxypropionate with p-(benzyloxy)phenol. Hydrogenolysis of 2 by Palladium on activated charcoal led to the formation of the phenol derivative 3. The final product 1 was obtained by reaction of the acid chloride of 1 with 3 in the presence of pyridine.
The corresponding copolymer was obtained through the hydrosilylation reaction between the olefinic derivative and the poly(dimethylsiloxane-co-methylhydrogenosiloxane).
For the preparation of copolymers of formula (II) in which repeating units (c) having two mesogenic groups are present, the above-described synthesis is changed by starting with a polysiloxane copolymer containing repeating units of the formula (SiH 2 --O).
An alternative for the preparation of these materials, namely a base catalyzed polymerization technique, may be considered. However, this method is less efficient than the above-described hydrosilylation reaction because it leads to the formation of side products which are difficult to eliminate, and shows less reproducibility related to the preparation of these materials (e.g., molecular weight, polydispersity, fixation ratio in mesogenic side groups).
The present side chain liquid crystal polymers are useful in a number of applications, including liquid crystal display devices, transducers, pyroelectric detectors, and non-linear optics. The use of side chain liquid crystal polymers in such devices is well known in the art. For example, electrooptic light modulator devices containing side chain liquid crystal polymers are described in U.S. Pat. Nos. 4,944,896 and 4,948,532, which are incorporated herein by reference. Similarly, a display device may be prepared by disposing an amount of the present liquid crystal polymer between two electrodes. The present side chain liquid crystal polymers may also be used in erasable and reconfigurable memory devices.
It should be understood that a key feature of the present side chain liquid crystal polymers is the fact that by selecting the proper value of the ratio b/(a+b) for the copolymers of formula (I) or (b+c)/(a+b+c) for the copolymers of formula (II) it is possible to control the viscosity and, thus the switching time of the side chain liquid crystal polymers. Thus, the present invention provides tunable liquid crystal polymers.
In some applications, it may be desirable to add an amount of a low molecular weight chiral compound which is miscible with the side chain liquid crystal polymer. Such mixtures are described in U.S. Pat. No. 4,293,435, which is incorporated herein by reference.
Other features of the invention will become apparent in the course of the following descriptions of exemplary embodiments which are given for illustration of the invention and are not intended to be limiting thereof.
EXAMPLES
In the following examples, the structures of the copolymers were determined by 1 H NMR, IR and elemental analysis.
The phases exhibited by the materials have been identified by optical microscopy and the phase transition temperatures were detected both by optical microscopy and by differential scanning calorimetry. The electro-optic switching times were determined with a photo diode measuring the transmitted light of the sample placed between polarizers. The switching time is defined as the time required for an intensity change from 0% to 90% on applying a square wave. The spontaneous polarization has been measured by the triangular wave method. A 20 V amplitude triangular wave (frequency range 0.1 Hz to 100 Hz) was applied across 4 μm thick and the current was determined by measuring the voltage drop across a reference resistance with a storage oscilloscope.
The phase states are represented by the following abbreviations: (Cry, crystal; Iso, isotropic; SmA, smectic A phase; SmC*, chiral smectic C phase; SmX, unidentified high ordered smectic phase; and g, glassy state.
EXAMPLE 1
Preparation of the liquid crystalline copolymer represented by the formula: ##STR19## 1.1 Synthesis of 4'-(9-decenyloxy)biphenyl-4-carboxylic acid
To a nitrogen flushed flask, kept at 0° C., containing 960 mg (40 mmol) of oil-free sodium hydride was added 150 ml of dry DMF. A solution of 6.57 g (30 mmol) of 10-bromo-1-decene in 20 ml of DMF was added dropwise to the suspension. The resulting mixture was allowed to stir for 1 h at room temperature, and 8 h at 80° C. The solvent was removed by rotary evaporation in vacuo, and excess sodium hydride was quenched by addition of water. A 1N HCl solution was poured into the mixture, and the resulting precipitate was filtered and washed with 10% aqueous sodium bicarbonate solution and water. The crude product was recrystallized twice from ethanol to afford 8.7 g (79%) of 4'-(9-decenyloxy)biphenyl-4-carboxylic acid methyl ester. Hydrolysis of the ester derivative in the presence of KOH/ethanol led to the acid derivative which was recrystallized from acetic acid to yield 90% of the product.
1.2 1-(Benzyloxy)-4-[(R)-1-carboethoxy-ethoxy]benzene
To 4.48 g (38 mmol) of ethyl (S)-2-hydroxypropanoate, 10 g (50 mmol) of p-(benzyloxy)phenol, and 13.1 g (50 mmol) of triphenylphosphine was added 200 ml of dichloromethane. To this mixture was added dropwise a solution of 20 ml of dichloromethane and 8.2 ml (50 mmol) of diethyl azodicarboxylate. The reaction mixture was stirred overnight at room temperature. After evaporation of the solvent, the residue was subjected to column chromatography on silica gel to yield 7 g (61%) of pure product (mp 52° C.).
1.3 p-[(R)-1-ethoxycarbonyl-1-ethoxy]phenol
Hydrogen was allowed to bubble through a stirred suspension of 10% palladium on carbon (0.4 g) in 40 ml of dichloromethane. After 15 min, 7 g (23 mmol) of benzyl ether 2 was added, and the reaction mixture was stirred overnight. The suspension was filtered through a celite pad, the solvent was removed by rotary evaporation, and the crude product was obtained by distillation under vacuum to yield 4.5 g (91%) of the product.
1.4 (R)-440 -(1-carboethoxy-ethyoxy)phenyl 4-[4-(9-decenyloxy)phenyl]benzoate
A mixture of 1 (2.11 g, 6 mmol), thionyl chloride (20 ml) and two drops of DMF was refluxed for 3 h at 80° C., and then the remaining thionyl chloride was removed under vacuum. Into the mixture of the acid chloride and the phenol derivative 3 (1.3) g, 6.2 mmol) were added 1 ml of pyridine and a few crystals of 4-(dimethylamino)pyridine (DMAP) in dichloromethane (30 ml) under an atmosphere of nitrogen. After three days of stirring at room temperature, the reaction mixture was quenched with 10% HCl aqueous, washed with 5% sodium hydroxide solution and brine, and then dried over MgSO 4 . The removal of the solvent gave a thick oil which was purified by column chromatography on silica gel. The product was further purified by two recrystallizations from ethanol to yield 1.8 g (55%) of the expected material.
1.5 Synthesis of the ferroelectric liquid crystalline copolymer
To a solution of poly[(65-70%)dimethylsiloxane-co-(30-35%)methylhydrogenosiloxane] (0.73 mmol of Si-H function) dissolved in 50 ml of dry toluene was added 500 mg (0.92 mmol) of the vinyl derivative described above. The reaction mixture was heated to 100° C. under nitrogen and 20 μl of dicyclopentadienylplatinum (II) chloride catalyst solution was then injected (1 mg/ml in dichloromethane). The mixture was refluxed under nitrogen for about two days. The resulting liquid crystalline copolymer was purified by gel permeation chromatography, and was isolated by precipitation from tetrahydrofuran solution into methanol. The copolymer was dried under vacuum at 60° C. (yield: 57%).
The liquid crystalline copolymer exhibits the following phase transition temperatures:
g 15° C. SmC* 136° C. SmA 155° C. Iso
The electro-optical properties of the copolymer are:
Response time: 0.15 msec at 129° C.
Spontaneous polarization: 180 nC/cm 2 at 35° C.
EXAMPLE 2
Preparation of the liquid crystalline copolymer having the following formula: ##STR20## 2.1 (R)-2-(benzyloxy)phenoxypropanoic acid
To a solution of benzyl ether 2 (6 g, 20 mmol) prepared in example 1, in 150 ml of methanol and 40 ml of water, were added 3.75 g (90 mmol) of LiOH; H 2 O. The reaction mixture was stirred overnight at room temperature. After evaporation of the solvent, the residue was neutralized by HCl in water. The suspension was filtered, and the crude product was recrystallized from an ethanol/water mixture. Yield 5 g (91%); mp 96.6°-97.6° C.
2.2 2,2,3,3,3-pentafluoropropyl (R)-2-(4-benzyloxy)phenoxypropanoate
To a suspension of (R)-2-(benzyloxy)phenoxypropanoic acid (3.5 g, 13 mmol) and 60 ml of benzene, were added 2.8 ml (32 mmol) of oxalyl chloride and two drops of pyridine. After stirring the reaction mixture overnight at room temperature, the solvent was removed in vacuo. The acid chloride was dissolved in toluene and added dropwise to a solution of 2,2,3,3,3-pentafluoro-1-propanol (2.1 g, 14 mmol), 10 ml of pyridine, few crystals of 4-dimethylaminopyridine (DMAP) in 80 ml of toluene. The mixture was heated for 1 h at 80° C. and left overnight at room temperature. The solvent was removed, and the residue was dissolved in dichloromethane, washed with water, HCl solution, sodium bicarbonate, and dried with Na 2 SO 4 . Evaporation of the solvent led to the final compound: 3.5 g (66%) of a clear liquid.
2.3 p-[(R)-1-ethoxycarbonyl-1-(2,2,3,3,3-pentafluoro-1-propanoxy)]phenol
This compound was prepared by the same procedure used in Example 1.3. The final product (white crystals, 90% yield) was used for the next step without further purification. Mp 81°-82° C.
2.4 (R)-4-(1-carbo-(2,2,3,3,3-pentafluoropropoxy)ethoxylphenyl 4-(9-decenyloxy-4'-phenyl)benzoate
To a mixture of the phenol derivative (1.9 g, 5.93 mmol) prepared above, compound 1 (2.09 g, 5.93 mmol) of Example 1, and DMAP (61 mg, 0.49 mmol) in 100 ml of dichloromethane, was added 1-(3-dimethylaminopropyl)-3-ethyl-carbodiimidemethiodide (2.43 g, 8.2 mmol). The mixture was stirred for 24 h at room temperature. After dilution with dichloromethane, the organic phase was washed with water, a saturated solution of sodium bicarbonate, brine and finally dried over sodium sulfate. The solvent was evaporated and the residue was purified by column chromatography on silica gel. The product was further purified by recrystallization from ethanol to yield 2.44 g (61%) of white crystals.
2.5 Synthesis of the ferroelectric liquid crystalline copolymer
The synthesis of the copolymer was performed by the same procedure used in the preparation of the copolymer in Example 1 and using the same starting copolysiloxane. The final product was dried under vacuum at 60° C. (yield: 65%).
The liquid crystalline copolymer exhibits the following transition temperatures:
g 30° C. SmX 52° C. SmC* 139° C. SmA 170° C. Iso
The electro-optical properties of the copolymer are:
Response time: 0.13 msec at 135° C.
Spontaneous polarization: 330 nC/Cm 2 at 55° C.
EXAMPLE 3
Preparation of the liquid crystalline copolymer represented by the formula: ##STR21## 3.1 Ethyl (R)-2-(4-hydroxyphenyl)-4'-phenoypropanoate
To 4 g (21 mmol) of p,p'-biphenol, 2.36 g (20 mmol) of ethyl (S)-2-hydroxypropanoate, and 5.5 g (21 mmol) of triphenylphosphine in 100 ml of THF, was added dropwise a solution of diethyl azodicarboxylate 3.6I ml (23 mmol) in 20 ml of THF. The reaction mixture was stirred overnight at room temperature. After evaporation of the solvent, the residue was purified by column chromatography on silica gel to yield 2.9 g (51%) of the expected product.
3.2 (R)-4-[4'-(1-carbo(ethoxy)ethoxyphenyl]phenyl-4-(9-decenyloxy)benzoate
The preparation of this material was performed following the procedure used to make compound 4 in Example 2. The final product was purified by column chromatography on silica gel. The material was further purified by recrystallization from hexane to give a yield of 58%.
3.3 Synthesis of the ferroelectric liquid crystalline polymer
The synthesis of the ferroelectric liquid crystalline copolymer was performed by the same procedure used in the preparation of the copolymer in Example 1. The final product was dried under vacuum at 70° C.: yield 70%.
The liquid crystalline copolymer exhibits the following transition temperatures:
Cryst 57° C. SmC* 118° C. Iso
The electro-optical properties of the copolymer are:
Response time: 0.31 msec at 117° C.
Spontaneous polarization: 161 nC/cm 2 at 40° C.
EXAMPLE 4
Preparation of the liquid crystalline copolymer represented by the formula: ##STR22## 4.1 [{(S)-1-carboethyl-ethoxy]-4-benzyloxy benzoate
2.96 g (13 mmol) of p-benzyloxybenzoic acid, 2.3 ml (26 mmol) of oxalyl chloride and 50 cm 3 of dry benzene were mixed and stirred overnight at room temperature. The solvent was then removed by distillation and the residue was solubilized in 30 cm 3 of dry pyridine. To this solution, 1.55 g (13 mmol) of the ethyl-(S)-2-hydroxypropanoate in 20 cm 3 of dry pyridine were added and stirred overnight at room temperature. The resulting mixture was extracted with ether and the organic layers were washed with sulfuric acid, water, sodium hydrogen carbonate solution and finally with water. After drying the ether solution over anhydrous magnesium sulfate, the solvent was removed by evaporation and the residue was purified by column chromatography on silica gel to give 4.0 g of pure product (yield: 95%).
4.2 p-(S)-1-ethylcarbonyl-1-ethoxy]phenol
This compound was prepared using the same procedure as in Example 1.3. The product was further purified by column chromatography on silica gel to give 2.3 g of a clear oil (yield: 95%).
4.3 Ferroelectric liquid crystalline copolymer
The synthesis of the copolymer was performed by the same procedure used in the preparation of the copolymer in Example 1 and using the same starting copolysiloxane. The final product was dried for 2 days under vacuum at 60° C. (yield: 75%).
The copolymer exhibits the following phase transition temperature:
g 6° C. Cry 10° C. SmC. 163.5° C. SmA 191° C. Iso
Spontaneous polarization: 140 nC/cm 2 at 40° C.
The present invention provides novel ferroelectric liquid crystalline copolymers. These materials exhibit wide range of temperature of ferroelectric smectic C phase, large polarization and fast electro-optical switching times. The liquid crystalline copolymers may be used as a film which can be produced by known film forming techniques such as casting or stretching techniques. Such a film can find applications in various fields of optoelectronics, i.e., large displays or curved display screens, electronic optical shutters, memory devices, etc. Furthermore, the liquid crystalline copolymers may be further improved by blending these materials with a specific low molecular weight liquid crystalline compound; or by mixing them with additives such as some organic compounds or metals.
Obviously, numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.
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Liquid crystal polymers containing 0.1 to 0.9 mole % of repeating units bing a mesogenic side group and 0.1 to 0.9 mole % of repeating units which do not bear a mesogenic side group in which the mesogenic side group has the formula:
--(CH.sub.2).sub.n O--R.sub.1 --X--R.sub.2
R 1 is 1,4-phenylene or 4,4'-biphenylene;
X is --COO-- or --OCO--;
R 2 is ##STR1## wherein k is 0 or 1, * indicates an optically active center;
Z is NO 2 , F, or Cl;
R 3 is C l H 2l+1 , --*CH(CH 3 )C p H 2p+1 --CH 2 C q F 2q+1 , --*CH(CH 3 )COOC t H 2t+1 (wherein l and p are each independently an integer of from 1 to 10 and q and t are each independently an integer of from 1 to 6); and n is an integer of 4 to 12;
exhibit fast response times.
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BACKGROUND OF THE INVENTION
This invention relates to a life preserver and more particularly to a new and improved life preserver of a hybrid type that has an inflatable rectangular body or envelope with a closed chamber with buoyancy elements or pads therein.
Most life preservers have either an inflatable tube or buoyancy elements attached thereto to maintain the wearer's head out of the water. Many of these life preservers are cumbersome and bulky, taking up considerable room for maneuvering when being worn. The present invention is directed to a life preserver that is compact in size, can be worn while in a boat without interfering with one's mobility yet can be easily activated for positive inflation to hold the wearer in a proper attitude in the water, assuring full support. While being worn in the deflated condition, the life preserver of the present ivention provides positive visual indication that the life preserver is in its full operative condition and that there is no leakage in the gas impervious material of the life preserver. This is achieved by having a pad of open cell foam material, which can be an elastomeric material, within the chamber and when deflated, the open cell pad is compressed and retains its compressed condition since all the air within the chamber has been extracted. Where a tear in the material occurs, the air leakage into the closed chamber will fill the open cell foam, which will then expand to its full condition. Further, the inflation elements in this life preserver provide sufficient emergency buoyancy to the wearer without inflation. The shape of the life preserver in a stored condition is flat and easily packed. Such life preserver can be quickly positioned on a wearer and wrapped around the wearer's chest and secured for use thereon.
SUMMARY OF THE INVENTION
A life preserver worn around the torso or chest of a wearer, wherein the preserver is a generally rectangular shaped gas impervious support with an inflatable chamber. Valve means are mounted on the support and is operable to inflate the chamber which can be secured into an annular form by fastening means. Such fastening means includes manually operable valve to inflate the chamber and capsule or cartridge operable means to inflate the chamber. Flotation means are located and secured within the chamber to the support and to provide buoyancy to the wearer. Such flotation means includes open and closed cell foam pads wherein such can also act as leak detection indication means.
DESCRIPTION OF THE DRAWINGS
The invention will be explained in conjunction with an illustrative embodiment shown in the accompanying drawings, in which
FIG. 1 is a front elevational view of a preferred form of the invention, a life preserver as it appears when inflated and fastened upon a user;
FIG. 2 shows the life preserver of FIG. 1 when it is unfolded and flattened with the outside surface displayed;
FIG. 3 is a bottom view of the life preserver as unfolded in FIG. 3;
FIG. 4 is a cross sectional view taken in line 4--4 of FIG. 2, with the life preserver in an inflated condition; and
FIG. 5 is a cross sectional view of the life preserver similar to FIG. 4 but with the preserver in a deflated condition.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to the drawings wherein like reference numerals designate like or corresponding parts throughout the several views, there is shown in FIG. 1 and 2 a life preserver 10 which is a hybrid type of inflatable torso or chest support 11 comprising a generally rectangular flat flexible gas impervious envelope of polyurethane material with a closed chamber 12 (FIG. 4). Such rectangular shaped chest support 11 may be constructed from a single longitudinally extending piece of material folded over to form the envelope or a pair of rectangular panels heat sealed along the entire periphery to form such closed chamber 12 of chest support 11. The preferred form is shown in FIGS. 2 and 4 as consisting of a single panel which is heat sealed along its end portion as at 13 and 14 and along its one side 15.
The one end portion 14 of rectangular shaped chest support 11 has a pair of laterally spaced flat strips 18--18 suitably adhered thereto, while the other end portion 13 of rectangular shaped chest support 11 has the respective ends only of a pair of laterally spaced flat strips 19--19 secured thereto. Such strips 18--18 and 19--19 are fastener means with face-to-face bristle hook and loop type material respectively, which when placed into engagement provides a ready means to adjustably secure the chest support into an annular bend around the torso of a wearer, just below the shoulders. Such fastener means 18--18 and 19--19 is well known as VELCRO® fastener material. The fastener means are used to secure the life preserver 10 onto the wearer's torso to provide a snug fit so that the support 11 does not interfere with the movement of the wearer. Closely adjacent to the respective ends 14 and 13 are straps 20 and 21, whose end portions are provided with fastening means 22-23 respectively, such as quick-release fastening means.
The life preserver 10 has the ends of a pair of spaced straps 25 and 26 suitably attached to one side edge 15 of the chest support 11. Straps 25 and 26 have quick release fastening means 27 and 28 suitably secured thereto. Straps 25 have an adjustable buckle thereon to adjust the length thereof. Such straps 25 and 26 extend over the shoulder of the wearer as shown in FIG. 1 with the adjustable buckle permitting the adjustment to the wearer's size.
Also mounted on the one side edge 15 of life preserver 10 are a pair of spaced straps 29 and 33 having quick release fastening means 30 and 31 secured to the respective end portions thereof. Strip 29 has an adjustable buckle 32 mounted thereon to facilitate adjusting the length thereof. Straps 29 and 33 are used to buckle in the front of the wearer as a safety belt to assure the wearer of the proper mounting of the life preserver around the chest of the wearer.
Located within the chamber 12 of the life preserver are a pair of spaced closed cell pads or blocks 35 and 36 of foam or elastomeric foam suitably adhered to one inside wall of the envelope of polyurethane material. Such blocks of foam 35 and 36 provide a built-in buoyancy of 4 to 14 pounds, preferably 7 to 10 pounds. Such buoyancy pads or blocks 35 and 36 provide sufficient flotation to the wearer to assure a minimum flotation which together with the inflated envelope can then provide the wearer enough flotation to keep his head completely out of the water assuring the wearer of proper attitude, position and unrestricted breathing without fear of banking water under adverse conditions. The degree or extent of buoyancy can be adjusted on each life preserver by the extent of inflation of the chamber 12.
An open cell foam block 38 is suitably adhered or secured to the polyurethane material to provide a visual leak detection means. Such block 38 can be compressed to one-third its normal size whenever the life preserver 10 is relieved of all its trapped air. In this instance, the foam block 38 is compressed and remains in its compressed condition since the open cell structure is relieved of all air or gases. Should the gas impervious envelope develop a leak, atmosphere air will be taken on or absorbed by the open cell foam and expand to its normal size, which is two-thirds greater than its compressed condition as illustrated by FIGS. 4 and 5. Under these conditions, the wearer is made aware of the defective life preserver and can take immediate steps to correct and replace the life preserver. In the event that such leak occurs while the life preserver is in use, the buoyancy blocks 35 and 36 provide sufficient buoyancy as an emergency flotation device.
There is provided two means for inflating the chamber 12 of the life preserver 10. A mouth valved tube 40 located on the gas impervious envelope of the chest support 11 provides means by which the wearer can inflate the chamber by mouth. Such valved tube 40 is of a size and shape to facilitate its use as the prime means for inflating the life preserver or to help keep up the pressure in the chamber 12 should there be a slow leak.
The second means or inflation assembly 42 for inflating the chamber 12 contains a gas cylinder or capsule 43, mounted on the same side of the chest support 11 as the valved tube 40. The valved tube 40 and the capsule 43 are located closely adjacent to each other to assure easy access to the wearer and full control at one location. The gas capsule or cylinder 43 may be a carbon dioxide cylinder and is connected to a molded activator housing 44 which is connected to a lanyard 45 for actuating the carbon dioxide cylinder to inflate and pressurize chamber 12. Such inflation assembly 42 is illustrated more fully by U.S. Pat. Nos. 3,754,731; 3,809,288 and 4,887,987. Both inflation means are available from the Halkey-Roberts Corporation of Spring Valley Avenue, Paramus, N.J. 07652.
In the use of such life preserver 10, the wearer will wrap the chest support 11 abut his torso or chest using the VELCRO® fastening means 18-19, the safety belt of fastening means 30 and 31 to secure the chest support 11 in place. The straps 25 and 26 are then secured, with the strap 25 passing over the wearer's shoulder as illustrated in FIG. 1. Such strap 25 is then adjusted to firmly secure the chest support in its position on the wearer in cooperation with face-to-face bristle hook and loop type strips 18--18 and 19--19. The chamber 12 is then ready for inflation by either the valved tube 40 or the inflation assembly 42 as described above.
In the deflated condition of chamber 12 of the support 11, the VELCRO® fastening means are engaged as the support is snugly wrapped around the wearer's chest to firmly secure the support thereon so the support 11 does not interfere with the arm movement or general movement of the wearer. The shoulder straps 25 and 26 are used to assure the wearer that the support 11 remains in its adjuted position on the wearer. The straps 29 and 33 are adjusted on the wearer to provide slack or clearance space for the expansion that occurs when chamber 12 is inflated.
Upon inflation of chamber 12 by the wearer, either by mouth valved tube 40 or via gas cylinder 43, the rectangular shaped chest support 11 will enlarge its outer circumference materially and break the bonds between the VELCRO® fastener strips 18--18 and strips 19--19 which in effect renders them inoperative and thence the straps 29 and 33 in cooperation with the support 11 take over to snugly encompass the wearer. Such action places the respective closed cell pads 35 and 36 directly under the arms of a wearer to provide a balanced flotation to the wearer, i.e. keeps the person upright. On such inflation of the chamber 12, the straps 29 and 33 are firmly abutting the chest of the wearer as the inflated support 11 comes into firm contact with the wearer's back and sides to prevent projecting the wearer's head forwardly into the water.
While a certain representative embodiment and details have been shown and described for the purpose of illustrating the invention, it will be apparent to those skilled in the art that various changes and modifications other than those referred to may be made therein without departing from the spirit and scope of the invention.
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An inflatable life preserver that is made from a gas impervious material in a generally rectangular shape with a closed chamber. A valve is connected thereto for inflating the chamber. The life preserver has fasteners to retain the life preserver into an annular shape that encompasses the wearer around the chest as a chest support. Such fasteners include a strap that extends over the shoulder and a safety snaps for the front of the chest with provisions for quickly releasing the fasteners. Positive flotations are provided in the chamber and provide buoyancy to the weaver. Such positive flotations include closed cell pads and an open cell pad wherein the latter in its compressed condition is a leak detector indicator when the life preserver is in a deflated condition.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of the priority of U.S. Provisional Patent Application No. 60/582,513 filed Jun. 25, 2004, the entirety of which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] This invention relates generally to structures produced by techniques of nanotechnology, and methods of producing such structures.
[0004] More specifically, the invention relates to such structures and devices incorporating at least one element, essentially in one-dimensional form, which is of nanometer dimensions in its width or diameter, which is produced with the aid of a catalytic particle, and which is commonly termed a “nanowhisker.”
[0005] The invention relates also to a method of forming a nanowhisker of a certain material on a substrate of a dissimilar material.
[0006] 2. Brief Description of the Prior Art
[0007] Nanotechnology covers various fields, including that of nanoengineering, which may be regarded as the practice of engineering on the nanoscale. This may result in structures ranging in size from small devices of atomic dimensions, to much larger scale structures—for example, on the microscopic scale. Typically, nanostructures are devices having at least two dimensions less than about 1 μm (i.e., nanometer dimensions). Ordinarily, layered structures or stock materials having one or more layers with a thickness less than 1 μm are not considered to be nanostructures. Thus, the term nanostructures includes free-standing or isolated structures that have two dimensions less than about 1 μm, that have functions and utilities different from those of larger structures, and that are typically manufactured by methods different from conventional procedures for preparing somewhat larger, i.e., microscale, structures. Although the exact boundaries of the class of nanostructures are not defined by a particular numerical size limit, the term has come to signify such a class that is readily recognized by those skilled in the art. In many cases, an upper limit of the size of the at least two dimensions that characterize nanostructures is about 500 nm. In some technical contexts, the term “nanostructure” is construed to cover structures having at least two dimensions of about 100 nm or less. In a given context, the skilled practitioner will recognize the range of sizes intended. In this application, the term “nanostructure” is broadly intended to refer to an elongated structure having at least two transverse dimensions less than about 1 μm, as indicated above. In more preferred applications, such dimensions will be less than about 100 nm, more preferably less than about 50 nm, and even more preferably less than about 20 nm.
[0008] Nanostructures include one-dimensional nanoelements, essentially in one-dimensional form, that are of nanometer dimensions in their width or diameter, and that are commonly known as nanowhiskers, nanorods, nanowires, nanotubes, etc.
[0009] The basic process of whisker formation on substrates by the so-called VLS (vapor-liquid-solid) mechanism is well known. A particle of a catalytic material, usually gold, is placed on a substrate and heated in the presence of certain gases to form a melt. A pillar forms under the melt, and the melt rises up on top of the pillar. The result is a whisker of a desired material with the solidified particle melt positioned on top. See Wagner, Whisker Technology , Wiley, New York, 1970, and E. I Givargizov, Current Topics in Materials Science , Vol. 1, pages 79-145, North Holland Publishing Company, 1978. In early applications of this technique, the dimensions of such whiskers were in the micrometer range, but the technique has since also been applied for the formation of nanowhiskers. For example, International Patent Application Publication No. WO 01/84238 (the entirety of which is incorporated herein by reference) discloses in FIGS. 15 and 16 a method of forming nanowhiskers, wherein nanometer sized particles from an aerosol are deposited on a substrate and these particles are used as seeds to create filaments or nanowhiskers.
[0010] Although the growth of nanowhiskers catalyzed by the presence of a catalytic particle at the tip of the growing whisker has conventionally been referred to as the VLS (Vapor-Liquid-Solid process), it has come to be recognized that the catalytic particle may not have to be in the liquid state to function as an effective catalyst for whisker growth. At least some evidence suggests that material for forming the whisker can reach the particle-whisker interface and contribute to the growing whisker even if the catalytic particle is at a temperature below its melting point and presumably in the solid state. Under such conditions, the growth material, e.g., atoms that are added to the tip of the whisker as it grows, may be able to diffuse through a the body of a solid catalytic particle or may even diffuse along the surface of the solid catalytic particle to the growing tip of the whisker at the growing temperature. Persson et al., “Solid-phase diffusion mechanism for GaAs nanowires growth,” Nature Materials, Vol. 3, October 2004, pages 687-681, shows that, for semiconductor compound nanowhiskers there may occur solid-phase diffusion mechanism of a single component (Ga) of a compound (GaAs) through a catalytic particle. Evidently, the overall effect is the same, i.e., elongation of the whisker catalyzed by the catalytic particle, whatever the exact mechanism may be under particular circumstances of temperature, catalytic particle composition, intended composition of the whisker, or other conditions relevant to whisker growth. For purposes of this application, the term “VLS process,” or “VLS mechanism,” or equivalent terminology, is intended to include all such catalyzed procedures wherein nanowhisker growth is catalyzed by a particle, liquid or solid, in contact with the growing tip of the nanowhisker.
[0011] For the purposes of this specification the term “nanowhisker” is intended to mean a one-dimensional nanoelement with a width or diameter (or, generally, a cross-dimension) of nanometer size, the element preferably having been formed by the so-called VLS mechanism, as defined above. Nanowhiskers are also referred to in the art as “nanowires” or, in context, simply as “whiskers” or “wires,”
[0012] Several experimental studies on the growth of nanowhiskers have been made, the most important reported by Hiruma et al. They grew III-V nanowhiskers on III-V substrates in a metal organic chemical vapor deposition (MOCVD) growth system. See Hiruma et al., J. Appl. Phys. 74, page 3162 (1993); Hiruma et al., J. Appl. Phys 77, page 447 (1995); Hiruma et al., IEICE Trans. Electron., E 77C, page 1420 (1994); Hiruma et al., J. Crystal Growth, 163, pages 226-231 (1996).
[0013] More recently, growth of Si nanowires on Si substrates has been demonstrated. See, e.g., Westwater et al., J. Vac. Sci. Technol., B 1997, 15, page 554. Very recently, growth of Ge nanowires on Si substrates was also demonstrated. See Kamins et al., Nano Lett. 2004, 4, pages 503-506, Web published Jan. 23, 2004.
[0014] In the prior art in general, many different approaches have been tried in order to realize perfect epitaxial growth of III-V materials on silicon substrates. The primary motivation for these strong efforts is that, if such a technology could be developed, a very wide spectrum of so called III-V heterostructure devices may be incorporated with main-stream silicon technology, thus opening the way to highly advanced high-speed and opto-electronic devices incorporated with silicon.
[0015] Besides the efforts toward integrating III-V materials on Si, other approaches toward the specific goal of efficient light-emission using Si have been proposed—for example, the formation of porous Si via electrochemical etching (Canham, L. T., Appl. Phys. Lett., 1990, 57, page 1046) and the incorporation of luminescent defects, such as rare-earth impurities (Michel et al, Semiconduct. Semimet., 1998, 49, page 111.
[0016] Epitaxial growth of III-V semiconductors on Si presents a number of difficulties, such as lattice mismatch, differences in crystal structure (III-V's have a polar zinc blende or wurtzite structure whereas Si has a covalent diamond structure), and a large difference in thermal expansion coefficient. Much work has been done on planar growth of layers of III-V materials on Si substrates using different approaches such as buffer layers, growth on patterned Si surfaces, and selected area growth from small openings. See, for example, Kawanami, H., Sol. Energy Mater. Sol. Cells, 2001, 66, page 479.
[0017] A major challenge has been to avoid the formation of antiphase domains related to the initiation of III-V growth on two atomic planes of silicon differing by one atomic layer, which leads to the formation of anti-phase domain walls and defective material. In Ohlsson et al., “Anti-domain-free GaP, grown in atomically flat (001) Si sub-μm-sized openings”, Appl. Phys. Lett., Vol 80, No. 24, 17 Jun. 2002, pages 4546-4548, to address the problem of antiphase domains, GaP nanocrystals were grown on a Si(001) substrate surface through openings in a mask of SiO 2 . The mask openings were defined by e-beam lithography. Etching and chemical stripping followed, and organic residues were removed by oxygen plasma. A high annealing temperature of 1000° C. was used to remove Si oxide and to provide atomic flatness on the silicon surface on which GaP is nucleated. An atomically flat surface is a surface that presents a single crystal facet and does not exhibit atomic steps.
[0018] In prior U.S. patent application Ser. No. 10/613,071, published as No. 2004-0075464, to Samuelson et al., and International Patent Application Publication No. WO-A-04/004927 (both of which publications are incorporated herein by reference), there are disclosed methods of forming nanowhiskers by a chemical beam epitaxy method. Nanowhiskers are disclosed having segments of different materials, with abrupt or sharp heterojunctions therebetween. Structures are disclosed comprising nanowhiskers of, for example, gallium arsenide extending from a silicon substrate. Processes are disclosed for forming epitaxial layers of III-V materials on a silicon substrate, involving initial formation of nanowhiskers on the substrate and using the nanowhiskers as nucleation centers for an epitaxial layer.
[0019] Improvements are desirable in the formation of nanowhiskers of III-V materials (or having at least a base portion of III-V material) on a substrate of Group IV material to ensure that the nanowhiskers are grown in a highly reliable way with accurate predetermined dimensions and structure, and with accurately predetermined physical characteristics for implementing the above structures and processes. More generally, improvements are desirable in the formation of nanowhiskers having at least a base portion of a predetermined material on a substrate of a dissimilar material.
SUMMARY OF THE INVENTION
[0020] One object of the invention is to provide a method for forming, on a substrate of a Group IV material, a nanowhisker having at least a base portion of a III-V semiconductor material.
[0021] A more general object of the invention is to provide a method for forming a nanowhisker, having at least a base portion of a predetermined material, on a substrate of a dissimilar material.
[0022] A further object of the invention is to provide a nanostructure comprising a nanowhisker upstanding form a substrate of a Group IV material and having at least a base portion of a III-V semiconductor material.
[0023] A further object of the invention is to provide a nanostructure including a nanowhisker formed on a substrate of a Group IV material, the nanowhisker having at least a base portion of a III-V semiconductor material and one or more segments of a further material bounded with abrupt or sharp heterojunctions.
[0024] In accordance with a first aspect, the invention provides a method for forming a nanowhisker, having at least a base portion of a first material, on a substrate of a second material, different from said first material, comprising:
[0025] providing a substrate of said second material having a surface that is prepared to remove impurities and to provide at least one atomically flat growth region;
[0026] providing on said growth region at least one catalytic particle;
[0027] introducing into the atmosphere surrounding the substrate, gases for forming the nanowhisker, and heating the substrate to a predetermined growth temperature at which the nanowhisker is grown on said growth region via a said catalytic particle.
[0028] In accordance with a more specific aspect, the invention provides a method for forming a nanowhisker, having at least a base portion of a III-V first semiconductor material on a substrate of a Group IV second material, comprising:
[0029] providing a substrate of said second material having a surface that is prepared to remove impurities and to provide at least one atomically flat growth region;
[0030] providing on said growth region at least one catalytic particle; and
[0031] introducing into the atmosphere surrounding the substrate, gases for forming the nanowhisker, and heating the substrate to a predetermined growth temperature at which the nanowhisker is grown via a said catalytic particle.
[0032] It has been found that an issue in achieving growth of III-V nanowhiskers (i.e., nanowhiskers of which at least the initial growth or base portion is of a III-V material) on a silicon substrate, or other Group IV material, is to provide essentially a perfect surface from which catalytic growth is initiated. In order to provide for the formation of an ideal group III-V (or Group II-VI) semiconductoron the substrate, the interface between the metallic nanoparticle and the substrate has to be of a character that only a single-domain of the crystalline nanowhisker material is formed. This may ideally be obtained by keeping the interface atomically flat over the diameter of the nanowire, or more generally by nucleation conditions that lead to a single nucleus from which the nanowhisker nucleates and grows. Thus, it is desirable to have a totally clean surface that is free from impurity and oxide and that is preferably also atomically flat at the whisker growth site (or at least sufficient that the nanowhisker nucleates and grows from a single nucleus). In this way, growth of the nanowhisker material in bulk form that might occur at imperfections on the substrate surface is inhibited, and factors that promote nanowhisker growth are encouraged, such as migration of nanowhisker material along the surface of the substrate to the catalytic growth particle.
[0033] In practice of the invention, it is desirable to employ one or more cleaning operations to remove organic residue that is commonly found on a substrate surface. It is also desirable to employ steps such as etching to remove existing oxide formations on the substrate surface. In order to prevent further oxide growth on the substrate surface, subsequent to these removal steps, it is desirable to passivate the surface, at least temporarily, such as by HF etching.
[0034] It would in principle be possible to provide a surface with a layer of passivating material such as silicon nitride or silicon dioxide, and to form apertures in the passivating layer (for example, by etching) and to treat the exposed substrate surface in the apertures to achieve the ideal conditions as described above. Catalytic particles would then be formed within respective apertures by a suitable deposition process.
[0035] In a currently preferred embodiment, however, the entire substrate surface is processed towards an ideal condition, followed by deposition on the surface of catalytic particles by an aerosol process. To this end, it is preferred to passivate the surface by means of etching with an acid such as HF. This has the effect that free or dangling bonds on the substrate surface are terminated with hydrogen ions. This prevents further oxide growth on the substrate surface, and maintains ideal surface conditions while aerosol deposition takes place. Aerosol deposition, and any further processing on the substrate surface takes place in accordance with the invention before any significant degradation of the passivation properties of the hydrogen termination. In practice, a time period of about 2 hours may be permissible.
[0036] As regards the catalytic particles, any metal that is commonly used for nanowhisker growth, such as Au, may be used with this invention. In particular applications where it is not desirable to use Au on silicon substrates, because of the tendency for Au to diffuse into the silicon and create deep level defects, other materials such as In or Ga may be used, where the nanowhisker to be formed contains such materials.
[0037] The catalytic particles are preferably provided on the substrate surface in the form of an aerosol deposition, as noted above. This has an advantage that very accurate control may be exerted over the size of the particles (see International Patent Application Publication No. WO 01/84238, the entirety of which is incorporated herein by reference). Alternatively, the catalytic particles may be formed by deposition from a liquid suspension (colloids from a solution), or may be defined by a NIL (nano imprint lithography) process. In yet another alternative method of forming catalytic particles, a thin film of catalytic material may be formed over substrate surface in a manner similar to that disclosed in the above-referenced publications to Hiruma et al. When the substrate is heated in an initial annealing step, the film liquifies and breaks up into catalytic particles, from which nanowhiskers may be grown.
[0038] It has been found that in order to achieve epitaxial nanowhisker growth, it is desirable to anneal the substrate surface prior to nanowhisker growth. Such annealing preferably occurs at a temperature between 600° C. and 650° C. for a silicon surface. Further, it has been found that gases containing elements for nanowhisker growth should not be present in the atmosphere surrounding the substrate during this annealing process. This is in contrast to prior procedures where it is common to expose the substrate during the annealing process to a gas containing Group V elements, such as arsenic or phosphorous.
[0039] VLS growth may occur by the chemical beam epitaxy method or MOCVD (MOVPE) method. In these methods, it is common to employ two sources of gas, one being a organometallic compound containing a metal, such as gallium or indium, that is required to form part of the nanowhisker material, and another gas containing a Group V or VI element, such as phosphine or arsine, that is desired to react with said metal to produce the compound of the nanowhisker.
[0040] In MOCVD techniques, it is common to introduce the gases together for growth. In addition, it is common to have the phosphine, arsine or similar hydride gas, introduced during the annealing step. However, in contrast to this, it has been found in accordance with the present invention that such gas should not be introduced during the annealing step.
[0041] With the above measures, it has been found that very accurately determined nanowhiskers having precise dimensions and physical characteristics can be formed on substrates of dissimilar material. In particular, materials of a III-V semiconductor material, such as indium phosphide, gallium arsenide, gallium phosphide etc., may be formed on Group IV material substrates such as silicon. Silicon substrates are especially preferred in practice of the invention, in that such substrates are inexpensive and commonly used in industry, as opposed to substrates of III-V materials that are much more expensive. Any surface of the silicon or other substrate material may, in principle, be used for whisker growth in practice of the invention, e.g. (001), (111).
[0042] It has been found that the crystalline perfection of nanowhiskers grown in accordance with the invention is such that, at the base of the nanowhisker at its junction with the substrate, crystal planes are epitaxially formed within the nanowhisker one upon the other, to form a transition of crystal material where the crystalline orientation of the substrate surface is preserved in the epitaxially grown layers of the whisker. That is to say, there is not an indistinct region of amorphous material and crystal segments at the base, between the substrate and the aligned crystal planes of the nanowhisker. Defects or dislocations may exist at the base, e.g. stacking faults, but these are not such as to disturb the essential crystallinity and the crystal directions of the substrate surface that are transferred to the epitaxial growth of the whisker. The problems of lattice mismatch are largely accommodated by radial expansion of the diameter of the base of the nanowhisker.
[0043] Accordingly, in yet another aspect, the invention provides a nanostructure comprising a nanowhisker upstanding from a substrate of silicon and having at least a base portion formed of a III-V material, wherein at a junction of the base portion with the substrate, crystal planes are epitaxially formed within the nanowhisker one upon the other, and crystallographic directions of the substrate surface are transferred to the epitaxially formed crystal planes of the nanowhisker.
[0044] It will be appreciated that with the present invention, structures and processes that have been previously proposed and demonstrated (for example, in the aforementioned U.S. patent application Ser. No. 10/613,071, published as No. 2004-0075464, and International Patent Application Publication No. WO-A-04/004927) may be more accurately and reliably implemented. In particular, the processes disclosed for forming epitaxial layers on silicon substrates may be implemented with a reduced risk of non-epitaxial growth.
[0045] The present invention is in principle applicable to any of the materials that may be used in the manufacture of nanowhiskers and substrates therefor. Such materials are commonly semiconductors formed of Group II through Group VI elements. Such elements include, without limitation, the following:
[0046] Group II: Be, Mg, Ca; Zn, Cd, Hg;
[0047] Group III: B, Al, Ga, In, Tl;
[0048] Group IV: C, Si, Ge, Sn, Pb;
[0049] Group V: N, P, As, Sb;
[0050] Group VI; 0, S, Se, Te.
[0051] Semiconductor compounds are commonly formed of two elements to make III-V compounds or II-VI compounds. However, ternary or quaternary compounds are also commonly employed involving, e.g., two elements from Group II or from Group III. Stoichiometric and non-stoichiometric mixtures of elements are commonly employed.
[0052] III-V materials and II-VI materials include, without limitation, the following:
[0053] AlN, GaN, SiC, BP, InN, GaP, AlP, AlAs, GaAs, InP, PbS, PbSe, InAs, ZnSe, ZnTe, CdS, CdSe, AlSb, GaSb, SnTe, InSb, HgTe, CdTe, ZnTe, ZnO.
[0054] In accordance with the invention, a substrate may be selected from one of the above Group IV, III-V or II-VI materials, and the nanowhiskers (or at least the base portions thereof) may be selected from another of the Group IV, III-V or II-VI materials. Thus, the substrate may in principle be of Group IV, Group III-V or Group II-VI material, and the nanowhiskers may similarly be materials within these groups. Other substrates that are commonly used, such as aluminium oxide (sapphire) or silicon carbide, may also be employed in principle. In its most preferred practice, however, the invention is specifically concerned with substrates of silicon or other Group IV materials that are commonly available in the industry, and nanowhisker compounds of III-V material.
[0055] It will be understood that there may have been proposed and demonstrated other methods for producing nanowhiskers of III-V material on Group IV material, particularly those Group IV materials that are easier to work with than silicon. However, it is generally recognized that silicon is the most difficult of the Group IV materials to work with. The present invention achieves successful growth of III-V nanowhiskers on silicon, and may readily be applied to Group IV and other substrate materials generally, without the exercise of inventive ingenuity.
[0056] As one of its principal advantages, the invention demonstrates epitaxial nucleation and growth of III-V semiconductor nanowhiskers on silicon substrates. This addresses the long-time challenge of integrating high performance III-V semiconductors with mainstream silicon technology.
[0057] The present invention additionally permits the formation of light emitting or light detecting devices within nanowhiskers grown in accordance with the principles herein described. In prior U.S. patent application Ser. No. 10/613,071, published as No. 2004-0075464, to Samuelson et al., and International Patent Application Publication No. WO-A-04/004927, there are disclosed various light emitting and light detecting devices incorporated within a nanowhisker. For example, a p-n junction may be formed by doping two adjacent segments of the nanowhisker with oppositely charged dopant ions. This may be used as a light emitting diode, or as a photodetector. A heterojunction between two segments of different material within a nanowhisker may provide similar functions to a p-n junction. A segment of an optically active material forming heterojunctions with adjacent portions of the nanowhisker may form laser devices, resonant tunneling diodes, heterobipolar transistors, and other electronic and photonic devices. Further there is disclosed a method of forming heterojunctions within a nanowhisker, which are accurately formed and may extend over a width of between one and eight atomic layers of the nanowhisker crystal. Such heterojunctions may be atomically abrupt, extending over as few as one or two atomic layers. As stated in the above referenced application U.S. patent application Ser. No. 10/613,071, “sharp heterojunction” means a transition from one material to another material over five or less atomic monolayers. However, for the purpose of the present specification, heterojunctions may extend over five or more than five atomic monolayers, but yet still provide a desired function of quantum confinement and defining a quantum well. Heterojunctions that define a quantum well may, in this specification, be referred to as “sharp.”
[0058] In a further aspect, the invention permits the incorporation of double heterostructure segments in such nanowhiskers, allowing efficient room-temperature generation of light from, e.g., III-V nanowires grown on Si substrates. Advanced heterostructure devices presently realized on very expensive, silicon-incompatible III-V substrates, such as resonant tunneling diodes, superlattice device structures and heterostructure photonic devices for on-chip communication, are, in accordance with the invention, available as complementary device technologies for integration with silicon.
[0059] Thus, in another aspect, the invention is concerned with a nanowhisker having at least a base portion of a III-V semiconductor material, and the nanowhisker being formed on a substrate of a Group IV material and including a segment of a further material disposed along the length of the nanowhisker, wherein accurately formed heterojunctions are provided at the boundaries of the segment with adjacent portions of the nanowhisker.
[0060] It has been found that such heterojunctions may be very precisely and accurately formed with sharp or abrupt junctions extending over only a few atomic lattice planes. The material of the nanowhisker in general is single crystal, single domain, pure epitaxial growth without defect or dislocation. It has been found that the optical characteristics of such nanowhiskers are very high quality, with the luminescence properties remaining constant from very low cryogenic temperatures up to room temperatures, without quenching of the luminescence. This arises, in significant part, because the confining potential of the quantum well formed by the heterojunctions bounding the segment is well defined (at least 200 meV up to 500 meV) and much greater than the thermal energy at room temperature, kT (˜25 meV), so that the thermal movement of free charge carriers does not disturb the energy distributions of the carriers within the quantum well.
[0061] Thus, in a further aspect, the present invention provides a structure, including a nanowhisker formed on a substrate of a Group IV material, the nanowhisker having at least a base portion of a III-V semiconductor material and a segment of a further material disposed along the length of the nanowhisker, wherein accurately formed heterojunctions are provided at the boundaries of the segment with adjacent portions of the nanowhisker such as to create a quantum well bounding the segment, wherein the height of the quantum well is much greater than the thermal energy at room temperature so as to provide a device that is one of a photonics device and an electronics device.
[0062] Further, the luminescence properties of the segment remain essentially constant, with substantially no quenching, from cryogenic temperatures up to room temperature, thereby providing for highly reliable photonics devices. In accordance with the invention, the provision of nanowhiskers containing optically active material on a silicon substrate permits a very effective implementation of optical interconnects on a silicon chip. As processor speeds increase, a limiting factor in silicon chips is speed of transmission of optical pulses along buses formed as conductive lines on the substrate. A means of avoiding this limitation is to provide a data bus in the form of an optical interconnect comprising an optical path including a light emitter and a light receiver positioned on the substrate surface.
BRIEF DESCRIPTION OF THE DRAWINGS
[0063] Preferred embodiments of the invention will now be described with reference to the accompanying drawings.
[0064] FIGS. 1A to 1C show a first embodiment of the invention, comprising growth of GaP nanowhiskers on Si (111). FIG. 1A is a 45° tilt SEM image of GaP nanowires growing vertically from the Si (111) surface in the [111] direction. FIG. 1B shows a top view from the same sample, scale bar 1 μm. FIG. 1C is an HRTEM image of the Si substrate-nanowhisker interface of a nanowhisker of FIG. 1A , scale bar 10 nm. The crystal directions from the Si substrate (lower) are transferred to the nanowhisker (upper).
[0065] FIGS. 2A and 2B show modifications of the first embodiment, specifically SEM images of vertical GaAs ( FIG. 2A ) nanowhiskers and InP ( FIG. 2B ) nanowhiskers grown from and Si (111) substrate, tilt 45°, scale bars 1 μm.
[0066] FIGS. 3A and 3B show a second embodiment of the invention, HAADF STEM images of a light-emitting GaAsP segment incorporated in a GaP nanowire during growth. The segment is approximately 500 nm long corresponding to a growth time of 1 min of a total of 5 min. In FIG. 3A , the location of the segment in the nanowire is seen as a brighter region in the mid section, scale bar 500 nm. FIG. 3B is an XEDS line scan of the GaP nanowire with GaAsP segment showing the sharp nature of the interface, scale bar 200 nm.
[0067] FIGS. 4A to 4C show photoluminescence from the nanowhiskers of FIG. 3 . FIG. 4A shows room-temperature PL from standing wires as-grown on a Si(001) surface as seen from above, scale bar 5 μm. When excited with a 458 nm laser source the wires emit at 725 nm. The luminescence was visible to the naked eye and the image was recorded using a standard digital camera with 15 s integration time. FIG. 4B shows a top view SEM image of the same sample, scale bar 1 μm. Four nanowhiskers grow in the four different <111> directions. The nanowhiskers form an angle of 35.3° with the Si(001) surface as illustrated in the inset. FIG. 4C shows 10 K and room-temperature PL spectra from individual wires scraped off and resting on a SiO 2 surface. The luminescence from the wires remained bright at room temperature, with negligible quenching observed.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0068] The integration of III-V compound semiconductors, which are dominant in applications such as light-emitting diodes and optoelectronics, with mainstream Si technology is a long sought-after goal for the semiconductor industry. If mastered, significant limitations of the otherwise ideal Si material could be compensated: first, the low efficiency in light generation in Si and, second, the lack of a versatile heterostructure technology required for many high-speed electronic and photonic devices.
[0069] The present invention, in an especially preferred mode, provides III-V nanowhiskers (i.e., nanowhiskers of which at least the initial growth or base portion is of a III-V material) grown epitaxially on Si substrates. By the term “epitaxially,” it is meant that the crystallographic directions are transferred from the substrate to the nanowhiskers. GaP has a lattice mismatch of less than 0.4% relative to Si and is therefore a preferred candidate for epitaxial growth on Si among the III-V compounds. The GaP—Si junction has applications in heterojunction bipolar transistors with GaP as large band gap emitter with sharp and ideal interfaces to Si. Successful synthesis is demonstrated of epitaxially oriented GaP nanowhiskers on Si(111) and Si(001) substrates. To demonstrate room temperature light generation on silicon, light emitting GaAsP heterostructure segments were inserted. The present invention provides epitaxial growth of nanowhiskers on Si for more heavily lattice-mismatched compounds such as InP (4.1%) and GaAs (8.1%).
[0070] In a first embodiment, size-selected gold aerosol nanoparticles were used as seeding particles for nanowire growth. Prior to aerosol deposition, the Si substrates were cleaned and organic residues removed. As a final step before deposition, the samples were treated with hydrofluoric acid to create a hydrogen-terminated surface. The samples were then immediately transferred to a controlled nitrogen atmosphere where the aerosol deposition took place. Typically, 40 nm diameter Au aerosol particles at a density of 2 μm −2 were used. After aerosol deposition, the sample was exposed as little as possible to open air since the hydrogen-terminated surface is known to deteriorate with time. The nanowire growth was performed in a low-pressure, 10 kPa, MOVPE system. Samples were annealed at 625° C. in a hydrogen atmosphere for 10 min before growth. The temperature was then ramped down to the growth temperature of typically 475° C. Growth of GaP nanowhiskers was initiated when the precursors, trimethyl gallium and phosphine, were introduced simultaneously into the growth cell. A typical growth time was 4 min. For incorporation, in a second embodiment of the invention, of an optically active GaAsP heterosegment, arsine was switched on at a certain time during growth. The GaAs x P 1-x composition was then controlled by adjusting the arsine-to-phosphine ratio. For growth of InP and GaAs on Si, the procedure was very similar but with different temperatures and precursors as appropriate to those materials.
[0071] Samples were then characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and photoluminescence (PL) spectroscopy. Specifically, FIG. 1A shows a 45° tilt SEM micrograph of GaP nanowhiskers growing vertically from the Si(111) surface in the [111] direction. A thin planar film of GaP on the Si substrate can be seen as a corrugation of the surface between the wires. TEM investigations estimate the film thickness to be about 20 nm, i.e., the uncatalyzed planar growth rate is approximately 10-2 of the nanowire growth rate. The wires were grown using 40 nm seed Au nanoparticles. Top wire diameter is close to 40 nm. FIG. 1B is a top view of the same sample showing the perfection in the vertical alignment. FIG. 1C is a HRTEM image of the Si substrate-GaP nanowhisker interface. The crystal directions from the Si substrate are transferred to the nanowhisker.
[0072] The preferred III-V nanowhisker growth direction in most reported cases in the literature is the [111]B direction, i.e., corresponding to vertical growth from a (111) oriented surface. The Si(111) surface actually has four possible <111> growth directions, one vertical and three forming an angle of 19.5° with the substrate surface, distributed 120° apart azimuthally. Only the vertical [111] direction is observed, which is expected if the gold-silicon interface is flat, as the only facet available for nucleation is then the (111) facet, the other facets simply not being present during nucleation. This is indisputably the case when looking at FIGS. 1A and B and clearly demonstrates the perfect epitaxial nature of the growth. Well-aligned vertically oriented nanowhiskers were reproducibly obtained in a large number (20+) of growth runs.
[0073] To investigate the interface between the Si substrate and the GaP nanowire, samples were prepared for high-resolution transmission electron microscopy (HRTEM) by cleaving polishing, and ion milling the silicon substrate after wire growth ( FIG. 1C ). The transfer of crystallographic information from the Si substrate to the GaP nanowhiskers can clearly be seen, in that the crystal directions of the Si substrate are transferred to the epitaxial layers at the base of the nanowhisker.
[0074] In modifications of the first embodiment, III-V compounds with a large lattice mismatch such as GaAs ( FIG. 2A ) and InP ( FIG. 2B ), with lattice mismatch of 4.1% and 8.1% respectively, are also be grown epitaxially on Si. Specifically, FIGS. 2A and 2B show SEM images of vertical (A) GaAs nanowhiskers and (B) InP nanowhiskers grown on Si(111) substrates. The small wire cross-section enables the wires to accommodate and relax strain from the large lattice misfits of otherwise incompatible materials.
[0075] It was found that passivation (e.g., hydrogen passivation) of the Si surface is particularly advantageous. On samples where the native oxide was not removed prior to aerosol deposition, no epitaxial orientation was observed. It was also noticed that for samples that were kept in a glovebox atmosphere for a longer time (˜3 months), the yield of straight epitaxial wires was lower than from freshly prepared samples. As the reoxidation of the HF-etched surface is moderately slow, this suggests that even a very thin layer of native oxide is detrimental to epitaxial wire growth.
Examples
[0076] Starting material was “Toyo” Epitaxial Silicon Wafers, P type substrate with a P type epilayer orientation (111).
[0000]
Dopant
Resistivity
Thickness
Substrate
Boron
<0.015 Ω cm
245 μm
Layer
Boron
12 Ω cm
27 μm
[0077] Preparation Prior to Growth
[0078] 1) Clean with ultrasonic Tri-clean to remove organic residues and particles.
[0079] The wafer was placed in a test tube and solution a) below was added. The test tube was put in ultrasonic bath at 35 KHz for 2-3 minutes. After, the bath the solution was decanted and the next solution was added. The process repeated for solutions b)-d) in that order.
[0080] a) Trichloroethylene (proanalysi)
[0081] b) Acetone (proanalysi)
[0082] c) Ethanol (95%)
[0083] d) Milli-Q-H 2 O
[0084] The water was decanted and refilled 2-3 times in Milli-Q-H 2 O (18.2 W cm 25° C.). Rinse the wafer.
[0085] 2) The wafer was removed from the rinse water and immediately cleaned with Piranha Etch to remove any remaining organic residues.
[0086] The following were measured and mixed in a separate container:
7 parts sulphuric acid (95-97% proanalysi) 3 parts hydrogen peroxide (30% proanalysi)
[0089] When mixed, an exothermic reaction causes the solution to heat to over 70° C. This mixture was poured over the samples and was stirred occasionally for 6 min.
[0090] The Piranha Etch was decanted and the wafer was rinsed as before 3-4 times.
[0091] 3) The wafer was taken directly from the rinsing water and put in a Hydrofluoric acid (HF) dip to remove silicon dioxide on the surface.
[0092] A 5% HF solution was prepared by measuring and mixed in a separate container:
1 part HF (40% proanalysi) 7 parts in Milli-Q-H2O (18.2 M W cm 25° C.)
[0095] The solution was stirred occasionally for 2 min.
[0096] The wafer was removed from the HF solution and care was taken that there were no visible droplets remaining on the polished side of the wafer. The backside of the wafer was blotted on a filter paper to remove any liquid on the backside of the wafer. It was then transferred directly into an atmospherically controlled glove box (H 2 O and O 2 levels <1 ppm) via a load lock for the aerosol deposition.
[0097] A standard aerosol particle diameter of 40 nm was used with particle surface densities ranging from ˜0.05 to 40 μm −2 .
[0098] After aerosol deposition, the samples were stored up to 2 weeks in an atmospherically controlled glove box until they were transferred in air to the MOVPE glove box chamber for loading and growth.
[0099] The samples were then mounted in the growth chamber of the MOVPE system (low pressure 100 mbar).
[0100] A typical growth run, GaP nanowhiskers:
[0101] 1. Temperature was raised to an annealing temperature of 625° C. and annealed for 10 min under hydrogen atmosphere. Temperature was ramped down linearly during 5 min to growth temperature, 475° C.
[0102] 2. Growth started when the two sources, TMG and phosphine were simultaneously introduced in the growth chamber. The molar fraction source flows were 1.5×10 −2 for phosphine and 1.25×10 −5 for TMG in 6 l/min hydrogen. A typical growth time was 4 minutes.
[0103] 3. Growth stops when the TMG is switched off. The temperature is then lowered and the phosphine is switched off as temperature drops below 300° C.
[0104] Comments to the procedure described above:
The HF-etch creates a hydrogen-terminated surface, i.e., a hydrogen atom is attached to each dangling bond of the Si (111) surface. Other surface preparations such as no cleaning at all, organic clean but no oxide removal, did not produce good wire growth. As a hydrogen terminated surface is oxidized over time, it is preferable to use freshly prepared samples. Samples kept in a glove box atmosphere for ˜3 months produced lower quality wires than freshly prepared samples. Annealing temperature was found to be an important parameter for the wire quality and investigated temperatures in the range 550 to 700° C. A high annealing temperature (700° C.) gave wires with a heavy base and irregular nucleation, resulting in many small wires around the main stem as well as many wires creeping along the surface with no orientation. A low annealing temperature (550° C.), on the other hand, resulted in loss of the epitaxial orientation from the substrate, i.e., the wires were no longer vertically aligned but had a random orientation. At this low temperature, many gold particles also did not nucleate to form wires but remained as dead particles lying on the surface. 625° C. was found to be a suitable compromise between the two extremes above. It was observed that if the phosphine was activated during the annealing step, as is the conventional procedure when growing GaP nanowhiskers on GaP substrates, there was no wire growth.
[0108] FIGS. 1A to 1C show GaP nanowhiskers grown on a silicon substrate. The formation of the nanowhiskers is ideal, with the nanowhiskers exhibiting perfect regularity. In general, the achievement of ideal nanowhiskers is due to the formation of perfect conditions for nanowire growth, including atomically flat surfaces with no impurity or oxide formation that might give rise to bulk growth and that might inhibit factors that promote nanowhisker growth.
[0109] Referring to FIGS. 3A and 3B and 4 A to 4 C, in a second embodiment of this invention, light-emitting segments of GaAs x P 1-x were inserted in GaP wires grown on Si. The composition can be tuned by controlling the arsenic to phosphorus ratio during growth, and the length of the segment is determined by the growth time.
[0110] The method of forming the nanowhiskers was essentially the same as that in Example 1, but conditions are changed during growth to produce the gallium arsenide phosphide heterojunctions. The procedure for changing conditions is described in earlier mentioned U.S. patent application Ser. No. 10/613,071, published as No. 2004-0075464, to Samuelson et al.
[0111] Using Si(001) substrates, the nanowhiskers grew in four different <111> directions ( FIG. 4B ). On the (001) surface orientation, four equivalent <111> directions make an angle of 35.3° with the substrate distributed 90° apart azimuthally. For epitaxial growth, all four directions can be expected since the <111> directions are equivalent.
[0112] FIG. 3A shows a high angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) image of a GaP nanowire with a 500 nm long segment of GaAs x P 1-x . An X-ray energy dispersive spectrometry (XEDS) composition line scan of the segment ( FIG. 3B ) shows that the interfaces are very sharp. From XEDS composition analysis, a composition of ˜30% P and ˜70% As in the segment can be inferred. The phosphorous content of the GaAsP segment measured with XEDS is probably somewhat higher than that of the actual segment core; after growth of the segment, a thin shell of GaP is deposited over the GaAsP core due to lateral growth when the end part of the GaP nanowire is grown.
[0113] The optically active segments were characterized using PL spectroscopy and PL imaging. FIG. 4A shows room temperature luminescence imaging in the deep red spectral region (725 nm) from standing wires, as grown on Si (001). The nanowhiskers were excited using an Ar+ laser, emitting at 458 nm and with an intensity of approximately 3 kW/cm 2 . A sample with a low wire density of ˜0.05 μm −2 was used to make it possible to resolve individual wires. The (001) substrate orientation was chosen to ease the collection of the light since light is mainly emitted in lobes from the segment and the light is collected from above. The elongations of the spots in two perpendicular directions correspond to the projection of the four different <111> directions ( FIG. 4B ). The fact that luminescence of individual nanowhiskers can be imaged at room temperature suggests that the radiative recombination from GaP/GaAsP/GaP double heterostructure segments is not thermally quenched even at room temperature.
[0114] For a detailed PL-spectroscopy study, standing nanowhiskers were scraped off from a (111) substrate and transferred to a grid-patterned SiO 2 surface. The advantage of placing the nanowhiskers on the grid structure is that, after PL spectroscopy, each wire can be located with SEM to confirm that it is a single wire with a well-defined segment. PL spectra from separate nanowhiskers were recorded at 100K and room temperature, demonstrating high uniformity ( FIG. 4C ) in the luminescence from the individual wires. The GaP/GaAsP/GaP nanowhiskers exhibit sharp peaks at about 1.78 eV with a full width half-maximum (fwhm) of about 60 meV at 10° K. The PL remains bright at room temperature with peaks shifted to 1.71 eV and with an average fwhm of about 75 meV, with negligible quenching of the emission. The spectral shift corresponds well with the band-gap shrinkage from 10° K to room temperature. Comparing the PL spectra with data in the literature for bulk GaAsP, a composition of GaAs 0.8 P 0.2 can be inferred, in reasonable agreement with the XEDS composition analysis. By changing the As x P 1-x composition in the segment, it is possible to continuously tune the emitting wavelength from the band gap of GaP to the band gap of GaAs, representing a wavelength span of 550-900 nm, corresponding to the spectral range achieved in GaAsP LED technology for growth on GaP.
[0115] Among its most important advantages, the present invention provides device-quality III-V semiconductor growth on silicon substrates with perfect epitaxial nucleation of oriented III-V nanowhiskers. The present invention additionally demonstrates visible room-temperature luminescence of heterostructure III-V nanowhiskers formed on silicon substrates as bright as at cryogenic temperatures.
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A method for forming a nanowhisker of, e.g., a III-V semiconductor material on a silicon substrate, comprises: preparing a surface of the silicon substrate with measures including passivating the substrate surface by HF etching, so that the substrate surface is essentially atomically flat. Catalytic particles on the substrate surface are deposited from an aerosol; the substrate is annealed; and gases for a MOVPE process are introduced into the atmosphere surrounding the substrate, so that nanowhiskers are grown by the VLS mechanism. In the grown nanowhisker, the crystal directions of the substrate are transferred to the epitaxial crystal planes at the base of the nanowhisker and adjacent the substrate surface. A segment of an optically active material may be formed within the nanowhisker and bounded by heterojunctions so as to create a quantum well wherein the height of the quantum well is much greater than the thermal energy at room temperature, whereby the luminescence properties of the segment remain constant without quenching from cryogenic temperatures up to room temperature.
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RELATED APPLICATIONS
[0001] This application is a continuation of U.S. patent application Ser. No. 10/159,518, filed May 31, 2002, and the aforementioned application is hereby incorporated by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to handheld devices. In particular, the present invention relates to a multi-functional handheld device having moveable segments.
BACKGROUND OF THE INVENTION
[0003] Handheld devices are used for a variety of applications. Such devices include, for example, personal digital assistants (PDAs), cellular phones, digital audio playback devices, and digital cameras. In general, small sizes are desired for handheld devices to enhance mobility.
[0004] With the advancement of technology, the functionality that can be provided by handheld devices has increased dramatically. For example, PDA's may be equipped with MP3 players, or outfitted with external cards that can be used to enable image capturing.
[0005] Even with the functional enhancements to such devices, size is a primary consideration. Often, the size of the handheld device is limited by the various hardware components that are used to operate the various functional features of the handheld device. For example, keyboards on PDAs must at least accommodate a user's fingers, so some portion of the available exterior surface on the handheld device must be of a minimum size to enable a keyboard that is usable. Several mechanisms have been developed to minimize the overall size of the handheld device while promoting additional functionality from the handheld device.
[0006] Sometimes the functionality from two different devices is combined into one unit. But combining devices such as handheld computers with other devices generally leads to a device that is larger than a device having the functionality of only one device. Usually, this is because each type of device has a particular set of hardware features that are exposed on the device. The physical presence of hardware features for each type of device cannot be eliminated when two or more different types of devices are combined.
SUMMARY OF THE INVENTION
[0007] Embodiments of the invention provide for a handheld device having different functional components distributed on a moveable or folding housing that reduces the overall size of the handheld device.
[0008] In an embodiment, a handheld device includes a housing having two or more segments and a plurality of exterior surfaces. The segments of the housing are moveably coupled to one another. A processor is configured to execute a plurality of applications, including a first application associated with a first set of hardware devices, and a second application associated with a second set of hardware devices. The handheld computer is configured to be held by a user so as to orient one of the plurality of exterior surfaces towards a user. The first segment and the second segment can be positioned so that a first exterior surface in the plurality of exterior surfaces can be oriented towards the user so as to favor the use of the first set of hardware devices in conjunction with execution of the first application. The second exterior surface in the plurality of exterior surfaces can be oriented towards the user so as to favor the use of the second set of hardware devices in conjunction with execution of the second application.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] Embodiments of the invention are illustrated by way of example, and not by way of limitation, in the figures of the accompanying drawings. Like reference numerals are intended to refer to similar elements among different figures.
[0010] FIG. 1 is a frontal view of a handheld device 100 having a housing 105 in a fully extended position.
[0011] FIG. 2 is a frontal view of a handheld device in a first contracted position.
[0012] FIG. 3 is a frontal view of a handheld device in a second contracted position.
[0013] FIG. 4 is a side view of a handheld device in one of two possible contracted positions.
[0014] FIGS. 5A-5D illustrate one of the first or second segment pivoting about the other of the first or second segment, under an embodiment of the invention.
[0015] FIG. 6 is an isometric view of a handheld device, under another embodiment of the invention.
[0016] FIG. 7 is an isometric view of a handheld device illustrating components on another exterior surface, under another embodiment of the invention.
[0017] FIG. 8 is an isometric view of a handheld device in a contracted position, under another embodiment of the invention.
[0018] FIG. 9 is a method for operating a multi-functional handheld device, under an embodiment of the invention.
[0019] FIG. 10 is a block diagram of an handheld device for use with an embodiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0020] Embodiments of the invention describe a multi-functional handheld device with moveable segments. In the following description, for the purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the present invention. It will be apparent, however, that the present invention may be practiced without these specific details. In other instances, well-known structures and devices are shown in block diagram form in order to avoid unnecessarily obscuring the present invention.
[0021] A. Overview
[0022] A multi-functional device is provided that can be rotated, or manipulated in its configuration, in order to favor the use of the handheld device for a particular function. In one embodiment, the handheld device combines the functionality of a PDA type device, with the functionality of other digital handheld devices. In addition to use of the handheld device as a PDA, specific examples of functions that can be integrated into the handheld device include one or more of the following functionalities: audio playback device, audio recorder, wireless voice and/or data communication device, digital camera, video recorder, and global positioning system.
[0023] According to an embodiment of the invention, a multi-functional handheld device is provided having a housing separated into a first segment and a second segment. The first segment and the second segment combine to provide the handheld device a plurality of exterior faces. The exterior faces extend substantially a length of one of the first segment or the second segment. A first set of features is provided on the a first exterior face. The first set of features are operable to cause the handheld device to input or output audio. A second set of features are provided on a second one of the exterior faces. The second set of features include at least a display. At least some of the features in the second set of features are operable to select content four output on the display. A third set of features are provided on a third one of the exterior faces. The third set of features are operable to cause the handheld device to capture an image.
[0024] According to embodiments of the invention, housing segments may be connected to one another so that one segment can pivot, rotate, or slide with respect to the other segment.
[0025] Other embodiments may provide different sets of features for functionalities other than playing back audio, selecting display content, and capturing images. For example, features for recording audio, enabling wireless communications (voice or data), and alternate input mechanisms (keyboard, handwriting recognition) may be provided on different exterior surfaces provided by the housing segments. Other examples are provided elsewhere in this application.
[0026] An external face of one of the housing segments is an external region of the handheld device that extends primarily in one direction. The faces may be substantially flat, or slightly arched. The face may correspond to the exterior surface of a panel or other housing component used to form the individual segments.
[0027] A “feature” is any logical component, including hardware, software and firmware, for causing the handheld device to perform functions or operations.
[0028] As used herein, the term “substantially” means 90% or more of a referenced quantity.
[0029] According to another embodiment, a handheld device includes a first housing segment, and a second housing segment moveably connected to the first housing segment. The first housing segment and the second housing segment combine to provide a plurality of exterior surfaces. A plurality of hardware devices are disposed on the exterior surfaces. A processor of the handheld device is configured to execute a plurality of applications, including at least a first application that is associated or designated for use with the first set of hardware devices, and a second application that is associated or designated for use with the second set of hardware devices. The handheld device is configured so as to be held by a user so as to orient one of the plurality of exterior surfaces towards the user. The first housing segment and the second housing segment can be positioned relative to one another so that a first exterior surface can be oriented towards the user so as to favor the use of the first set of hardware devices in conjunction with execution of the first application, and so that a second exterior surface can be oriented towards the user so as to favor the use of the second set of hardware devices in conjunction with execution of the second application.
[0030] Use of the term “favor” is intended to mean that the location and/or orientation of an identified component of the handheld computer makes that component easier to use under normal conditions than another component not similarly situated, assuming that the handheld device is being operated in an ordinary fashion.
[0031] Examples of specific types of applications that can be associated with hardware devices of the handheld device include audio playback applications, audio recording applications, camera applications (such as applications for capturing still images or for video recording), GPS applications, and wireless communication applications. Wireless communication applications may include applications for voice communications, as well as applications for receiving or sending data over wireless networks, such as through BlueTooth or other radio-frequency mediums.
[0032] Several advantages are provided by embodiments of the invention. Among the advantages, a handheld device is provided that is capable of performing various functions, each of which require surface area on the handheld device. The handheld device provides the surface area for such input and output devices, but maintains a relatively small overall dimension for the handheld device.
[0033] B. Configurations for Handheld Computer with Moveable Segments
[0034] FIG. 1-4 illustrate different views of a multi-functional handheld device with moveable housing segments, under an embodiment of the invention. According to an embodiment described, a handheld device 100 includes features for operating the device as a PDA, a music playback device, and a digital camera. Features for operating handheld device 100 as one of these three types of devices are provided on different exterior surfaces of the handheld device.
[0035] FIG. 1 is a frontal view of a handheld device 100 having a housing 105 in a fully extended position. The first segment 110 and second segment 120 are pivotably coupled to one another so that the first segment 110 can be moved between contracted and extended positions. Moving the first segment 110 and second segment 120 facilitates use of different features or hardware components for performing specific functions. In an embodiment such as shown by FIG. 1 , an extended state corresponds to second segment 120 being pivoted about first segment 110 so that first segment 110 and second segment 120 are about coplanar.
[0036] According to one embodiment, first segment 110 includes a first exterior surface 132 , a top end 114 and a bottom end 116 , and a pair of lateral sides 115 . A length l 1 extends between top end 114 and bottom end 116 of first segment 110 . A width w 1 extends between lateral sides 115 of first segment 110 . A first set of hardware devices are disposed so as to be accessible on the first exterior surface 132 .
[0037] The second segment 120 includes a second exterior surface 134 , a top end 124 , and a bottom end 126 . A length l 2 extends between top end 124 and bottom end 126 of second segment 120 . A width w 2 extends between lateral sides 125 of first segment 120 .
[0038] The bottom end 126 of the second segment 120 is pivotably connected to the top end 114 of first segment 110 . A frontal view of first segment 110 and second segment 120 shows that the first exterior surface 132 and second exterior surface may be aligned, or otherwise viewable to a user at the same time. When handheld device 100 is in the extended position, the overall length of the handheld device may range somewhere between l 1 and l 1 +l 2 . For example, handheld device 100 may be fully extendable so that the overall length of the device is l 1 +l 2 .
[0039] In an embodiment, the first set of hardware devices are used to operate handheld device 100 as a PDA. The first set of hardware devices may include a touch-sensitive display 118 , and an alphanumeric input area 119 . The alphanumeric input area 119 may be used to enter input, and to select content that is displayed on display 118 . The display 118 may be contacted to select content appearing on it, and to enter input.
[0040] In the example shown, alphanumeric input area 119 is a handwriting recognition area, such as provided by GRAFFITI in the PALM OS (manufactured by PALM INC.). Other types of alphanumeric input areas include keyboards. Actuation keys (not shown in FIG. 1 ) be may used to launch applications, and to select input or content appearing on display 118 . Examples of applications that may be launched or otherwise operated by a PDA type device include personal information management (PIM) applications, including calendar applications for maintaining appointments, address book applications for maintaining contact information, to-do applications to maintain lists, and memo applications to allow entries of memos. Other applications that may be used by a PDA type device include word processing applications, graphic applications for jotting illustrations, and spreadsheets. A PDA type device is any device that operates such applications, or that is able to receive alphanumeric input.
[0041] In an embodiment, the second set of hardware devices may be used to operate handheld device 100 as a digital camera, or other device that captures images. Accordingly, the second set of hardware devices may include a lens 135 for using handheld device 100 as a digital camera.
[0042] In one embodiment, first segment 110 and second segment 120 may be pivotably connected to one another by a first hinge element 144 and a second hinge element 146 . The first and second hinge elements 144 , 146 may extend from the top end 114 of first segment 110 and bottom end 126 of second segment 120 . The hinge elements 144 , 146 may carry electrical connectivity between first segment 110 and second segment 120 . The hinge elements 144 and 146 enable first segment 110 and second segment 120 to pivot relative to one another between the fully-extended position and one or more contracted positions.
[0043] As will be described, other exterior surfaces of handheld device 100 may carry features or hardware devices for operating other functions of the handheld device. For example, an exterior surface opposing second exterior surface 134 on second segment 120 may carry hardware components for enabling the handheld device 100 to playback audio files.
[0044] FIG. 2 is a frontal view of handheld device 100 in a first contracted position. In the example shown, the first contracted position corresponds to second segment 120 being pivoted so that second exterior surface 134 is outwardly oriented to overlay first exterior surface 132 . In this configuration, the lens 135 is directed in a first direction of intersecting axis Z. The display 118 may be directed in the opposite direction of axis Z (extending orthogonally with respect to the paper).
[0045] In the first contracted position, the overall length of handheld device 100 is reduced to the longer length of the two segments. In the example provided, the two segments are shown to be of equal length, thus the length of the contracted position may be assumed to be l 1 or l 2 . The second exterior surface 134 extends all of, or at least a substantial length of, second segment 120 . The overall width of the device is also the longer of the width of the two segments, which for simplicity is shown to be the same.
[0046] FIG. 3 is a frontal view of handheld device 100 in a second contracted position. In the second contracted position, second segment 120 may be flipped nearly 180 degrees with respect to first segment 110 . In this configuration, a third exterior surface 136 is outwardly oriented to be adjacent to first exterior surface 132 . However, in the second contracted position, third exterior surface 136 and first exterior surface 132 are oriented in the same direction of axis Z (extending orthanormally with respect to the paper).
[0047] A third set of hardware components may be provided on third exterior surface 136 . In an embodiment, the third set of hardware components may be for enabling a user to control playback of audio, recorded in a digital format. Thus, the third set of hardware components may correspond to mechanical and software user-interface features for signaling handheld device 100 to playback audio, volume control, menu and record selection, as well as numerous other examples. In the example provided by FIG. 3 , mechanical buttons 152 may be disposed on third exterior surface 136 along with a display 158 that indicates a status of the media playback. An audio jack (not shown in FIG. 3 ) may also be disposed on third exterior surface 136 .
[0048] FIG. 4 is a side view handheld device 100 in one of two possible contracted positions, under an embodiment of the invention. In either contracted position, one of the exterior surfaces of first segment 110 is adjacent to one of the exterior surfaces of second segment 120 . For example, second exterior surface 134 may be adjacent to first exterior surface 132 . The term adjacent in this context means that two proximate exterior surfaces are in contact, or close to it, so that the two exterior surfaces are about parallel.
[0049] FIG. 4 illustrates a hinge 145 that pivotably connects the first segment 110 to second segment 120 . The hinge 145 may be formed by hinge members 144 , 146 extending along one lateral side between the top 114 of first segment 110 and the bottom end 126 of second segment 120 (see FIG. 1 ). The hinge 145 allows for the first segment 110 and second segment 120 to be moveably connected so as to allow a pivoting or rotating motion of one of the segments about the other segment.
[0050] With embodiments described by FIGS. 1-4 , some or all of the hardware components and features described on each of the exterior surfaces 132 , 134 , 136 may be located on other surfaces. For example, side panels or external surfaces between second and third exterior surface 134 and 136 may be used to carry an audio jack.
[0051] C. Movement of Segments
[0052] FIGS. 5A-5D illustrate one of the first or second segments 110 , 120 pivoting about the other of the segments, under an embodiment of the invention. For purpose of description, first segment 110 is assumed to be on the bottom, and second segment 120 is assumed to be on top and rotating about first segment 110 .
[0053] FIG. 5A is a side view illustrating the first contracted position for handheld device 100 . In the first contracted position, third exterior surface 136 is oriented towards a first direction of axis Z, and a fourth exterior surface 138 is oriented towards a second direction of axis Z. In FIG. 5A , handheld device 100 is oriented so that user, indicated by reference point A, favors use of third exterior surface 136 . The hardware components and features of third exterior surface 136 may be favored because the third exterior surface 136 is oriented towards the user at reference point A, and also because the third exterior surface is proximate to reference point A.
[0054] In the example shown for the first contracted position, first exterior surface 132 and the second exterior surface 134 are positioned adjacent to one another. In the implementation shown, fourth exterior surface 138 may include openings or attachment mechanisms for enabling the mechanical attachment of an external device to handheld device 100 . Alternatively, fourth exterior surface 138 may include another set of hardware devices, which may be used for other functions of handheld device 100 .
[0055] In one embodiment, the configuration shown in FIG. 5A may correspond to handheld device 100 being used as a music playback device. The hardware components of the media playback device are provided on the third surface 136 . The other components of handheld device 100 are folded onto one another so as to not interfere with the user's operation of the media playback device.
[0056] FIG. 5B is a side view illustrating a partially extended position for handheld device 100 . The second segment 120 may be pivoted about first segment 110 so as to separate first exterior surface 132 and second exterior surface 134 . In this position, hardware components and features of both first exterior surface 132 and second exterior surface are accessible to the user in the direction of reference point A. The hardware components and features of third exterior surface 136 are not readily accessible to the user from reference point A.
[0057] A configuration such as shown by FIG. 5B may favor use of handheld device 100 as either a PDA type device or an image capturing device. For example, a wireless video conferencing application may be provided for the handheld device 100 as the configuration for the device may include hardware for capturing an image on second exterior surface 134 , and hardware for displaying an image on first exterior surface 132 .
[0058] FIG. 5C is a side view illustrating a partially contracted position for handheld device 100 . In this position, first exterior surface 132 is primarily accessible to the user at reference point A. The third exterior surface 136 is the least accessible.
[0059] FIG. 5D is a side view illustrating a second contracted position for handheld device 100 . In this position, first exterior surface 132 is favored because it is oriented towards reference point A, along axis Z. Second exterior surface 134 is oriented substantially in the opposite direction along the axis Z. The third and fourth exterior surfaces 136 and 138 are interior and adjacent to one another.
[0060] This configuration may correspond to a tri-pod position for handheld device 100 . In the tri-pod position, the first exterior surface 132 and second exterior surface 134 are available. The first segment 110 and second segment 120 can support the handheld device 100 in an upright position. This may have particular use for image capturing functionality, where second exterior surface 134 provides lens 135 .
[0061] D. Alternative Construction
[0062] FIGS. 6-8 illustrate alternative constructions for a handheld device. In addition, a handheld device such as shown by FIGS. 6-8 may include components and features for different functions.
[0063] FIG. 6 is an isometric view of a handheld device 200 in an extended position. A first segment 210 is pivotably connected to a second segment 220 by a hinge body 250 . A top end 214 of first segment 210 is connected to hinge body 250 to enable the first segment to pivot about the hinge body. A bottom end 225 of second segment 220 is connected to hinge body 250 to enable the second segment to pivot about the hinge body. A flex circuit 255 (not shown) extends electrical connectivity between components of first segment 210 and components of second segment 220 .
[0064] According to an embodiment such as shown by FIG. 6 , a first exterior surface on first segment 210 includes a screen 205 . A second exterior surface 234 on second segment 220 includes a lens 235 , to be used with image capturing logic internal to handheld device 200 . The screen 205 may output images captured using lens 235 and the internal image capturing logic. For example, lens 235 and screen 205 may be positioned so that a user at reference point B can use handheld device 200 for mobile video conferencing.
[0065] FIG. 7 is an isometric view of a third exterior surface 236 on the second segment 220 of handheld device 200 . The third exterior surface 236 may include hardware components and features for audio playback of digitally recorded sounds, such files recorded in the MP3 format. The components on third exterior surface 236 include buttons 244 and a screen 246 to indicate a playback status. An audio jack 237 may be incorporated into one of the surfaces extending between the second and third exterior surfaces 234 and 236 .
[0066] FIG. 8 is a side isometric view of handheld device 200 in another contracted position with lens 235 facing outward on exterior surface 234 . The screen 205 on first exterior surface 232 may face the other direction.
[0067] Several other mechanisms may be used to enable a housing construction where moveably connected housing segments are used to provide exterior surfaces where components and surface features may be disposed. For example, U.S. application ser. No. 09/932,213, entitled HANDHELD COMPUTER HAVING MOVEABLE SEGMENTS THAT CAN BE ADJUSTED TO AFFECT A SIZE OF THE HANDHELD COMPUTER, filed Aug. 17, 2001, and naming William Webb et al. as inventors, hereby incorporated by reference in its entirety, illustrates another way in which a handheld computer may be constructed to have moveable housing segments. Another exemplary housing construction having moveable segments for use with embodiments of the invention is disclosed in U.S. patent application Ser. No. 10/006,537, entitled INTEGRATED HANDHELD DATA PROCESSING DEVICE HAVING A SLIDING FORM FACTOR, filed Nov. 30, 2001, and naming Huy Nguyen and Lawrence Lam as inventors, the aforementioned patent application being hereby incorporated by reference in its entirety.
[0068] E. Method for Operating Handheld Device
[0069] FIG. 9 is a method for operating a multi-functional handheld device, under an embodiment of the invention. According to an embodiment, one or more applications may be launched on a handheld device in response to a processor of the handheld device detecting a relative position of the first segment 110 ( FIG. 1 ) and second segment 120 ( FIG. 1 ). Reference to numerals in other figures is intended to show exemplary components for practicing an embodiment of the invention.
[0070] In step 310 , a relative position of first segment 110 and second segment 120 is detected. A sensor or other similar device that can obtain relative position information between first segment 110 and second segment 120 . As an alternative, changes in the relative position of the first segment 110 and second segment 120 may detected, rather than the actual positions of the two segments.
[0071] In step 320 , an application previously associated with the detected relative position of the first segment 110 and second segment 120 is identified. The application may, for example, be one for operating handheld device 100 as a music playback device, as a digital camera, or as a video conferencing device.
[0072] In step 330 , the identified application is executed automatically. Thus, for example, when the relative position of first segment 110 and second segment 120 corresponds to that shown in FIG. 5A , an audio playback application may be executed by the processor of handheld device 100 . As another example, when the relative position of first segment 110 and second segment 120 corresponds to that shown in FIG. 5B , a video conferencing application may be executed by the processor of handheld device 100 .
[0073] F. Hardware Diagram
[0074] FIG. 10 is a block diagram of a handheld device 400 for use with an embodiment of the invention. The handheld device 400 may be separated into a first portion 410 and a second portion 440 , corresponding to first segment 110 and second segment 120 in FIGS. 1-4 . Each portion may be electrically connected through a connector, such as a flex circuit 450 .
[0075] In an embodiment, handheld computer includes a processor 440 coupled to a first memory 444 (non-volatile) and a second memory 446 (volatile). The processor 440 is coupled to a display driver 422 . The processor 440 combines with display driver 422 to process and signal data for presentation on a display assembly 420 . The display assembly 420 includes screen and digitizer. A set of buttons 425 or other actuation mechanisms may be connected to signal interrupts or other actuation signals to processor 440 .
[0076] An analog-digital (AD) converter 432 is coupled to processor 440 . One or more channels from A/D converter 432 maybe used to convert analog input provided by the digitizer, or by another analog input mechanism.
[0077] The processor 440 may be electrically connected to one or more set of components on second portion 420 via flex connector 450 . In an example shown, a set of camera components 460 and a set of playback components 470 may be connected to processor 440 . The set of camera components 460 may include, for example, a lens, light-detecting sensors, and circuitry to send signals corresponding light being detected. The set of playback components 470 may include, for example, speakers.
[0078] The hardware devices designed to appear on the surface of handheld device 400 may be provided on separate external surfaces formed by the different housing segments of the handheld device 100 . For example, in one embodiment, a lens from the set of camera components 460 may be provided on one exterior surface; buttons, speakers and other user-interface features from the media playback component 470 may be provided on another exterior surface; and the display 420 and buttons 425 may be provided on still another exterior surface.
[0079] G. Conclusion
[0080] In the foregoing specification, the invention has been described with reference to specific embodiments thereof. It will, however, be evident that various modifications and changes may be made thereto without departing from the broader spirit and scope of the invention. The specification and drawings are, accordingly, to be regarded in an illustrative rather than a restrictive sense.
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A handheld computer is provided that includes a first module combined with one or more modules. The first module includes a housing having one or more coupling surfaces, with each coupling surface including a coupling mechanism. A second module is coupleable to the first module. The second module includes a third coupling surface having a second coupling mechanism for mating with the first coupling mechanism. The third coupling surface is positioned on the second module so as to abut at least partially against the second coupling surface when the first coupling mechanism is mated with the second coupling mechanism.
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TECHNICAL FIELD
[0001] The present invention relates to a cell growth media and its composition; and also methods of producing cell culture growth media.
BACKGROUND
[0002] DNA transfection methods of mammalian cells often result in massive cell death. In a transfection most cells die prior to stable DNA integration of incoming plasmid DNA into the host genome.
[0003] A large proportion of the transfected cells undergo apoptosis and although some may have successfully integrated incoming DNA, they are destined to die via a programmed cell death response by the host. Those cells surviving stable integration of DNA and who manage to avoid apoptosis are cultured in media containing the appropriate selection for 1-2 weeks to allow them to expand into a population or pool of cells that have stably integrated foreign DNA in their genome. The stable pool has low genetic heterogeneity with respect to the incoming DNA. This is due to the expansion of only a few clones that actually survived transfection, DNA integration and selection.
[0004] A major cause of cell death in cultures is the lack of ingredients within the cell media to promote strong and robust cell growth. Additionally sonic strains of eukaryotic cells are relatively weak or not robust enough to allow for commercial products to he developed from these strains. An improved cell culture media may improve robustness, cell viability and survivability of less robust strains of eukaryotic cells.
[0005] Additionally, many cell culture media include human or animal serum, which is not preferred from a contamination risk.
[0006] It is an object of the present invention to address or meliorate one or more of the abovementioned disadvantages [background art list].
[0007] Any discussion of the prior art throughout the specification should in no way be considered as an admission that such prior art is widely known or forms part of common general knowledge in the field.
SUMMARY
Problems to be Solved
[0008] [insert discussion of background art]
[0009] It is an object of the present invention to overcome or ameliorate at one of the disadvantages of the prior art, or to provide a useful alternative.
Means for Solving the Problem
[0010] A first aspect of the present invention provides for a serum free cell culture media, wherein the media is adapted to be conditioned by culturing a first set of eukaryotic cells in the media wherein the first set of eukaryotic cells use an expression vector to excrete levels of desired complex proteins into the media; and wherein the media is adapted to grow a set of eukaryotic cells.
[0011] Preferably, the second set of eukaryotic cells is Chinese Hamster Ovary Cells (CHO) cells. More preferably, the CHO cells are selected from the following group or strains: CHO-K1, CHO-DG44 DHFR- and CHO-S.
[0012] Preferably, the desired complex proteins are selected from the following group: human Growth Hormone (hGH), Growth Hormone-like growth factors, insulin-like growth factors, insulin, modified insulins, cytokines, mitogenic proteases and mixtures thereof.
[0013] Preferably, the media may comprise additional supplements to promote the growth of the second set of eukaryotic cells.
[0014] Preferably, the first set of eukaryotic cells is NeuCHO cells; and may be as deposited with the Cell Bank Australia located at 214 Hawkesbury Rd, Westmead, NSW, 2145, Australia and assigned deposit no. CBA20130024, or a subculture thereof.
[0015] The preferred media is used to promote transfection of the second set of eukaryotic cells.
[0016] A second aspect of the present invention provides for a cell culture media that includes a layer to feed a set of cells to be cultured, wherein the layer comprises CHO cells including an expression vector that promotes the secretion of human growth hormone (hGH) and wherein the layer secretes hGH into the media.
[0017] Preferably, said layer is formed by CHO cells seeded in single wells of microtitre plates prior to single cell cloning of a stable transfected pool.
[0018] A third aspect of the present invention provides for a method of producing a serum free cell culture media wherein the media is conditioned by culturing a first set of eukaryotic cells in the media wherein the first set of eukaryotic cells use an expression vector to excrete levels of desired complex proteins into the media; and wherein the media is adapted to grow a set of eukaryotic cells.
[0019] The second set of eukaryotic cells may be preferably CHO cells. These CHO cells tray be selected from the following group or strains: CHO-K1, CHO-DG44 DHFR- and CHO-S.
[0020] Preferably, the desired complex proteins is selected from the following group: human Growth Hormone (hGH), Growth Hormone-like growth factors, insulin-like growth factors, insulin, modified insulins, cytokines, mitogenic proteases and mixtures thereof.
[0021] Preferably, the media may comprise additional supplements to promote the growth of the second set of eukaryotic cells. The preferred first set of eukaryotic cells is NeuCHO cells, NeuCHO cells, may be as deposited with the Cell Rank Australia located at 214 Hawkesbury Rd, Westmead, NSW, 2145, Australia and assigned deposit no. CBA20130024, or a subculture thereof.
[0022] The preferred media is used or is suitable for use to promote transfection of the second set of eukaryotic cells.
[0023] In the context of the present invention, the words “comprise”, “comprising” and the like are to be construed in their inclusive, as opposed to their exclusive, sense, that is in the sense of “including, but not limited to”.
[0024] The invention is to be interpreted with reference to the at least one of the technical problems described or affiliated with the background art. The present aims to solve or ameliorate at least one of the technical problems and this may result in one or more advantageous effects as defined by this specification and described in detail with reference to the preferred embodiments of the present invention.
BRIEF DESCRIPTION OF THE FIGURES
[0025] Embodiments of the present invention will now be described with reference to the drawings in which:
[0026] FIG. 1 is a graph depicting viable cell density plotted against time of various cell cultures; and
[0027] FIG. 2 is a set of two graphs depicting an increasing hit rate of finding a high producer clone cell line wherein various proteins are plotted against protein concentration.
DESCRIPTION OF THE INVENTION
[0028] The most preferred embodiment of the present invention is cell culture media produced by use of modified CHO cells to secrete growth factors in the cell media to improve the potential growth characteristics of the conditioned cell culture media.
[0029] Preferably, the first embodiment of the present invention uses NeuCHO cell which are modified CHO DG44 cells that include an expression vector to secrete human growth hormone (hGH) into the cell culture media that they are used to condition.
[0030] The NeuCho cell line, deposited under the provisions of the Budapest Treaty with the Cell Bank Australia located at 214 Hawkesbury Rd, Westmead, NSW, 2145, Australia as of 4 Feb. 2013 and assigned accession no. CBA20130024, as is particularly suitable for use in pharmaceutical manufacture as described within the present application.
[0031] The advantage of using NeuCHO cells is that hGH is excreted into the cell culture media where it can be utilised by other microorganisms which are typically difficult to grow or lack suitable cell viability for in vitro growth.
[0032] One embodiment of the present invention describes the use of conditioned media from NeuCHO cell cultures to improve the efficiency of transfection in mammalian cells. NeuCHO cells secrete human-growth hormone (hGH).
[0033] Transfection efficiency is defined here as the number of cells surviving transfection, DNA integration and selection before the individual cells are allowed to expand to form a stable pool. Transfection efficiency is improved with the addition of conditioned media from NeuCHO cell cultures. The use of NeuCHO conditioned media maximizes the number of high producing clones that can be isolated from a stable transfected cell population. The method results in a population of cells with greater genetic heterogeneity which significantly increases the likelihood of identifying high expressing clones more quickly and with more certainty than conventional methods. This embodiment simplifies cell line development by enabling rapid identification, selection, isolation and collection of high-value clones. It improves cell line productivity, shortens timelines and reduces cost.
[0034] in a further embodiment of the present invention the NeuCHO cells may be utilised as feeder cell layer for improving efficiency of single cell cloning.
[0035] Single cell cloning methods are generally inefficient but may be greatly improved by the use of conditioned cell culture media as described within the present invention or embodiment. The expansion from a single cell to a culture can be improved through the use of NeuCHO cells and/conditioned media from NeuCHO cells.
[0036] In another embodiment of the present invention relates to the use of NeuCHO as feeder cells to facilitate the growth and expansion of high clones. The use of NeuCHO feeder cells increases the survival rate and number of clones that can be isolated in a single cloning procedure.
[0037] This invention relates to methods of Transient Gene Expression for the production of recombinant bio-pharmaceuticals and other desirable proteins, polypeptides and peptides using mammalian cell cultures. In particular, the methods of the invention involve the use of specially bioengineered cell culture media which maintains very high Viable Cell Densities during and after Transient Gene Expression. Cells cultured in the mentioned media have the ability to maintain high growth in cheap, reproducible, fully-defined protein-free medium.
[0038] The number of recombinant proteins used for therapeutic applications in recent years has increased dramatically, a market expected to reach approximately $70 billion by 2010 (Walsh 2006). Recombinant antibodies currently represent over 20% of biopharmaceuticals in clinical trials as highlighted by the US Food and Drug Administration (Pavlou and Betsey 2005). However, the production of recombinant proteins is itself expensive and time consuming and the biotechnology industry is already experiencing a shortage of manufacturing capacity (Garber 2001; Dyck, Lacroix et al. 2003). Thus, factors such as scale up, total annual manufacturing capacity, post translational modifications, choice of expression system for the biosynthesis of therapeutic proteins and speed of process set up need to be evaluated in order to make both upstream and downstream production of therapeutic proteins a cost-effective process (Verma, Boleti et al. 1998; Werner, Noe et al. 1998; Fischer, Drossard et al. 1999; Bulleid, John et al. 2000; Morton and Potter 2000).
[0039] The high throughput screening required in the drug discovery process has intensified the need for a rapid technique to produce milligram amounts of recombinant protein. In order to achieve this, transient gene expression technology has attracted much interest over the traditional stable expression technology. The speed of transient gene expression represents its major economic advantage over standard stable cell line development (Durocher, Perret et al. 2002; Meissner, Pick et al. 2001; Girard, Derouazi et al. 2002; Kunaparaju, Liao et al. 2005). However many transfection procedures result in massive cell death of the transfected cell line from a very early stage (within hours), which leads to a concomitant reduction in recombinant protein production. In order to counteract this problem, many cell lines are transfected in the presence of serum containing media. The use of such media however also poses other drawbacks. Front a regulatory perspective, there are concerns regarding the use of animal derived materials and the inherent possibility of introducing adventitious agents to the culture (Sunstrom, Sugiyono et al. 2000). The use of serum is also associated with high costs, batch to batch variability, and product purification difficulties associated with the use of such media (Zang, Trautmann et al. 1995). Alternatively, CHO cells can be cultured in the presence of media containing growth factors which confer protection to the cells during the transfection procedure, thereby allowing the cells to maintain high Viable Cell Densities consequently leading to concomitant increase in the expression of recombinant proteins.
[0040] The embodiments of the present results in increasing recombinant proteins, polypeptides and peptides production by utilizing defined NeuCHO Media capable of maintaining high Viable Cell Densities during Gene Expression in mammalian cells. Host cells are transfected using NeuCHO Media which contains human-growth hormone (hGH) so that mammalian cells transfected in the presence of NeuCHO Media have very high Viable Cell Densities post transfection consequently leading to increased protein production.
[0041] The embodiment may also a method for producing high levels of desired recombinant protein, polypeptide or peptide comprising the step of: culturing a mammalian host cell in NeuCHO Media wherein said media:
[0042] (i) NeuCHO Media may be used in culturing or transfecting any of those commonly used cell lines used in the art of expressing recombinant proteins, polypeptides and peptides. For example, the host cell may be a Chinese Hamster Ovary (CHO) cell line such as CHO-K1, CHO-DG44 DHFR- and CHO-S. These include both adherent and suspension cell lines.
[0043] FIG. 1 is a graph depicting viable cell density plotted against time of various cell cultures. Expression of human growth hormone increases transfection efficiency by increasing survival rate of cultures following transfection. The graph represents the number of viable cells 48 hrs following transfection with plasmids encoding different recombinant proteins. DG44 cells transfected with plasmid encoding human Growth hormone gene, (DG44-hGH), has the highest viable cell density after control (no DNA) post transfection implying that hGH confers protection to DG44 cells from harsh conditions during transfection thereby leading to a higher number of cells surviving transfection. Viable Cell Density is plotted on the Y-axis in cells/mL, and the number of days in culture is plotted on the X-axis. Six line graphs are shown in the figure, namely line graph A (negative control, DG44 cells—Freestyle Reagent only, no DNA, B (DG44 pNAS-hGH or NeuCHO), C (DG44 Rmab), D (DG44-EPO), E (DG44-Imab) and F (DG44 IFN).
[0044] FIG. 2 is a set of two graphs depicting an increasing hit rate of finding a high producer clone cell line wherein various proteins are plotted against protein concentration. NeuCHO conditioned media or NeuCHO cells as feeder layer increases efficiency of single cell cloning. In an embodiment, NeuCHO cells were seeded in single wells of microtitre plates prior to single cell cloning of a stable transfected pool to form a layer in the cell culture media. Secretion of human growth hormone from NeuCHO cells results in an increased survival rate of single cells following Limiting Dilution Cloning.
[0045] Various additional modifications and variations are possible within the scope of the foregoing specification and accompanying drawings without departing from the scope of the invention.
[0046] Although the invention has been described with reference to specific examples, it will be appreciated by those skilled in the art that the invention may be embodied in many other forms, in keeping with the broad principles and the spirit of the invention described herein.
[0047] The present invention and the described preferred embodiments specifically include at least one feature that is industrial applicable.
REFERENCES
[0048] Walsh, G. (2006). “Biopharmaceutical benchmarks 2006.” Nat Biotechnol 24(7): 769-76.
[0049] Pavlou, A. K. and M. J. Belsey (2005). “The therapeutic antibodies market to 2008.” Eur Pharm Biopharm 59(3): 389-96.
[0050] Garber, K. (2001). “Biotech industry faces new bottleneck.” Nat Biotechnol 19(3): 184-5.
[0051] Dyck, M. K., D. Lacroix, et al. (2003). “Making recombinant proteins in animals—different systems, different applications.” Trends Biotechnol 21(9): 394-9.
[0052] Durocher, Y., S. Perret et al. (2002). “High-level and high-throughput recombinant protein production by transient transfection of suspension growing human 293-EBNA1 cells.” Nucleic Acids Res 30(2):E9.
[0053] Girard, P., M. Derouazi et al. (2002). “100-liter transient transfection.” Cytotechnology 38(1-3):15-21.
[0054] Meissner P., H. Pick et al. (2001). “Transient gene expression: Recombinant protein production with suspension-adapted HEK293-EBNA cells.” Biotechnol Bioeng 75(2):197-203.
[0055] Kunaparaju, R., M. Liao et al. (2005). “Epi-CHO, an Episomal Expression System for Recombinant Protein Production in CHO Cells.” Biotechnol Bioeng 91(6):670-677.
[0056] Verma, R., E. Bole (1998). “Antibody engineering: comparison of bacterial, yeast, insect and mammalian expression systems.” J Immunol Methods 216(1-2): 165-81.
[0057] Werner, R. G., W. Noe, et al. (1998). “Appropriate mammalian expression systems for biopharmaceuticals.” Arzneimittelforschung 48(8): 870-80.
[0058] Fischer, R., J, Drossard, et al. (1999). “Towards molecular farming in the moving from diagnostic protein and antibody production in microbes to plants.” Biotechnol Appl Biochem 30 (Pt 2): 101-8.
[0059] Bulleid, N. J., D. C. John, et al. (2000). “Recombinant expression systems for the production of collagen.” Biochem Soc Trans 28(4): 350-3.
[0060] Morton, C. L. and P. M. Potter (2000). “Comparison of Escherichia coli, Saccharomyces cerevisiae, Pichia pastoris, Spodoptera frugiperda, and COS7 cells for recombinant gene expression. Application to a rabbit liver carboxylesterase.” Mol Biotechnol 16(3): 193-202.
[0061] Barnes, D. and G. Sato. (1980) “Methods for growth of cultured cells in serum-free medium.” Anal Biochem 102: 255-270.
[0062] Mendiaz, E., M. Mamounas, et al. (1986). “A defined medium for and the effect of insulin on the growth, amino acid transport, and morphology of Chinese hamster ovary cells, CHO-K1 (CCL61) and the isolation of insulin “independent” mutants.” In Vitro Cell Dev Biol 22: 66-74.
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A serum free cell culture media, wherein the media is adapted to be conditioned by culturing a first set of eukaryotic cells in the media, wherein the first set of eukaryotic cells use an expression vector to excrete levels of desired complex proteins into the media; wherein said desired complex proteins include human Growth Hormone (hGH), Growth Hormone-like growth factors, insulin-like growth factors, insulin, modified insulins, cytokines, mitogenic proteases and mixtures thereof; and wherein the media is adapted to grow a set of eukaryotic cells.
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CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional of U.S. application for patent Ser. No. 14/531,025 filed Nov. 3, 2014, which is a continuation of U.S. application for patent Ser. No. 13/751,549 filed Jan. 28, 2013 which claims priority from French Application for Patent No. 1251151 filed Feb. 8, 2012, which are hereby incorporated by reference to the maximum extent allowable by law.
TECHNICAL FIELD
[0002] The present disclosure relates to the protection of an integrated circuit chip against laser attacks.
BACKGROUND
[0003] In certain secure devices such as payment cards, integrated circuit chips are likely to process and/or store critical data, for example, encryption keys. Such chips may be fraudulently manipulated in order to obtain protected confidential data.
[0004] To intentionally cause disturbances in the circuits of a chip, an attack mode comprises bombarding chip areas with a laser beam while the chip is operating. Due to the presence of interconnection metal tracks on the front surface side of the chip, laser attacks are often carried out on the back side.
[0005] To avoid fraud, chips comprising attack detection devices have been provided. The attack detection device is coupled to a chip protection circuit. When an attack is detected, the protection circuit implements certain measures of protection, modification, or destruction of the critical data. For example, it may be provided, when an attack is detected, to interrupt the power supply of the chip or to cause it to reset, in order to reduce the time during which the attacker can study the chip response to a disturbance.
[0006] Existing detection devices have various disadvantages. They require, for example, creating new structures on chip to enable the detection of a laser attack. Further, they may increase the bulk and/or the complexity of secure devices.
SUMMARY
[0007] An embodiment provides a device for detecting a laser attack in an integrated circuit chip, which overcomes at least some of the disadvantages of the above-described devices.
[0008] Thus, an embodiment provides a device for detecting a laser attack in an integrated circuit chip, formed in the upper P-type portion of a semiconductor substrate incorporating an NPN bipolar transistor having an N-type buried layer, comprising a detector of the variations of the current flowing between the base of said NPN bipolar transistor and the substrate.
[0009] According to an embodiment, the substrate comprises a substrate contact provided to be grounded, and the base contact of the NPN bipolar transistor is connected to a comparator and to a terminal of application of a bias voltage by a resistor.
[0010] According to an embodiment, the collector and the base of the NPN bipolar transistor are interconnected.
[0011] According to an embodiment, the resistor is embodied by a P-channel MOS transistor.
[0012] According to an embodiment, the comparator comprises an inverter.
[0013] According to an embodiment, the inverter comprises an N-channel MOS transistor and a P-channel MOS transistor, the gate width of the N-channel MOS transistor being at least two times smaller than that of the P-channel MOS transistor.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] The foregoing and other features and advantages will be discussed in detail in the following non-limiting description of specific embodiments in connection with the accompanying drawings, wherein:
[0015] FIG. 1 is a cross-section view schematically showing a portion of an integrated circuit chip;
[0016] FIG. 2A is an electric diagram illustrating a device for detecting a laser attack; and
[0017] FIG. 2B illustrates a variation of FIG. 2A .
DETAILED DESCRIPTION
[0018] For clarity, the same elements have been designated with the same reference numerals in the different drawings and, further, as usual in the representation of integrated circuits, FIG. 1 is not drawn to scale.
[0019] FIG. 1 is a cross-sectional view schematically showing a portion of an integrated circuit chip comprising an NPN bipolar transistor having an N-type buried layer 3 . Such a transistor is a component commonly provided in existing integrated circuit structures.
[0020] The NPN transistor is formed in the upper P-type doped portion of a semiconductor substrate 1 . An N-type doped buried layer 3 and a ring-shaped wall 5 , also N-type doped, which extends from the upper surface of the substrate to buried layer 3 , delimit a P-type doped well 7 .
[0021] A heavily-doped N-type region 9 extends at the surface and at the center of P-type well 7 . Regions 11 , more heavily P-type doped than well 7 , extend at the surface of well 7 and surround region 9 . Contact regions 13 , more heavily N-type doped than regions 5 , extend at the surface of regions 5 .
[0022] A vertical NPN transistor with an N-type buried layer, having its emitter formed of region 9 , its base formed of well 7 embedded with base contact region 11 , and its collector formed of buried layer 3 connected by wall 5 to collector contact region 13 , is thus obtained.
[0023] Substrate contact regions 15 , more heavily P-type doped than substrate 1 , extend at the surface of substrate 1 and surround regions 5 . Substrate contact regions 15 are, for example, intended to be grounded.
[0024] To detect a laser attack in an integrated circuit chip of the type illustrated in FIG. 1 , incorporating an NPN bipolar transistor having an N-type buried layer, the present inventors provide a detection device capable of detecting variations of the current flowing between the base of the NPN bipolar transistor and the substrate.
[0025] FIG. 2A is an electric diagram illustrating an example of a device for detecting a laser attack.
[0026] The detection device is based on the use of a parasitic PNP bipolar transistor 21 present in an integrated circuit chip incorporating an NPN bipolar transistor having an N-buried type layer, of the type illustrated in FIG. 1 . The emitter of PNP transistor 21 corresponds to P-type well 7 , that is, to the base of the NPN transistor. The base of PNP transistor 21 corresponds to N-type buried layer 3 , that is, to the collector of the NPN transistor. The collector of PNP transistor 21 corresponds to substrate 1 . Thus, the emitter, base, and collector contacts of PNP transistor 21 approximately correspond to regions 11 , 13 , and 15 .
[0027] Collector contact 15 of PNP transistor 21 is grounded. Base 13 of PNP transistor 21 is floating. A node 22 corresponding to emitter contact 11 of PNP transistor 21 is connected to a bias voltage V dd by a resistor 23 . Resistor 23 may be embodied, as shown, by a transistor assembled as a resistor, for example, having a P channel, or by a current source. Node 22 is also connected to an input of a comparator 24 . In the shown example, comparator 24 is formed of a simple inverter 27 .
[0028] When a laser beam reaches the rear surface of the chip, electron/hole pairs are photogenerated in substrate 1 . The electrons cross N-type buried layer 3 and are attracted by regions 11 connected, via resistor 23 , to positive voltage V dd . This turns on PNP transistor 21 and a current I PNP then flows between emitter contact 11 and collector contact 15 of PNP transistor 21 . The voltage at node 22 switches from V dd to V dd −R*I PNP , R being the value of resistance 23 . The output of comparator 24 then switches from a low level to a high level, which corresponds to a laser attack detection signal. Various measures of protection, modification, or destruction of the confidential data of the chip may then be implemented.
[0029] FIG. 2B illustrates a variation of the device for detecting a laser attack illustrated in FIG. 2A . Base 13 of PNP transistor 21 is connected to emitter 11 of PNP transistor 21 . This enables to decrease the sensitivity of the detection device with respect to that of the detection device illustrated in FIG. 2A .
[0030] As an example of order of magnitude, in the case where resistor 23 is embodied by a P-channel MOS transistor, the gate length and width of the MOS transistor, for example, respectively range between 3 and 5 μm and between 2 and 4 μm, for example, respectively, being on the order of 4 μm and 3 μm. This corresponds to a current I PNP of approximately 10 μA.
[0031] In the case where comparator 24 is embodied by a simple inverter 27 , the gate width of the N-channel MOS transistor of inverter 27 is selected to be small as compared with the gate width of the P-channel MOS transistor of this inverter, to avoid that a laser attack directly affects the transistors. For example, the gate width of the N-channel MOS transistor of the inverter is at least two times smaller than the gate width of the P-channel MOS transistor.
[0032] The surface of an NPN transistor of the type illustrated in FIG. 1 , for example, ranges between 2 and 25 μm 2 , for example, being on the order of 4 μm 2 .
[0033] Tests have shown that, in the case where a laser attack is performed with a beam having a diameter of approximately 5 μm, a detection device using such NPN transistors having an N-type buried layer enables to detect this attack over a radius for example ranging between 300 and 500 μm around the impact point of the beam on the rear surface of the chip, for example, over a radius on the order of 400 μm around the impact point of the beam.
[0034] An integrated circuit chip used for the processing or the storage of critical data for example has a surface area ranging between 2 and 3 mm 2 . To be able to detect a laser attack whatever its impact point on the chip, the present inventors provide integrating several NPN transistors having an N-type buried layer of the above-described type in the chip. An array of 20 NPN transistors having N-type buried layers, distributed in rows and in columns and spaced apart by a distance between 150 and 250 μm, for example, on the order of 200 μm, is, for example, formed.
[0035] An advantage of a laser attack detection device of the type described in relation with FIGS. 1, 2A, and 2B is that it can be formed by only using components commonly provided in integrated circuit chips used for the processing or the storage of critical data.
[0036] Another advantage of such a detection device is that it enables local detection of a laser attack.
[0037] Another advantage of such a detection device is that the surface area of the integrated circuit chip is almost unchanged with respect to that of a similar integrated circuit chip incorporating no laser attack detection device.
[0038] Another advantage is that the static power consumption of such a laser attack detection device is almost non-existent.
[0039] Specific embodiments have been described. Various alterations, modifications, and improvements will readily occur to those skilled in the art. In particular, instead of associating a comparator with each N-type buried layer NPN transistor, a single comparator may be used for a set of NPN transistors, if the laser attack is not desired to be accurately located.
[0040] Such alterations, modifications, and improvements are intended to be part of this disclosure, and are intended to be within the spirit and the scope of the present invention. Accordingly, the foregoing description is by way of example only and is not intended to be limiting. The present invention is limited only as defined in the following claims and the equivalents thereto.
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A device for detecting a laser attack made on an integrated circuit chip comprises a bipolar transistor of a first type formed in a semiconductor substrate, that bipolar transistor comprising a parasitic bipolar transistor of a second type. A buried region, forming the base of the parasitic bipolar transistor, operates as a detector of the variations in current flowing caused by impingement of laser light on the substrate.
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