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BACKGROUND OF THE INVENTION [0001] 1. Technical Field [0002] The present invention relates to a wind turbine generator, more specifically, a wind turbine generator that includes a support column and a rotor with multiple canvas blades attached to the support column, the support column detachably fixed to an inner part of a circular ring and provided with tapered end portions, and that can be rotated by even weak wind force and can also be rotated continuously by inertial force after the rotation. [0003] 2. Background Art [0004] In conventional wind power generation, propeller wind turbines and Darrieus wind turbines are the mainstreams of the horizontal axis wind turbines and the vertical axis wind turbines, respectively. However, it is said that these types of wind turbines can only deliver their performance with a wind speed of 10 m/s or faster. [0005] Especially in wind power generation using propeller wind turbines, it has been inevitable that the entire wind turbine results in being large in size due to the following reason. A small wind turbine of this type rotates at 40 to 100 rpm. However, to use such a small wind turbine as a commercial wind turbine, the rated speed needs to be 900 to 1,750 rpm. Accordingly, the wind turbine has to be equipped with a speed-increasing gear that is used to increase the rated speed 20 to 60 times. [0006] In addition, a disc or a brake is used for the control in strong winds to force the wind turbine to stop rotating, and this in turn causes an increase in price of the entire wind turbine. To improve these situations, a small and inexpensive wind turbine that is capable of increasing the rated speed by using a gear even when the wind force is weak has been developed (Japanese Patent Application Publication No. 2005-320865). [0007] In contrast, Savonius wind turbines, paddle wind turbines and rotating-blade wind turbines are examples of wind turbines capable of generating power by weak winds. Such wind turbines are drag type wind turbines, and operate efficiently when the tip speed ratio (the peripheral speed of rotor/wind speed) is small while having a disadvantage of decreasing in operating performance when the tip speed ratio is large. [0008] As a wind turbine for addressing these disadvantages, Japanese Patent Application Publication No. 2004-353637 discloses a “rotating-blade vertical axis wind turbine.” This rotating-blade wind turbine “includes canvas blades in a vertically-long shape, satisfying width:length=1:3 or larger, and each having a width 1.2 times or more longer than the length of the canvas blade frame to form a sag, and puts the power generator into operation by receiving wind force with lift force+drag force, causing sails having a high wind-receiving efficiency to rotate, and then causing a pinion for the power generator to rotate by the working of a rotation transmission gear.” [0009] Japanese Patent Application Publication No. 2005-9415 discloses a “mechanism for automatically adjusting rotations of wind turbine.” In this mechanism, “canvas blades made of flexible and strong canvas are provided, yard members are attached respectively to the front ends and the back ends of the canvas blades, the front yard members are attached to a doughnut-shaped front hub member, the back yard members are attached to a doughnut-shaped back hub member to form a radial pattern, a rotation shaft is inserted into the hub members so as to protrude from the hub members, speed control balancers are attached to the back hub member with the rotation shaft interposed between the speed control balancers, connecting rods parallel with the rotation shaft are connected to a slide cylinder integrated with the front hub member, a spring bearing is provided to the front end of the rotation shaft, a return spring is elastically provided between the slide cylinder and the spring bearing, a long spiral hole is formed in the slide cylinder, a lock pin implanted in the rotation shaft in a standing position is loosely fitted into the long spiral hole, and torque of the rotation shaft is transmitted to the power generator.” [0010] Patent Document 1 Japanese Patent Application Publication No. 2005-320865 [0011] Patent Document 2 Japanese Patent Application Publication No. 2004-353637 [0012] Patent Document 3 Japanese Patent Application Publication No. 2005-9415 SUMMARY OF THE INVENTION [0013] Recently, a lot of propeller wind turbines have been constructed in regions with strong winds. However, wind turbines of this type have the following disadvantages. A propeller wind turbine has a restriction that a support column for supporting the propeller needs to be strengthened rather than the propeller itself, which leads to an increase in construction cost. Moreover, since propeller wind turbines are constructed in a large site, they are more likely to be hit by lighting. [0014] Furthermore, propeller wind turbines make large wind noise since the blades constituting the propeller are made of metal or hard plastic. In addition, when the blades are hit by a gust of strong wind, they might break into pieces, and the scattered pieces might hurt humans and animals. Hence, there is also a location problem that propeller wind turbines need to be constructed in a large and remote site. [0015] Moreover, a starting motor is an essential for propeller wind turbines because of the following restriction. To cause the propeller to rotate at startup or in light winds, a separately-provided motor needs to be put into operation first to cause the propeller to rotate and to activate the power generation function in the meanwhile. [0016] On the other hand, in the above-described case of using canvas blades made of canvas, unlike the case of using blades made of metal or hard plastic, the blades do not brake into pieces which prevent the pieces to be scattered. However, disadvantageously, such blades might not rotate depending on the wind direction. [0017] The inventors of the present invention diligently carried out research to solve the above-described problems. Through the research, the inventors succeeded in developing a new wind turbine generator having the following features and a wind turbine generator system using the wind turbine generator. In this wind turbine generator, a rotor can easily start rotating by small wind force (1 to 2 m/s or more) by using bowl-shaped rotor blades made of canvas, and once the rotor starts rotating, it can continuously rotate because of the inertia force. Moreover, this wind turbine generator is inexpensive and can be constructed in a site having no power source. [0018] Specifically, a wind turbine generator rotor unit according to an embodiment of the present invention comprises: a support column being a rod having an upper end portion and a lower end portion each reduced in external diameter toward the tip of the end portion; a circular ring holding the end portions of the support column so that the support column itself rotates; a holder fixed to the support column; and a plurality of rotor blades attached to the support column by using the holder. Here, the wind turbine generator rotor unit is wherein the rotor blades each include: a frame unit including a frame having an opening, multiple first support frames each extending from the frame so as to form semielliptical shape, and a central support frame supporting the first support frames; and a sail attached to the frame unit so as to cover the frame unit. [0019] In a wind turbine generator rotor unit according to a further embodiment, the holder is a circular plate fixed to a central portion of the support column, and the rotor blades are each attached to the holder by sandwiching the holder. [0020] According to a wind turbine generator rotor unit according to another embodiment, the holder is a circular fixing member holding and fixing peripheries of the rotor blades. [0021] In a wind turbine generator rotor unit according to a further embodiment, fixing member main bodies are provided respectively on upper and lower central portions of an inner surface of the circular ring, and the end portions of the support column are fitted respectively to the insides of the fixing member main bodies by using adjustors which enable height adjustment. [0022] In yet another embodiment, in a wind turbine generator rotor unit, the rotor blades have a structure making the rotor blades foldable frontward and backward. [0023] A wind turbine generator may also comprise at least: the wind turbine generator rotor unit mentioned above; a power generator generating power by using torque of the wind turbine generator rotor unit; and a transmission mechanism transmitting torque of the support column of the wind turbine generator rotor unit to the power generator. [0024] The wind turbine generator may also further comprise a power storage storing power generated by the aforementioned power generator. [0025] The powers storage of the wind turbine generator is advantageously formed of any one of a secondary battery and/or an electric double-layer capacitor. [0026] In a wind turbine generator according to a further embodiment, the support column, serving as a rotation shaft of the wind turbine generator rotor unit, is provided with a plurality of longitudinal rails, and wires provided to end portions of each of the rotor blades are moved by a servomotor provided to one of the end portions of the support column, so that the frames are folded. [0027] A wind turbine generator according to a further embodiment comprises: a rotor unit including a circular suspension member having an opening in the bottom, a plurality of rotor blades suspended from the suspension member, and a circular holder holding one end portion of each of the rotor blades; a plurality of support rods supporting the suspension member; a power generator generating power by using torque of the circular holder; and a power storage storing power generated by the power generator. [0028] The wind turbine generator according advantageously further comprises a rotation stopper forcing the rotor unit to stop rotating. [0029] Another embodiment of a wind turbine generator system according to the invention comprises: the wind turbine generator as mentioned above; and a power control unit transmitting power generated in the wind turbine generator to a power system of a building. Here, the wind turbine generator supplies power generated by the power generator to the power storage through a rectifier, or directly from the power generator, and the power control unit includes a power convertor which converts power from the power storage into power having a voltage, a frequency and the like conforming with power system standards, and which has necessary protection functions. [0030] A first aspect of the present invention provides a wind turbine generator rotor blade comprising: a frame unit including a frame having an opening and a plurality of support frames each extending from the frame; and a sail attached to the frame unit so as to cover the frame unit. [0031] A second aspect of the present invention provides the wind turbine generator rotor blade, wherein the opening is in any one of a semicircular shape, a semielliptical shape, a leaf shape, or a comb shape. [0032] A third aspect of the present invention provides the wind turbine generator rotor blade, wherein the support frames include a plurality of first support frames each extending from the frame and a central support frame supporting the first support frames. [0033] A fourth aspect of the present invention provides the wind turbine generator rotor blade, wherein the first support frames each extend from the frame so as to form a semielliptical shape. [0034] A fifth aspect of the present invention provides the wind turbine generator rotor blade, wherein a hole is formed in an end portion of the sail, and a string is inserted into the hole to attach the sail to the frame unit so as to cover the frame unit. [0035] A sixth aspect of the present invention provides the wind turbine generator rotor blade, wherein the rotor blade is overall in a bowl shape expanding outwardly with a radius. [0036] A seventh aspect of the present invention provides the wind turbine generator rotor blade, wherein the frame of the rotor blade has a structure allowing the frame to be folded frontward and backward. [0037] An eighth aspect of the present invention provides a wind turbine generator comprising: a rotor unit including a support column, a holder fixed to the support column, and a plurality of rotor blades attached to the holder; a circular ring detachably holding end portions of the support column; and a power generator coupled to the rotor unit with a transmission mechanism interposed therebetween, and generating power by using torque of the rotor unit. [0038] A ninth aspect of the present invention provides the wind turbine generator, further comprising a power generating unit storing power generated by the power generator. [0039] A tenth aspect of the present invention provides the wind turbine generator, wherein the rotor unit further includes a circular fixing member having, in an inner circumferential surface, a recess for holding and fixing outer frames of the rotor blades. [0040] An eleventh aspect of the present invention provides the wind turbine generator, wherein the circular fixing member is formed of hard resin. [0041] A twelfth aspect of the present invention provides the wind turbine generator, wherein the holder is a flywheel fixed to a central portion of the support column. [0042] A thirteenth aspect of the present invention provides the wind turbine generator, wherein the support column is a rod having an upper end portion and a lower end portion each reduced in external diameter toward the tip of the end portion. [0043] A fourteenth aspect of the present invention provides a wind turbine generator, wherein the support column is an aluminum rod. [0044] A fifteenth aspect of the present invention provides the wind turbine generator, wherein fixing member main bodies are provided respectively on upper and lower central portions of an inner surface of the circular ring, a fixing member is provided in an inside of each of the fixing member main bodies, and the end portions of the support column are inserted respectively into the fixing members having a plurality of bearings, each of the fixing members provided in an inside of the corresponding fixing member main body with an adjustor for height adjustment interposed in between. [0045] A sixteenth aspect of the present invention provides the wind turbine generator, wherein the circular ring is formed of a thin stainless plate with a width of 10 cm. [0046] A seventeenth aspect of the present invention provides the wind turbine generator, wherein springs are attached to the adjustors, respectively. [0047] An eighteenth aspect of the present invention provides the wind turbine generator, wherein the transmission mechanism is provided around the lower end portion of the support column, and torque of the support column is thereby transmitted to the power generator through the transmission mechanism. [0048] A nineteenth aspect of the present invention provides the wind turbine generator, wherein the transmission mechanism includes any one of a combination of a torque pulley and a transmission belt and a combination of gear wheels meshing with each other. [0049] A twentieth aspect of the present invention provides the wind turbine generator, wherein the flywheel is a circular plate and is fixed to a substantially central portion of the support column by upper and lower fasteners. [0050] A twenty-first aspect of the present invention provides the wind turbine generator, wherein the upper and lower fasteners are: an upper fastener fixing the flywheel to the support column by inserting a rectangular pin into a shallow groove perpendicularly formed in the support column and a groove formed in a position of the flywheel, the position facing the groove in the support column; and a lower fastener including a bearer fixed to the support column by welding. [0051] A twenty-second aspect of the present invention provides the wind turbine generator, wherein the rotation shaft is provided with a plurality of longitudinal rails, and wires provided to end portions of each of the rotor blades are moved by a servomotor provided to one of the end portions of the rotation shaft, so that the rotor blades are folded. [0052] A twenty-third aspect of the present invention provides a wind turbine generator system comprising a power control unit transmitting power generated in the wind turbine generator to a power system of a building. Here, the wind turbine generator system wherein the wind turbine generator supplies power generated by the power generator to the power storage through a rectifier, or directly from the power generator, and the power control unit includes a power convertor which converts power from the power storage into power having a voltage, a frequency and the like conforming with power system standards, and which has necessary protection functions. [0053] A twenty-fourth aspect of the present invention provides the wind turbine generator system, wherein the power storage is formed of any one of a secondary battery and an electric double-layer capacitor. [0054] A twenty-fifth aspect of the present invention provides a wind turbine generator comprising: a rotor unit including a circular suspension member having an opening in the bottom, and a circular holder holding one end portion of each of a plurality of rotor blades suspended from the suspension member; a plurality of support rods supporting the suspension member; a rotation stopper forcing the rotor unit to stop rotating; a power generator generating power by using torque of the circular holder; and a power storage storing power generated by the power generator. [0055] A twenty-sixth aspect of the present invention provides the wind turbine generator, wherein the circular suspension member has an opening in the bottom, and the opening is in a substantially circular shape, which allows the spherical rotor blades to rotate. [0056] A twenty-seventh aspect of the present invention provides the wind turbine generator, wherein the power generator is coupled with a pinion for the power generator, so that when the pinion for the power generator is rotated by torque of the circular holder, a rotor of the power generator coupled with the pinion is rotated to generate power. [0057] A twenty-eighth aspect of the present invention provides the wind turbine generator, wherein the rotation stopper includes a pair of sandwiching members, and has a structure allowing the rotation stopper to sandwich the circular holder from both sides. BRIEF DESCRIPTION OF THE DRAWINGS [0058] FIG. 1 is a perspective view of a rotor blade for a wind turbine generator according to the present invention. [0059] FIG. 2 is an explanatory view showing a configuration of a frame unit in FIG. 1 . [0060] FIG. 3 is explanatory views showing variations of a frame. [0061] FIG. 4 is a perspective view of an external view of a circular ring according to the present invention. [0062] FIG. 5 is a cross-sectional view showing fasteners fastening a flywheel according to the present invention. [0063] FIG. 6 is an explanatory view showing a mechanism for rotating a support column according to the present invention. [0064] FIG. 7 is an explanatory view for explaining a wind turbine generator system according to the present invention. [0065] FIG. 8 is a perspective view of a rotor according to the present invention. [0066] FIG. 9 is a perspective view of another rotor according to the present invention. [0067] FIG. 10 is a perspective view of still another rotor according to the present invention. [0068] FIG. 11 is an explanatory view for explaining another wind turbine generator system according to the present invention. [0069] FIG. 12 is an explanatory view for explaining still another wind turbine generator system according to the present invention. [0070] FIG. 13 is a side view of FIG. 12 . DESCRIPTION OF REFERENCE NUMERALS [0000] 1 . . . rotor blade 1 a . . . end portion 1 a . . . end portion 2 . . . frame 3 . . . (first) support frame 4 . . . central support frame 5 . . . sail 6 . . . string 7 . . . support column 8 . . . flywheel 9 . . . circular ring 10 . . . frame unit 12 . . . power generator 13 . . . power storage 14 . . . upper fastener (wedge-shaped pin) 15 . . . lower fastener (bearer) 16 . . . groove 17 . . . fixing member main body 18 . . . bearing 19 . . . fixing member 20 . . . adjustor 21 . . . fastener 22 . . . circular fixing member (holder) 23 . . . recess 24 . . . rotating pulley 25 . . . transmission belt 26 . . . circular suspension member 27 . . . support bar 28 . . . rotor blade 29 . . . circular holder 30 . . . rotation stopper 31 . . . power generator 32 . . . power storage 33 . . . pinion for power generator 34 . . . lighting conductor 35 . . . mount 40 . . . power control unit 50 . . . slot 60 . . . anemometer 61 . . . servomotor 62 . . . wire 63 . . . housing 64 . . . shaft stopper ring 65 . . . base 66 . . . V-belt pulley 67 . . . small pulley 100 , 200 , 300 . . . rotor unit DETAILED DESCRIPTION OF THE INVENTION [0118] Detailed description will be given below of the present invention on the basis of the drawings. However, the scope of the present invention is not limited to the description. [0119] FIG. 1 shows a basic shape of a rotor blade 1 used in a wind turbine generator of the present invention, and FIG. 2 is an illustration showing a structure of a frame unit shown in FIG. 1 . FIG. 3 is illustrations showing variations of a frame 2 , and shapes for allowing a flywheel 8 to be sandwiched and fitted to a slot 50 (as shown in FIG. 7 or FIG. 8 ) are shown in FIGS. 3 a and 3 b , respectively. [0120] The rotor blade 1 includes a frame unit 10 . As shown in FIG. 1 and FIG. 2 , the frame unit 10 includes: the frame 2 having openings in a semicircular shape or a semielliptical shape, or a different shape such as a leaf shape or a comb shape; multiple first support frames 3 each provided in an extending manner from the frame 2 so as to form a semielliptical shape; and a central support frame 4 supporting the first support frames 3 . The rotor blade 1 is fixed to a support column 7 with a holder 8 interposed therebetween, in such a manner that a string 6 is inserted to holes (not shown) formed in a peripheral portion of a sail 5 attached to the frame unit 10 so as to cover the frame unit 10 , and is thus overall in a bowl shape expanding outwardly with a radius. [0121] As the holder, either the flywheel 8 partitioning the rotor blades as shown in FIG. 8 and FIG. 9 or fasteners 21 directly attached to the support column are used. [0122] As shown in FIG. 7 , the wind turbine generator of the present invention includes a rotor unit 100 , a power generator 12 generating power by using torque of the rotor unit 100 , and a power storage 13 storing power generated by the power generator 12 , in a circular ring 9 detachably holding the end portions of the support column 7 as shown in FIG. 4 . The rotor unit 100 includes the support column 7 , the flywheel 8 fixed to a central portion of the support column 7 , and multiple rotor blades 1 attached to a circular disc of the flywheel 8 . [0123] An example of the wind turbine generator of the present invention includes, as shown in FIG. 7 : the rotor unit 100 consisting of the circular ring 9 formed of a thin stainless plate with a width of 10 cm and holding the end portions of the support column 7 , the support column 7 made of metal and detachably attached to the inside of the circular ring 9 , the flywheel 8 made of metal and fixed to the central portion of the support column 7 , and the multiple rotor blades 1 attached to the flywheel 8 ; the power generator 12 generating power by using torque of the rotor unit 100 ; and the power storage 13 storing power generated by the power generator 12 . [0124] The support column 7 of the wind turbine generator of the present invention is a rod with the external diameter of each of the upper end portion and the lower end portion reduced toward the tip of the end portion. Accordingly, once this support column 7 starts rotating by the turning action of the rotor blades 1 attached to the flywheel 8 , the rotation continues for a long time because of the inertial force as the rotation of a commercially-available gyro-top. This is because as the finer the end portions are formed, the less the resistance in the event of rotation becomes, which allows the rotation to continue for a long time. [0125] The flywheel 8 fixed to the support column 7 is a circular plate, and fixed to an approximately central portion of the support column 7 with upper and lower fasteners 14 and 15 as shown in FIG. 5 . Here, the lower fastener 15 is a circular bearer fixed to the support column by welding, and the upper fastener 14 is one or more rectangle pines knocked and inserted into grooves 16 formed respectively in the support column 7 and the flywheel 8 , to hold and fix the support column and the flywheel 8 . [0126] The lower end portions of the support column 7 are inserted into fixing member main bodies 17 with adjusters 20 , the fixing member main bodies 17 provided respectively on upper and lower central portions of the inner surface of the circular ring 9 . Moreover, each of the lower end portions of the support column 7 is inserted into the inner portion of a fixing member 19 formed in a substantially conical shape in the corresponding fixing member main body 17 , the fixing member 19 including multiple bearings 18 aligned along the conical shape. With this structure, the rotation of the rotor unit 100 causes the support column 7 itself to rotate, and a rotation sensor (not shown) controls the rotation of the support column 7 to have a rated PRM of 700 to 2,000 in the event of rotation using the rotation sensor (not shown). [0127] To attach the support column 7 detachably to the inside of the circular ring 9 , the end portions of the support column 7 are inserted into the fixing member with the adjustors 20 including spring members provided inside the fixing member main bodies 17 to allow height adjustment, the fixing members each include the multiple bearings. The adjustors 20 include springs. [0128] Near the lower end portion of the support column 7 , a transmission mechanism is provided. As shown in FIG. 7 , in this transmission mechanism, a rotating pulley 24 is directly attached to the support column 7 to transmit the torque of the support column 7 to the power generator 12 through a transmission belt 25 . Alternatively, gear wheels which mesh with each other can be used as a transmission mechanism. [0129] Moreover, a protrusion serving as a lighting conductor is provided near the upper end portion of the support column 7 , while a ground wire is provided so as to extend from near the lower end portion of the support column 7 to the underground, to let energy occurring when lighting strikes flow into the underground. In addition, a circular ring with multiple strings or chains attached thereto (not shown) may be fitted to the protrusion serving as a lighting conductor to keep the support column 7 perpendicular. [0130] In the present invention, a rotation motor (not shown) can be provided as a means used to cause the rotor to start rotating in a case with no winds. [0131] A second wind turbine generator of the present invention includes a rotor unit 200 , the circular ring 9 detachably holding the end portions of the support column, the power generator 12 generating power by using torque of the rotor unit 200 , and the power storage 13 storing the power generated by the power generator 12 . As shown in FIG. 9 , the rotor unit 200 includes the support column 7 , the multiple rotor blades 1 fixed to the support column 7 by the fasteners 21 attached to the support column 7 , and a circular fixing member 22 holding and fixing the circumferences of the rotor blades same as those shown in FIG. 7 . [0132] In this example, as shown in FIG. 9 , one end of each of the rotor blades 1 is fixed to the support column 7 by the multiple fasteners 21 attached to the support column 7 beforehand. Moreover, the circular fixing member 22 made of hard resin is attached to the circumference of the other end side of each of the rotor blades 1 , and serves as a weight, which makes the rotation smooth. [0133] Here, the circular fixing member 22 has recesses 23 made of hard resin and holding and fixing the outer frames of the rotor blades 1 , in the inner circumferential surface. Thus, the outer circumferences of the rotor blades 1 are held and fixed by the recesses 23 . In addition, on the outer circumference of the circular fixing member 22 made of hard resin, commercial messages may be shown by using LED chips or the like, or a picture or a pattern may be printed. Thus, messages, a picture, or a pattern shown on the outer circumference of the circular fixing member 22 can be visually identified easily even from a distance. [0134] Means for operating the power generator 12 by using torque of the rotor is operated in the same manner as the first wind turbine generator of the present invention described above. [0135] A wind turbine generator system which is a third invention of the present invention includes: frame units each consisting of the frame 2 in a semicircular shape, a semielliptical shape or a leaf shape, the multiple support frames 3 extending from the frame 2 , and the central support frame 4 supporting the support frames 3 ; a rotor unit including the wind-power-generation rotor blades each consisting of the sail 5 attached to the frame unit so as to cover the frame unit; the circular ring 9 detachably holding the end portions of the support column; the power generator 12 generating power by using torque of the rotor unit; the power storage 13 storing the power generated by the power generator 12 ; and a power control unit 40 transmitting the power stored in the power storage 13 to a power system of a building. The rotor unit is either the rotor unit 100 including the support column 7 , the flywheel 8 fixed to the central portion of the support column 7 , and the multiple rotor blades 1 attached to the flywheel 8 , or the rotor unit 200 including the support column 7 , the multiple rotor blades 1 fixed by the fasteners 21 attached to the support column 7 , and the circular fixing member 22 holding and fixing the outer circumferences of the rotor blades, and causes the support column to rotate. The power generator 12 generates power by rotating a rotor (not shown) of the power generator 12 linked to the support column 7 with the rotating pulley 24 interposed therebetween. The power generated by the power generator 12 is supplied to the power storage 13 through a rectifier (not shown), or directly from the power generator 12 . Moreover, the power control unit 40 includes a power convertor (not shown) which converts the power from the power storage 13 to have a voltage, a frequency and the like conforming with the standards of the power system, and which has necessary protection functions. [0136] Here, the power storage 13 is formed of a secondary battery or an electric double-layer capacitor, which makes it possible to do maintenance by requiring as less human work as possible. [0137] A bottom portion of the circular ring 9 with the support column 7 and the rotor unit 100 provided therein is placed on and fixed to a mount 35 . Alternatively, a fastener (not shown) which allows chains or strings to be fastened to the lighting conductor 34 provided on the upper portion of the circular ring 9 may also be provided to stabilize the circular ring 9 by pulling the circular ring 9 to the front, the back, the right and the left. [0138] In this system of the present invention, the rotor with the rotor blades attached thereto rotates by receiving light winds (wind speed 1 to 2 m/s) blown from above, below, the right and the left. Here, a design may be made to include a small motor (not shown) for making the support column rotatable at startup of the case of forcing the rotor to rotate at startup by a man-induced operation. [0139] In this system, a rotation sensor (not shown) is attached to the support column 7 or the rotor blades 1 to measure the torque of the rotor unit, and to cause the power generation function to operate when the rated speed reaches a set value from 700 rpm to 2,000 rpm. [0140] In strong winds, the rotor unit is removed by a man-induced operation because the rotor can be detached easily, or, when the man-induced operation is not possible, fasteners may be separately provided in such positions that the fasteners can sandwich the support column, to force the rotation of the support column to stop rotating when the wind speed measured by the anemometer exceeds a predetermined wind speed value. [0141] A fourth wind power apparatus of the present invention includes, as shown in FIG. 10 and FIG. 11 : a rotor unit 300 consisting of a circular suspension member 26 having an opening in the bottom, multiple support bars 27 supporting the suspension member, and a circular holder 29 holding one end portion of each of multiple rotor blades 28 suspended from the suspension member 26 ; a rotation stopper 30 forcing the rotor unit to stop rotating; a power generator 31 generating power by using torque of the circular holder; and a power storage 32 storing the power generated by the power generator. [0142] Here, the circular suspension member 26 has an opening in the bottom, and the upper part of the opening is in a substantially circular shape. This allows the spherical rotor blades to rotate. [0143] The power generator 31 is coupled with a pinion 32 for the power generator. Accordingly, when the power generation pinion 33 is rotated by the torque of the circular holder 29 , a rotor (not shown) of the power generator 31 coupled with the pinion 33 is rotated, and power is generated by the action of a permanent magnet, for example. In this case, a commercially available alternating-current generator or direct-current generator may alternatively be used as the power generator. [0144] The rotation stopper 30 is connected to an anemometer (not shown), and includes a pair of sandwiching members (not shown) capable of stopping the rotation by sandwiching the circular holder 29 from the right and the left in strong winds. [0145] Another wind turbine generator system according to the present invention includes: the rotor unit 300 consisting of the circular suspension member 26 having an opening in the bottom, the multiple support bars 27 supporting the suspension member, and the circular holder 29 holding one end portion of each of the multiple rotor blades 28 suspended from the suspension member 27 ; the power generator 31 generating power by using torque of the circular holder 29 ; the power storage 32 storing the power generated by the power generator; and a power control unit 40 transmitting the power stored in the power storage 32 to a power system of a building. Here, the circular suspension member has an opening in the bottom, and the upper part of the opening is in a substantially circular shape, which allows the spherical rotor blades to rotate. The power generator is coupled with a pinion for the power generator. Accordingly, when the power generation pinion is rotated by the torque of the circular holder, a rotor of the power generator coupled with the pinion is rotated, and power is generated by the action of a permanent magnet, or by using a commercially available alternating-current generator or direct-current generator. The power generated by the power generator is supplied to the power storage through a rectifier, or directly from the power generator. Moreover, the power control unit includes a power convertor which converts the power from the power storage to have a voltage, a frequency and the like conforming with the standards of the power system, and which has necessary protection functions. [0146] The frames and the support frames of the rotor blades used in the wind turbine generator of the present invention is preferably made of a metal or resin material having a certain degree of strength. Moreover, the sails attached to the frame units are preferably made of a strong cloth material used for marine sails or a strong cloth material used for parachutes for heavy drop. [0147] A fifth wind turbine generator of the present invention uses rotor blades having a structure that the sails of the rotor blades can be folded in strong winds, as shown in FIG. 12 and FIG. 13 . [0148] Here, the support column 7 serving as a rotation shaft in this example is provided with multiple longitudinal rails. Wires provided to end portions 1 a and 1 b of each of the rotor blades 1 (blades made of cloth) are moved by servomotors 61 provided on the outer surface of an outer frame fixing member, and the rotor blades 1 are thereby folded. For example, a sensor (not shown) causes the servomotors 61 to operate, on the basis of a value showing strong winds with a wind speed of 25 m or more measured by an anemometer 60 . Thereby, wires 62 attached to the end portions 1 a and 1 b of each of the rotor blades move along the rails provided to the support column while folding the rotor blades from the end portions 1 a and 1 b. [0149] In this example, the rotation shaft is held by three bearing housings 63 at the top, on top of a base, and at the bottom of the base. A shaft stopper ring 64 is attached so as to be in connection with the housing disposed on top of the base to stop the rotations of the outer frame and the rotation shaft in strong winds. [0150] With this configuration, the rotor blades in the folded state do not rotate and let the strong winds pass. Accordingly, no maintenance due to strong winds is required; thus, this wind turbine generator is valuable when used in a region with few maintenance personnel. [0151] When the wind speed value measured by the anemometer indicates 25 m or smaller, on the other hand, the shaft stopper ring 64 is released. Thereby, the rotor blades start to open by the action of the servomotors 61 , and return to the original state. [0152] Inside the base 65 , a V-belt pulley 66 is disposed along the rotation shaft. The pulley 66 is configured to rotate, by using a belt (not shown), a small pulley 67 which is disposed so as to face the pulley 66 and which operates a power generator 68 . [0153] Here, multiple bearings (not shown) are buried into the inner circumference surfaces of the bearing housings so as to be in contact with the rotation shaft surface to facilitate the rotation of the rotation shaft. [0154] The wind turbine generator of the present invention is a sectional wind turbine generator that can easily be constructed on the roof of a mid-rise/high-rise building as well as in a large site such as a green field with few plants or a desert. In addition, maintenance can be done easily because the rotor blades can be replaced individually. [0155] In the case of constructing the wind turbine generator in a large site, a lighting conductor can be disposed in the center of the circular ring to let current occurring when lighting strikes flow into the underground. With this lighting conductor, damage to the rotor unit and the like can be prevented. [0156] The rotor blades and the support column can be assembled at a height of approximately several meters above ground, when the rotor blades and the like are installed. Accordingly, a machine such as a large-size crane is not required in the event of a failure, unlike a conventional propeller wind turbine; hence, the wind turbine generator of the present invention can easily be constructed even in a place which a machine such as an automobile is difficult to enter. [0157] While having a simple structure, the wind-power-generation rotor blades each have a circular or elliptic opening and a sail with a bowl-shaped radius. With such blades, even in light winds from any direction, above, below, the right or the left, the rotor unit can easily be rotated by receiving the winds by the entire blades. Moreover, once the rotor unit starts rotating, the support column serving as a support shaft continuously rotates at a rated speed from 700 rpm to 2,000 rpm by using the inertial force. [0158] Moreover, commercial messages or pictures can be drawn on the rotor blades used in the present invention and the circular fixing member for holding and fixing the peripheries of the rotor blades, to enhance the advertising effects. Besides, various advertisements can be shown in accordance with the rotation speed. [0159] Furthermore, the wind turbine generator system of the present invention can be remotely operated. Accordingly, this system is especially preferable for the operation in a place with few workers and the like. [0160] When the wind speed measured by the anemometer is equal to or larger than a predetermined value, the wires are moved by the working of the power transmission motor and the canvas blades connected to the wires can thereby be folded frontward and backward. Thus, the rotor blades used in the wind turbine generator of the present invention has a structure that enables a folded state in strong winds to avoid receiving strong winds. [0161] Priority is claimed to applications JP 2006-145911 filed Apr. 25, 2006, JP 2007-52025 filed Feb. 1, 2007 and PCT/JP2007/059417, and each of said foregoing applications is hereby explicitly incorporated by reference.
Provided is a wind power generating apparatus adopts a rotor blade including a frame body unit composed of a frame body having an opening and a plurality of support frames extending from the frame body, and a sail portion adhered to cover the frame body unit. The frame body unit is configured to be retractable using wires and a servo-motor to decrease the surface area of the rotor blade in high winds. As a result, the rotor blade can rotate easily with a low wind power and can rotate continuously with an inertial power, once it starts the rotations, so that it can run the power generating function at a set value of a rated speed of rotations of 700 to 2,000 rpm.
5
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a braking system for use in an automotive vehicle and particularly to a hydraulic braking system comprising a tandem master cylinder and a hydraulic booster which outputs hydraulic power pressure supplied from a power source in response to the depression of a brake pedal. 2. Description of the Prior Art In a conventional braking system for an automotive vehicle, there are provided a plurality of hydraulic circuits connecting wheel brake cylinders with a hydraulic braking pressure generator such as a master cylinder, so that when one of the hydraulic circuits is broken, braking operation is achieved by the rest of the hydraulic circuits. In general, a tandem master cylinder is used in a conventional dual circuit system. In order to reduce the force required to operate a brake pedal during a braking operation, the hydraulic braking system is provided with a servo unit which is commonly referred to as a servo or a booster and which utilizes compressed air, intake manifold vacuum (for a vacuum booster), or hydraulic pressure (for a hydraulic booster) as a power source. The hydraulic booster is a booster which actuates the hydraulic braking pressure generator such a the master cylinder by the hydraulic power pressure supplied from the power source in response to depression of the brake pedal. For example, the Japanese Patent Laid-open Publication No. 59-209948 has disclosed a system associating the hydraulic booster with the tandem master cylinder which operates as an ordinary tandem master cylinder when the hydraulic booster is not operated. With employment of such hydraulic booster, it has been proposed to use the hydraulic booster, in the hydraulic braking system, as a dynamic hydraulic pressure generator in addition to the master cylinder. In other words, a hydraulic pressure boosted by the booster (hereinafter referred to as boost pressure) in response to the depression of the brake pedal is applied directly to a hydraulic circuit. For example, as shown in Japanese Patent Laid-open Publication No. 59-227552, boost pressure of the hydraulic booster is applied to rear wheel brake cylinders in a front-and-rear dual circuits system in order to reduce the stroke of the brake pedal. However, if the hydraulic power pressure is lost due to a failure of the operation of the power source, the braking force of the rear wheels disappears, although the braking force of the front wheels can be maintained by the master cylinder. It is also known from Japanese Laid-open Publication No. 62-155167 that the boost pressure of a hydraulic booster can be transmitted to a pressure chamber of the tandem master cylinder for pressuring certain wheel cylinders. According to such a system, the various effects such as the shortening of the stroke of the brake pedal and so on are obtained. In case of the loss of hydraulic power pressure, the system functions as an ordinary tandem master cylinder and the braking force of all of the wheels can be maintained. In that system, a pressurizing reservoir (e.g., see brake chamber 60 in the publication) having a large capacity is provided, so that enough brake fluid is available when the hydraulic power pressure is not supplied to the second fluid chamber (e.g., see chamber 28 in the publication) of the tandem master cylinder due to the loss of operation of the power source. However, since the second fluid chamber of the tandem master cylinder is communicated with the boost chamber (e.g., see booster operation chamber 88 in the publication) of the hydraulic booster via the pressurizing reservoir, a closed space is formed therein when the communication with the power source is interrupted or the operation of the power source is ceased. Accordingly, since the volume of the boost chamber is expanded by the operation of the hydraulic booster in the above case, the volume of the closed space expands and a negative pressure is generated in that space. This negative pressure results in a decrease of the output hydraulic pressure of the master cylinder and a corresponding loss of the braking force. The occurrence of this phenomenon is especially evident when the brake pedal is depressed many times in a short period. As mentioned above, the pressurizing reservoir is recognized as being effective to compensate for the loss of operation of the power source and so on. However, it is difficult to form such reservoir in the housing. SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to ensure the presence of sufficient braking fluid in the second fluid chamber to maintain a stable braking force in case of a failure of the power source, even when pressurized booster fluid is applied to one of the pistons. It is another object of the present invention to minimize adverse braking action resulting from the generation of negative pressure in a conduit which contains the second fluid chamber and the hydraulic booster. It is a further object of the present invention to provide an improved hydraulic braking system which includes a tandem master cylinder having a bore with an opening and a closed wall at opposite ends thereof. A first piston is slidably fitted in the bore so as to define a first pressure chamber and a first fluid chamber therein and is operatively connected to a brake pedal. A second piston is slidably fitted in the bore so as to define a second fluid chamber adjacent to the first pressure chamber and a second pressure chamber and is operatively connected to the first piston. Both pressure chambers receive brake fluid from a reservoir through the fluid chambers, respectively, and transmit brake hydraulic pressure when the piston is caused to slide in response to the depression of the brake pedal. A power source generates a hydraulic power pressure. A hydraulic booster boosts the piston action in response to depression of the brake pedal, and also transmits a boost hydraulic pressure to the second fluid chamber. A plurality of wheel cylinders for braking respective road wheels is divided into a first group of wheel brake cylinders communicated with the first pressure chamber through one hydraulic circuit, and a second group of wheel brake cylinders communicated with the second pressure chamber through another hydraulic circuit. Conduit means containing the second fluid chamber and the hydraulic booster is communicated with the reservoir through a check valve. According to the improved hydraulic braking system including the above structure, when the brake pedal is depressed, the power hydraulic pressure is regulated in response to the depression of the brake pedal and the regulated hydraulic pressure is transmitted to the second fluid chamber. Since brake hydraulic boost pressure is transmitted to the second group of wheel cylinders through the second fluid chamber and the second pressure chamber before the first piston slides, the stroke of the brake pedal is shortened. Also, when negative pressure is generated in the conduit means connected between the second fluid chamber and the hydraulic booster, e.g., due to a failure of the power source, the check valve means opens so that brake fluid is sucked in from the reservoir. Thus, the brake fluid having a pressure greater than atmospheric pressure will occupy the conduit means to minimize any adverse movement of the second piston. Accordingly, the master cylinder will then be able to operate as a standard non-boosted tandem master cylinder, whereby static hydraulic pressure is applied to all wheels. BRIEF DESCRIPTION OF THE DRAWINGS Additional objects and advantage of the present invention will become more apparent from the following detailed description of preferred embodiments thereof when considered with reference to the attached drawings, in which: FIG. 1 is a schematic illustration of a hydraulic braking system according to a first embodiment of the present invention, including a longitudinal sectional view through a tandem master cylinder; FIG. 2 is a partial enlarged longitudinal sectional view through a check valve of the first embodiment; FIG. 3 is a longitudinal sectional view through a fragment of a hydraulic braking system according to a second embodiment of the present invention; and FIG. 4 is a view similar to FIG. 1 of a hydraulic braking system according to a third embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A hydraulic braking system in accordance with preferred embodiments of the present invention will be described with reference to the drawings. Referring to FIG. 1, there is schematically illustrated a hydraulic braking pressure generator 1 which includes a tandem master cylinder 10 and a hydraulic booster 20. As a result, a depression force applied on a brake pedal 2 is transmitted as a brake operating force to an input rod 3. In response to this brake operating force, hydraulic pressure from a power source 40 or a reservoir 41 is appropriately regulated and applied to wheel cylinders 51a and 52a of front wheels 51 and 52 through a first hydraulic passage 72 and to wheel cylinders 53a and 54a of rear wheels 53 and 54 through a second hydraulic passage 71. The tandem master cylinder 10 includes a housing 1a with a bore 10a. In the bore 10a, a first piston 11 and a second piston 15 are slidably and fluid-tightly fitted. At opposite ends of the first piston 11, there are formed a large-diameter land and a small-diameter land. A right side of the bore 10a is formed into a stepped configuration so as to receive the first piston 11. Between the two lands of the first piston 11, a first fluid chamber 13 is defined in the large-diameter portion of the bore 10a. Between the second piston 15 and the small-diameter land of the first piston 11, a first pressure chamber 12 is defined in the small-diameter portion of the bore 10a. The first pressure chamber 12 is in fluid communication with the first hydraulic passage 71 through a port 12a, and the first fluid chamber 13 is in fluid communication with a second reservoir chamber 412 of the reservoir 41 through a port 13a. The first piston 11 has holes 11a and 11b extending axially from its opposite ends towards its center, respectively, and a hole 11c formed radially and communicated with the hole 11a through a small hole 11d. The hole 11a opens into the first pressure chamber 12 and the hole 11c opens into the first fluid chamber 13. Axial holes 11e are formed in the small-diameter land of the first piston 11 and a cup seal 11f is fitted on the first piston 11 so as to cover the ends of holes 11e located on the first pressure chamber 12 side. As a result, a check valve is constituted by holes 11e and cup seal 11f. A valve member 14a mounted on a right end of a valve rod 14 is movably received in the hole 11a of the first piston 11 in opposing relation to the small hole 11d, and the valve member 14a is restricted from moving towards the second piston 15 by a retainer 14c mounted on the first piston 11. A large-diameter end portion of a left end of the valve rod 14 is movably received in a hole 15b formed in the second piston 15 and is restricted from moving towards the first piston 11 by a retainer 14b mounted on a right end of the second piston 15. A spring 14e is disposed between the retainer 14c and the valve rod 14 so as to urge the valve member 14a towards the small hole 11d. A head portion of the input rod 4 is received in the hole 11b. A return spring 14d is disposed between the retainer 14c and the retainer 14b so as to continually urge the first piston 11 and the second piston 15 away from each other. Thus, the opposite ends of the valve rod 14 are normally in engagement with the respective retainers 14b and 14c. Therefore, the valve 14a and the small hole 11d are spaced from each other, and brake fluid supplied from the reservoir 41 to the first fluid chamber 13 through the port 13a enters the first pressure chamber 12 through the hole 11e or the holes 11c, 11d, and 11a. Thus, when the first piston 11 is moved towards the second piston 15 against the urging force of the return spring 14d, the cup seal 11f and the valve member 14a close the hole 11e and hole 11d, respectively so that the first pressure chamber 12 is held in the closed state except for the port 12a. Accordingly, the pressure of the brake fluid is raised in response to movement of the first piston 11. The second piston 15 is disposed between a closed wall 10b at a left end of the bore 10a and the first piston 11 and is slidably and fluid-tightly fitted into the bore 10a similar to the first piston 11. At the ends of the second piston 15, a pair of small-diameter lands are formed thereon, and a second fluid chamber 17 is defined between those lands, and a second pressure chamber 16 is defined between the second piston 15 and the closed wall 10b. The second pressure chamber 16 is in fluid communication with the second hydraulic passage 72 through a port 16a, and the second fluid chamber 17 is in fluid communication with the third hydraulic passage 73 through a port 17a. Similar to the first piston 11, the second piston 15 has axial holes 15a, 15b and a radial hole 15c. The hole 15a is in fluid communication with the hole 15c through the axial small hole 15d. Axial holes 15e are formed in the land on the second pressure chamber 16 side of the second piston 14, and a cup seal 15f is fitted on the second piston 15 so as to cover the ends of holes 15e on the second pressure chamber 16 side. As a result, a check valve is constituted by holes 15e and the cup seal 15f. A valve member 18a mounted on a right end of a valve rod 18 is movably received in the hole 15a of the second piston 15 in opposing relation to the small hole 15d, and the valve member 15a is restricted from moving towards the closed wall 10b by a retainer 18c mounted on the second piston 15. A large diameter end portion of a left end of the valve rod 18 is movably received in a retainer 18b and is restricted from moving towards the first piston 11 by a retainer 18b mounted on a right end of the second piston 15. A spring 18e is disposed between the retainer 18c and the valve rod 18 so as to urge the valve member 18a towards the small hole 15d. A return spring 18d is disposed between the retainer 18b and the retainer 18c so as to space the second piston 15 from the closed wall 10b. Thus, the valve member 18a is located away from the hole 18d under normal conditions. When the hydraulic booster 20 which will be detailed later supplies output pressure into the second fluid chamber 17 through the third hydraulic passage 73 and the port 17a, the output pressure is transmitted to the second pressure chamber 16 through the hole 15e or the small hole 15d and the hole 15a. At the same time, an urging force towards the first piston 11 is applied to the land of the second piston 15 located at the first pressure chamber 12 side, whereupon the second piston 15 slides towards the first piston 11. When no output pressure from the hydraulic booster 20 is present in the third hydraulic passage 73, and when the first piston 11 is moved towards the second piston 15, the volume of the first pressure chamber 12 is decreased thereby increasing the pressure therein, and the second piston 15 is moved toward the wall 10b against the urging force of the return spring 18d. Thus, the small holes 11d and 15d are closed fluid tightly by the valve members 14a, 18a, respectively, thereby increasing the pressure of the brake fluid in both pressure chambers 12 and 16. At the second fluid chamber 17, a check valve 30 is provided and the second fluid chamber 17 is in fluid communication with a third reservoir chamber 413 of the reservoir 41 via a fourth hydraulic passage 74. This check valve 30 allows a flow of brake fluid from the reservoir 41 to the second fluid chamber 17 and prevents flow in the reverse direction. That is, the check valve 30 communicates the second fluid chamber 17 with the reservoir 41 when the hydraulic pressure in the second fluid chamber 17 becomes low compared with the brake hydraulic pressure (atmospheric pressure) in the reservoir 41 and prevents communication in any other condition. FIG. 2 is a cross sectional view of the check valve 30, the check valve 30 being fitted and fixed into a stepped port 30a formed in the housing 1a. Namely, a valve case 31 which is of generally cylindrical shape has a stepped hole 31a formed centrally therein in the axial direction. A flange portion 31b at one end of the case 31 is fitted into the stepped port 30a, and a tip portion 31c of the valve case 31 is engaged by a stop ring 36a. The flange portion 31b of the case 31 is engaged by a stop ring 36b at a large-diameter portion of the stepped port 30a. Thus, the valve case 31 is fixed in the stepped port 30a against movement in the axial direction. In the tip portion of the valve case 31, a retainer 34 is provided having a communication hole 34a at its center. Further, in a large-diameter portion of the stepped hole 31a of the valve case 31, a valve member 32 is received so as to be contactable with a valve seat 33 formed on a surface of the large-diameter portion of the stepped hole 31a and is urged toward the valve seat 33 by a spring 35 supported by the retainer 34. Also, in an outer circumference of the center of the valve case 31, a seal groove 31d is formed, and a seal member 37 is fitted into the seal groove 31d. Accordingly, in this check valve 30, the valve member 32 normally seats on the valve seat 33 and closes the stepped port 30a. When the brake fluid pressure in the second fluid chamber 17 becomes lower than the brake fluid pressure in the reservoir 41, the valve member 32 moves toward the retainer 34 against the urging force of the spring 35 and separates from the valve seat 33 to open the stepped port 30a. Next, the hydraulic booster 20 is described below together with a braking force input mechanism. In a housing 1b joined with the housing 1a, a boost chamber 20a and a low-pressure chamber 20b of the hydraulic booster 20 are defined, and a power piston 5 is fluid-tightly and slidably disposed in a bore 20c which is substantially coaxial with the cylinder bore 10a. The power piston 5 is provided with a retainer 6 at its end extending toward the brake pedal 2, and a spring 6a is mounted between the retainer 6 and the housing 1b so as to normally urge the power piston 5 toward the brake pedal 2. The power piston 5 has at its longitudinal middle portion a shoulder portion which abuts the housing 1b to restrict the power piston 5 from sliding toward the brake pedal 2. In the power piston 5, a recess 5a is formed at the end facing the first piston 11, and a stepped bore is formed axially in the center. This stepped bore comprises a small diameter bore 5b, an intermediate-diameter bore 5c, a large-diameter bore 5d and an open end bore 5e. In the stepped bore, received slidably are a reaction rod 22r received in the small-diameter bore 5b, and a reaction piston 22 which has a small-diameter portion received in the intermediate-diameter bore 5c and a large-diameter portion received in the large-diameter bore 5d. The axial length of the reaction rod 22r is larger than the length of the small-diameter bore 5b of the stepped bore. Formed in the reaction piston 22 are an elongated hole 22a extending coaxially with the axis of the reaction piston 22, and a through-hole 22b extending perpendicularly to the elongated hole 22a. A pin 5h fixed to the power piston 5 is disposed in the elongated hole 22a, so that the reaction piston 22 is restricted from sliding at least toward the brake pedal 2 with respect to the power piston 5. The large-diameter portion of the reaction piston 22 is provided with a recess at its end. One end of an input rod 3 is connected to the brake pedal 2, and the other end of the input rod 3 is provided with a spherical head which is inserted in the open end bore 5e of the power piston 5 and received in the recess of the reaction piston 22. Formed radially in the power piston 5 is a through-hole 5f which is aligned with the through-hole 22b when the reaction piston 22 is positioned most closely to the brake pedal 2 and which is larger in diameter than the through-hole 22b. Between the intermediate-diameter bore 5c and the reaction rod 22r, an annular space is defined due to the difference in axial length between the reaction rod 22r and the small-diameter bore 5b, that space communicating with the low-pressure chamber 20b through an inclined hole 5g. The large-diameter end portion of the output rod 4 is received in the recess 5a of the power piston 5 via an elastic reaction disk 4a and is held in the recess 5a by suitable means, such as under the urging of a leaf spring for instance. There exists normally a gap between the reaction disk 4a and the end of the reaction rod 22r. The output rod 4 is disposed in the hole 11b of the first piston 11, and the head of the output rod 4 is in contact with the bottom surface of the hole 11b. A support lever 24 is pivotally connected at one of its ends to the housing 1b by a pin 1c for pivotal movement within the boost chamber 20a, and a spherical head on the other end of the support lever 24 is fitted into the through-hole 22b of the reaction piston 22. A control lever 25 is pivotally connected with the support lever 24 by a pin 24a approximately in its center, and one head of the control lever 25 is fitted into the through-hole 5f of the power piston 5. Accordingly, when the reaction piston 22 slides toward the output rod 4 with respect to the power piston 5 which is pressed toward the brake pedal 2, a rotating force is exerted on the support lever 24 so as to pivotally move the support lever 24 clockwise about the pin 1c. At this time, since a lower head of the control lever 25 is retained in the through-hole 5f of the power piston 5, the upper head of the control lever 25 is rotated counterclockwise about the pin 24a and hence moved in the sliding direction of the reaction piston 22. As a result, the upper head of the control lever 25 is displaced in response to movement of the reaction rod 22r until the rod 22r comes into contact with the reaction disk 4a. The housing 1b has a spool-valve bore extending substantially in parallel with the power piston 5 and communicating with the boost chamber 20a, and a spool valve 28 is fitted into the spool-valve bore. The spool valve 28 includes a cylinder 27 and a spool 26 slidably received in a spool bore 27a formed in the cylinder 27 substantially in parallel with the power piston 5, and one end of the spool bore 27a is fluid-tightly plugged by a closure member 27f. Formed axially in the spool 26 is a through-hole 26a, and formed radially is a hole 26b communicating with the through-hole 26a. One end of the spool 26 is positioned in the boost chamber 20a and is connected to one end of a control rod 29. The other end of the control rod 29 is slidably mounted in a recess formed in the housing 1b, and the upper head of the control lever 25 is fitted into a through-hole 29a radially bored in the control rod 29. Between the cylinder 27 and a retainer 29b formed at one end of the control rod 29, a spring 29c is mounted so as to normally urge the spool 26 toward the control lever 25. The through-hole 26a normally opens to the boost chamber 20a at the junction of the spool 26 and the control rod 29. When the control lever 25 is in its initial position, the through-hole 26a of the spool 26 is communicated with the first reservoir chamber 411 of the reservoir 41 and the low-pressure chamber 20b through a hole 27b radially bored in the cylinder 27, a hole 27d communicating with the hole 27b via the peripheral groove formed around the outer surface of the cylinder 27, and the corresponding ports formed in the housing 1b. Thus, the boost chamber 20a is also communicated with the first reservoir chamber 411 of the reservoir 41 via through-hole 26a and hole 26b and is filled with brake fluid under atmospheric pressure. A hole 27c communicating with the power source 40 is formed in the cylinder 27 at a predetermined distance from the hole 27b toward the control rod 29. The hole 27c is normally closed by the peripheral surface of the spool 26. Between the hole 27c and the end of the spool 26 facing the control rod 29, an annular groove 27e is formed on the inner surface of the cylinder 27, and an annular groove 26c is formed on the peripheral surface of the spool 26 in opposing relation to the annular groove 27e. When the spool 26 is moved toward the closure member 27f in response to the movement of the control lever 25, the hole 27b of the cylinder 27 is closed. The hole 27c, in turn, faces the annular groove 26c of the spool 26, and the annular groove 27e faces the annular groove 26c and the hole 26b. Consequently, the hole 27c is communicated with the through-hole 26a. Accordingly, the hydraulic power pressure of the power source 40 is introduced into the boost chamber 20a to increase the hydraulic pressure therein, and the reaction force is thereby transmitted to the brake pedal 2 via the reaction piston 22, and at the same time the raised hydraulic pressure is applied to the first piston 11 via the power piston 5. The power piston 5 moves toward the left until the pin 5h comes into contact with the elongated hole 22a of the reaction piston 22. Thus, the relative position of the control lever 25 and the support lever 24 becomes similar to that of the initial state. Accordingly, the control lever 25 is moved clockwise about the pin 24a to retract the control rod 29 to the right. The hole 27c of the cylinder 27 is thereby closed, and in turn the hole 27b is communicated with the hole 26a of the spool 26 to lower the hydraulic pressure in the boost chamber 20a so that the power piston 5 is moved toward the brake pedal 2. With this operation performed repeatedly, the hydraulic pressure within the boost chamber 20a is regulated to a predetermined boost pressure. Also, a port 20d which is formed in the housing 1b so as to communicate with the boost chamber 20a is in fluid communication with the second fluid chamber 17 of the tandem master cylinder 10 via the third hydraulic passage 73 and the port 17a. Accordingly, the output hydraulic pressure of the boost chamber 20a is supplied to the second fluid chamber 17. The power source 40 comprises an accumulator 44 for generating a hydraulic power pressure along with a fluid pump 43 which is connected to the accumulator 44 via check valve 45 and connected to the reservoir 41 which stores an amount of hydraulic fluid. The power source 40 is arranged to supply the power hydraulic pressure to the necessary regions via the accumulator 44. The fluid pump 43 is operated by a motor 42 which is actuated by an electric control signal from an electric control device (not shown). Namely, the power hydraulic pressure is maintained at a predetermined value by means of an intermittent controlled of the motor by the electric control device in response to the electric control signal from a pressure sensor (not shown). Also, the reservoir 41 is divided into three chambers, namely, the first reservoir chamber 411 communicated with the power source 40 and the hydraulic booster 20, the second reservoir chamber 412 communicated with the first fluid chamber 13 and the third reservoir chamber 413 communicated with the second fluid chamber 17 via the fourth hydraulic passage 73 and the check valve 30. These three reservoir chambers are communicated with each other at their upper ends, i.e., only in the region of the fluid surface, so that the necessary brake fluid quantity in each reservoir chamber is not influenced by a change of the other reservoir chamber. The above-described embodiment of the hydraulic braking system 1 operates as follows. FIG. 1 shows a condition under which the brake pedal 2 is not depressed. In this condition, the first fluid chamber 13 which is communicated with the reservoir 41 is in fluid communication with the first pressure chamber 12 which is communicated with the wheel cylinders 53a and 54a of the rear wheels 53 and 54; thus the brake fluid contained therein is under the pressure in the reservoir 41, namely atmospheric pressure. The power hydraulic pressure of the power source 40 is supplied to the hole 27c. But, in this condition, since the hole 27c is shut, the hydraulic booster 20 is not operated. Also, since the brake fluid in the second pressure chamber 16 and the second fluid chamber 17 is in fluid communication with atmospheric pressure in the reservoir 41 via the port 17a, the third hydraulic passage 73, the port 20d, the boost chamber 20a and the hole 27b the brake fluid in the wheel cylinders 51a and 52a (which is communicated with the second pressure chamber 16 via the port 16a and the second hydraulic passage 72) is also at atmospheric pressure. When the brake pedal 2 is depressed, the reaction piston 22 is pushed via the input rod 3 until the reaction rod 22r abuts the reaction disk 4a of the power piston 5. Accordingly, the control lever 25 is rotated counterclockwise relative to the support lever 24 about the axis of the pin 24a so that the head of the control lever 25 pushes the spool 26 to the left. Thus, the hydraulic pressure from the power source 40 is introduced into the boost chamber 20a to push the power piston 5 to the left to apply the boost force to the first piston 11 with the reaction force transmitted to the brake pedal 2 via the reaction piston 22. At the same time, the hydraulic pressure is supplied from the port 20d to the second fluid chamber 17 via the third hydraulic passage 73, and from the second fluid chamber 17 to the second pressure chamber 16 via the small hole 15d and the hole 15e. From the pressure chambers 17, 16 the pressure is supplied to the wheel cylinders 51a and 52a via the second hydraulic passage 72. Also, the second piston 15 is forced to slide toward the first piston 11 against the return spring 14d by the hydraulic pressure introduced into the second fluid chamber 17. This causes the valve rod 14 to become separated from the retainer 14b and move toward the small hole 11d by the spring 14e, so that the valve member 14a closes the small hole 11d fluid-tightly. As a consequence of the motion of the piston 15 toward the piston 11, the volume of chamber 12 is reduced. Thus, there will remain no voids in the hydraulic passage 71 and wheel cylinders 53a, 54a, so that hydraulic braking pressure is transmitted to the wheel cylinders 53a and 54a as soon as the first piston 11 is caused to slide by the power piston 5. Meanwhile, in the boost chamber 20a, the hydraulic pressure is kept at the predetermined boost pressure since the spool valve 28 will be operated by the control lever 25 in response to relative displacement of the power piston 5 as explained earlier herein. As will be appreciated from the foregoing explanation, since the brake hydraulic pressure is transmitted to the wheel cylinders 51a and 52a by the hydraulic booster 20 before the first piston 11 slides, the stroke of the brake pedal 2 is shortened, and since the valve member 14a closes the small hole 11d in response to the movement of the second piston 15 toward the first piston 11 before the first piston 11 slides, no idle (non-working) stroke of the first piston 11 will occur since the movement of the second piston 15 eliminates all voids in the first pressure chamber 12. Further, the brake fluid of first stage fills the hydraulic circuit communicated with the first pressure chamber 12 in response to the decrease of the volume of the first pressure chamber 12 produced by the sliding of the second piston 15; hence, the stroke of the brake pedal 2 required to decrease of the volume of the first pressure chamber 12 is reduced. Thus, the increasing of the brake hydraulic pressure occurs rapidly whereby the magnitude of the braking force with respect to the magnitude of the stroke of the brake pedal 2 is a linear relationship. Also, in the event that the operation of the power source ceases and the power pressure is lost, a negative pressure will be generated in the boost chamber 20a and the second chamber 17 since the volume of the boost chamber 20a is expanded by the sliding of the power piston 5 in response to the operation of the brake pedal 2. However, this causes the check valve 30 to be opened, whereupon the second fluid chamber 17 (which defines a fluid conduit together with the hydraulic booster 20) is communicated with the third reservoir chamber 413 of the reservoir 41 via the fourth hydraulic passage 74. Therefore, the necessary brake fluid is supplied to the second fluid chamber 17, and the hydraulic pressure of the brake fluid in the second fluid chamber 17 is controlled to about atmospheric pressure without the generation of a negative pressure therein. Accordingly, the boost function of the hydraulic booster 20 ceases, but in the tandem master cylinder 10, since the hydraulic pressure in the first pressure chamber 12 is increased (by the sliding movement of the first piston 11 in response to the depression of the brake pedal 2) and the hydraulic pressure in the second pressure chamber 16 is increased (by the sliding movement of the second piston 15 due to the increase of pressure in the first pressure chamber 12), the system operates as an ordinary tandem master cylinder having a stable braking force. As mentioned above, in this embodiment, since the hydraulic braking system operates the same as an ordinary tandem master cylinder when the hydraulic pressure of the power source 40 has been lost, the first hydraulic passage 71 and the second hydraulic passage 72 defining the two hydraulic circuits can be connected individually to the front-rear wheels without the need for a more complicated hook-up. FIG. 3 shows a second embodiment of the present invention. In FIG. 3, the same parts as compared with FIG. 1 are identified by the same reference numerals as in FIG. 1. The main difference between FIG. 1 and FIG. 3 is that the fourth hydraulic passage 74 extends to the hydraulic booster portion of the fluid conduit defined by the booster and the second fluid chamber 17, and that the check valve 30 is provided in the hydraulic booster 20. Namely, the check valve 30 is fitted and fixed into a port 1d formed in the housing 1b. Thus, the third reservoir chamber 413 of the reservoir 41 is communicated with the boost chamber 20a via the fourth hydraulic passage 74, the check valve 30, the hole 27g formed in the housing 1b, the spool bore 27a and the through-hole 26a. Now, in this embodiment, since the operation is same as the operation of the embodiment shown in FIG. 1, a detailed description is unnecessary. FIG. 4 shows a third embodiment of the present invention. In FIG. 4, the same parts as compared with FIG. 1 are identified by the same reference numerals utilized in FIG. 1. The main difference between FIG. 1 and FIG. 4 is that a cut-off valve 60 is disposed in the third hydraulic passage 73, and check valve 61 is disposed in the third hydraulic passage 73 in a line disposed parallel with the cut-off valve 60. The cut-off valve 60 is a two port-two position solenoid operated directional control valve arranged for opening or closing the third hydraulic passage 73 upon energization of a solenoid coil 60a by a relay 62 controlled in response to the electric output signal from a fluid sensor 41a provided in the reservoir 41. The cut-off valve 60 is constituted as a normal open valve in this embodiment. Accordingly, the boost chamber 20a is normally in fluid communication with the second fluid chamber 17. When an insufficiency of brake fluid is detected by the fluid measure sensor 41a, the relay 62 is operated and the solenoid coil 60a is energized to close the third hydraulic passage 73. Alternatively, the cut-off valve 60 may function such that the closing of the valve requires an energization of the solenoid. Also, the cut-off valve 60 may be operated in response to a pressure sensor (not shown) which detects the output hydraulic pressure of the power source 40 instead of the fluid quantity sensor 41a. The check valve 61 functions to accelerate the return of the brake fluid from the second fluid chamber 17 to the boost chamber 20a of the hydraulic booster 20 under the opening condition of the cut-off valve 60. When the output hydraulic pressure of the hydraulic booster 20 has been lost, the valve member 18a closes the small hole 15d by the sliding movement of the second piston 15 due to the brake pressure of the first pressure chamber 12, and then the brake pressure of the second pressure chamber 16 is increased and the operation of the system as an ordinary tandem master cylinder is ensured, as in the first embodiment. When the brake fluid level in the reservoir 41 lowers so that an electric output signal from the fluid measure sensor 41a is generated, the relay 62 is operated and the cut-off valve 60 is closed. However, if there has occurred not only a loss of output hydraulic pressure of the hydraulic booster 20, but also a lowering of the output hydraulic pressure of the hydraulic booster 20 to a valve below the hydraulic pressure in the second fluid chamber 17, the brake fluid in the second fluid chamber 17 flows to the hydraulic booster 20 through the check valve 61. In the absence of the check valve, the necessary brake fluid would be unavailable when the volume of the second pressure chamber 16 is expanded. But in this embodiment, in the first embodiment shown in FIG. 1, the necessary brake fluid measure is supplied from the third reservoir chamber 413 of the reservoir 41 to the second fluid chamber 17 via the check valve 30, so that the fourth hydraulic passage 74 and the second fluid chamber 17 is maintained at about atmospheric pressure. When a leakage of the brake fluid occurs in a hydraulic circuit including the wheel cylinders 51a and 52 of front wheels 51 and 52, the brake fluid level in the reservoir 40 is decreased and a signal from the fluid measure sensor 41a is generated. In response, the cut-off valve 60 is closed. In this case, too, as mentioned above, the brake fluid is supplied to the second fluid chamber 17 via the check valve 30. However, the outflow of the brake fluid is restricted to the third reservoir chamber 413 of the reservoir 41, so that the presence of sufficient brake fluid in the first and second reservoir chambers 411, 412 is ensured. Accordingly, an outflow of the boost pressure to the hydraulic circuit communicated with the second pressure chamber 16 is prevented and the braking force is operated at the rear wheels 53 and 54 during operation of the hydraulic booster 20. Now, since the remaining structure, operation and the effect of FIG. 4 are as same as in the first embodiment shown in FIG. 1, no further explanation is necessary. As mentioned above, according to the present invention, as to the hydraulic circuit communicated with the second pressure chamber of the tandem master cylinder, the stroke of the brake pedal is shortened since the output pressure of the hydraulic booster is transmitted to the second fluid chamber of the tandem master cylinder, (the second piston does not slide after the first piston slides). Further, the need to reduce the volume of the pressure chamber is fulfilled by the sliding movement of the second piston toward the first piston during the first stage of the depression of the brake pedal, rather than be fulfilled by a sliding of the first piston. Thus, it is possible to shorten the stroke of the brake pedal. Further, according to the present invention, in case negative pressure is generated in the second fluid chamber due to a stopping of the operation of the power source, the second fluid chamber is communicated with the reservoir via the check valve. Thus, since the second fluid chamber is maintained at about atmospheric pressure and sufficient brake fluid is supplied to the second fluid chamber, it is ensured that a stable braking force will occur without the creation of either: (i) a shortage of brake fluid for the subsequent brake releasing operation or (ii) an excessive loss of braking force by the negative pressure. Moreover, due to the use of a check valve, it is not necessary to form the pressurizing reservoir in the master cylinder as shown in the prior art. Thus, the invention can be easily incorporated in an existing hydraulic braking system. Although certain specific embodiments of the present invention have been shown and described it is apparent that many modifications thereof are possible. The present invention, therefore, is not intended to be restricted to the exact showing of the drawings and description thereof, but is considered to include reasonable and obvious equivalents thereof.
A tandem master brake cylinder has first and second pistons, each piston associated with a fluid chamber and a pressure chamber. The pistons are displaced in response to actuation of a brake pedal. A hydraulic booster is coupled to a power source and is operable to enhance the piston movement and for conducting pressurized fluid to a second of the fluid chambers associated with a second piston to displace that piston in a manner reducing the volume of the pressure chamber associated with the first piston. In the event that a negative pressure is communicated with the second fluid chamber, e.g. by a loss of pressurized fluid from the power source, brake fluid is supplied through a one-way check valve to the second fluid chamber to prevent the negative pressure from reversing the motion of the second piston.
1
BACKGROUND OF THE INVENTION [0001] 1. Field of the Invention [0002] The present invention relates to a process of producing high content natural carotenoids, especially relating to Escherichia coli ( E. coli ) that may produce high content carotenoids through genetically engineered modifications, and its high cell density fermentation process and recovery and purification method. [0003] 2. Description of the Prior Art [0004] Utilizing genetic engineering technology to generate exogenous proteins as medical purpose proteins is a well known process in biotechnology, however, other than proteins, there are many other secondary metabolites that are essential to the human body, such as vitamins etc. Carotenoid is a natural pigment that may be applied to feed additives, food additives, cosmetic manufacturing etc. and is abundant in a number of common plants and microorganisms, at the present, more than 600 carotenoids have been identified. With the advances and analysis in molecular biology, various metabolic pathways for carotenoids are continually being discovered, as shown in FIG. 1 . Within these varieties of carotenoids, only a few may be chemically synthesized for commercial production, and some may be extracted from natural sources or obtained through fermentation (P. C. Lee, 2002), thus, utilizing biotechnology to produce these types of chemical compounds is a target that scientists are hoping to achieve. [0005] Lycopene is the first metabolite to form colors in the previously mentioned metabolic paths of carotenoids, the synthesis path may be formed from pyruvate and glyceraldehyde-3-phosphate (G-3-P) after a series of reduction, dehydration, phosphorylation and other biochemical reactions. It can be further catalyzed into β-carotene, zeaxanthin, β-cryptoxanthin, canthaxanthin and astaxanthin etc. (refer to FIG. 1 ) through cyclic reaction catalyzed by different cyclases. Lycopene have been recognized as an industrially important natural food coloring agent due to its high safety and high staining power in the red region. Recently, lycopene has been proved to be a strong antioxidant which neutralizes free radicals, especially those derived from oxygen and also has the ability of inhibiting LDL (low-density lipoprotein) oxidation. This will result in reducing cholesterol levels in the blood and prevent the body from the attacks of free radicals. [0006] Clinic researches have shown that lycopene has the potency to protect against prostate cancer, breast cancer and cardiovascular disease. In addition, other preliminary researches also suggest that lycopene may reduce the risk of macular degeneration, serum lipid oxidation and cancers of the lung, bladder, cervix and skin. Some of the chemical properties and effects of lycopene mentioned above may be referred to the publications by Giovannucci et al. in J. Natl. Cancer Inst. 87(23):1767-1776, Dec. 6, 1995, and Morris et al. in J. Amer. Med. Assoc. 272(18):1439-1441, 1994. [0007] The existing productions of lycopene are carried out via chemical synthesis (produced by BASF and DSM), where lycopene is produced through the extraction of tomatoes and fermentation of Blakeslea trispora (refer to U.S. Pat. Nos. 3,097,146 and 3,369,974), on the other hand, productions via biotechnology are still mainly at the research and development stage, for instance, in 2006, Yoon et al. utilized the recombination of E. coli to produce lycopene, and have achieved the content of 102 mg/L in 72 hours. In 2005, Kang et al. utilized the common performance of other related genes, and have achieved the content of 4.7 mg/g under shake flask incubation. In 2007, Jin YS also employed the genes' common performance and destruction method to achieve a lycopene yield of 16 mg/g under shake flask incubation. [0008] In order to raise the lycopene yield, the research conducted by W. R. Farmer et al. pointed out that the precursor of carotenoids, isopentenyl pyrophosphate (IPP) is composed of pyruvate and glyceraldehydes-3-phosphate (G-3-P), thus, the critical gene (pykFA) associated with the reverse reaction of glycolysis in the E. coli chromosome DNA has been blocked to increase the pyruvate and glyceraldehydes-3-phosphate (G-3-P) contents, also raising the IPP content and therefore increase the yield for carotenoids (as published by W. R., Farmer and J. C., Liao in Biotechnol. Prog. Vol. 17 Pg. 57-61, 2001). [0009] In addition, if bacteria are used to mass represent exogenous genes, it would usually result in the imbalance of metabolism, thus cause the feedback inhibition mechanism. In order to prevent the activation of feedback inhibition mechanism, J. C. Liao has utilized the saccharide metabolism (acetyl phosphate, ACP), NRI (glnG product) and glnAP2 promoter to form a dynamic control ring to further control idi (isopentenyl diphosphate isomerase, isoenzyme of IPP) genes, thus raising the lycopene yield (U.S. Pat. No. 7,122,341 and as published by W. R., Farmer and J. C., Liao in Nature Biotechnology Vol. 18 Pg. 533-537, 2000). [0010] According to the biosynthetic pathway of carotenoids, once lycopene is catalyzed by lycopene cyclase enzymes (crtY) and β-carotene hydroxylase (or crtZ), it may be biosynthesized into zeaxanthin. In the daily diet, zeaxanthins are mainly found in cabbages, spinaches, leaf mustards, corns and other vegetables (as published by A R. Mangels et al. in J. Am. Diet Assoc . Vol. 93 Pg. 284-296, 1993), it cannot be synthesized by the human body and needs to be assimilated from foods. Researches have shown that zeaxanthin can be found within the milk and blood of the human body (as published by F. Khachik et al. in Investig. Ophthamol. Vis. Sci . Vol. 38 Pg. 1802-1811, 1997), thus, the body needs to acquire zeaxanthin via food assimilation. The main physiological activities of zeaxanthin are centralized at the cornea region and the eye cells to absorb the anti-oxidation effect of free radicals. In addition, it clearly offers protection against age-related macular degeneration (AMD) caused by long term ultraviolet (UV) rays and photolethal effects, and against cataracts caused by aging of eye lens (as published by S. Beatty, J. Nolan et al. in Arch. Biochem Biophys Vol. 430 Pg. 70-76, 2004). [0011] Currently, methods for zeaxanthin production are categorized into: fermentation of natural microorganisms, plant extraction, and chemical synthesis. The production of zeaxanthin via fermentation of natural microorganisms has only been used on microorganisms such as Flavobacterium multivorum (U.S. Pat. No. 5,427,783, RE38009E, and U.S. Pat. No. 6,291,204), Neospongiococcum excentrium (U.S. Pat. No. 5,360,730) and Paracoccus (U.S. Pat. No. 5,935,808) etc. The major sources of plant extraction are marigold, alfalfa and Lycium Chinese Mill (LCM) berries (U.S. Pat. Nos. 7,173,745 and 7,109,360). Chemical synthesis methods for zeaxanthin production may be referred to U.S. Pat. Nos. 6,818,798, 6,747,177 and 6,743,954. [0012] During the biosynthesis process of zeaxanthin, the resulting product of β-cryptoxanthin may be obtained via the appropriate truncation of N-terminal amino acid sequences in the β-carotene hydroxylase (as published by Zairen Sun et al. in J. Biol. Chem . Vol. 271 No. 40 Pg. 24349-24353, 1996). β-cryptoxanthin is a type of natural carotenoid commonly contained in yellow or orange vegetables and fruits, such as citruses, mangoes, kiwifruits etc., wherein higher contents of β-cryptoxanthin are found in citrus peels. β-cryptoxanthin not only provides coloring effects and anti-oxidation, it can also be used as the precursor for vitamin A. In addition, recent academic researches have shown that β-cryptoxanthin may lower the risk for developing arthritis. [0013] Due to the previously mentioned beneficial efficacies of β-cryptoxanthin toward the human body, it has become a striving goal for the industry to find a quick and effective way to obtain the substance. The major sources and production methods of β-cryptoxanthin include: (1) chemical synthesis production, such as U.S. Pat. No. 7,115,786, where a method of utilizing lutein as the initial reagent to obtain β-cryptoxanthin and alpha-cryptoxanthin has been disclosed; (2) via the extraction of existing plants, such as the method described by U.S. Pat. No. 6,262,284, where a small amount of β-cryptoxanthin and a considerable quantity of zeaxanthin may be obtained through the extraction of LCM berries; (3) via the fermentation of microorganisms, such as the fermentation production method utilizing natural microorganisms described in U.S. Pat. No. 5,935,808. [0014] From the biosynthetic pathway of carotenoids, it is known that β-carotene may be biosynthesized into canthaxanthin when β-carotene is catalyzed by β-carotene ketolases (crtW). Usually, canthaxanthin exists naturally in fungi, crustaceans, fishes, green alga and eggs. Canthaxanthins are mainly used as additives for animal feeds, giving salmons, egg yolks and poultry products a light red and brighter color; it may also be applied to jams, candies, syrups, sauces, carbonated drinks and other foods as coloring agent. Canthaxanthins are more commonly used as animal feeds, rather than coloring agents. In fact, salmon is slightly pink in color because it eats shrimps for food, the market acceptance rate would be higher if farmed salmons are able to display the same color, which explains why canthaxanthins are used as food additives; the same goes to poultries, as the skins and egg yolks of poultries may display a brilliant yellow color with the use of canthaxanthins. Using this type of additive does not affect the quality of foods but only change the colors of foods. Canthaxanthin is also found in common plants or microorganisms as a type of photochemical, at present, the major production method for canthaxanthin is production through chemical synthesis. Fermentation production examples utilizing microorganisms have also been documented (Prakash Bhosale, 2005), however, the yield is too low and does not meet the requirements for commercial production. [0015] Astaxanthin is the end product in the biosynthetic pathway of carotenoids, it may be formed via the transformation of canthaxanthin with the help of β-carotene hydroxylase (crtZ), or it can be formed via the transformation of zeaxanthin with the help of β-carotene ketolases (crtW). Astaxanthin generally exists in animals (birds or fishes), plants, alga and microorganisms (especially yeasts), it is a natural coloring and also a very strong anti-oxidant, with an anti-oxidation ability 500 times than that of vitamin E. Astaxanthins' ability to eliminate reactive oxygen free radicals may be expected to be applied for medical purposes, to treat certain illnesses, such as cancer. At present, astaxanthins are mainly used as coloring agents in industrial applications, by adding astaxanthins into feeds for the cultivation of salmons and trout, red and flavorful meat may be obtained within a short period of time. Also, the anti-oxidation characteristic of astaxanthins is also widely applied to skin care and cosmetic products. [0016] There are mainly three types of production methods for astaxanthin: extraction method, chemical synthesis method (U.S. Pat. No. 2005/0214897) and fermentation method. Extraction methods are mainly applied to crustaceans and flowers of plants (Adonis aestivalis, refer to U.S. Pat. No. 5,453,565). Yeasts and alga are used to produce astaxanthins in most fermentation methods, the most widely used yeast is usually improved strains of Phaffia Rhodozyma or changing the nutrient medium to improve its yield (Taiwan Pat. No. 83100549 and U.S. Pat. No. 5,356,809), U.S. Pat. No. 2005/0124032 utilizes Xanthophyllomyces Dendrorhous to produce astaxanthin, its yield may reach 425 mg/L. On the other hand, green alga ( Chlorella zofingiensis ) may also be used for the fermentation production of astaxanthin (U.S. Pat. No. 2005/0214897). If red alga Haematococcus (U.S. Pat. No. 6,022,701) is used for the production, light source and a longer cultivation time would be required. The production methods mentioned above are not only time consuming but would also result in low yields. [0017] From the above, it can be seen that at present, the key methods for producing carotenoid products include chemical synthesis, natural extraction and fermentation, each with their own problems and shortcomings. For example, chemical synthesis may be difficult to synthesize due to the complexity of carotenoid structures, or chemical synthesis may produce some isomers that do not exist in nature. If natural extraction is employed, it will be limited by the low content and purity of the original material; if fermentation is used, it would usually be limited to producing one single product per bacterium. [0018] In view of the above, the present invention is based on metabolic control (U.S. Pat. No. 7,122,341), where a strain is obtained through classical and genetic engineering strain improvement, it may produce high yield carotenoid compounds under the existence of carotenoid biosynthetic genes and regulatory genes, and via high cell density fermentation, in addition, these compounds include lycopene, zeaxanthin, β-cryptoxanthin, canthaxanthin and astaxanthin. SUMMARY OF THE INVENTION [0019] The present invention is mainly based on the metabolic engineering control method suggested by Liao et al. (2000), and further performs strain improvement to obtain a higher lycopene yield production strain, at the same time, based on the biosynthetic pathways, further constructs production strains for other compounds, such as zeaxanthin, β-cryptoxanthin, canthaxanthin and astaxanthin etc. with the assistance of high cell density fermentation technology, and recovery purification technology. The present invention has already dealt with the bottleneck problem of producing carotenoids with biotechnology, and has reached the goal of commercial production. The present invention provides a mode of production utilizing biological cell factories, and techniques involved with respect to a series of products will be described in detail below, in order to show the technical characteristics of the present invention. [0020] The present invention will describe in detail some preferred embodiments. However, it should be noted that other than these detailed descriptions, the present invention may be practiced in a wider range of other embodiments besides those explicitly described, and the scope of the present invention is not expressly limited except as specified in the accompanying claims. [0021] The present invention provides a biological cell platform for diversified production of large quantities of carotenoids, which, along with high cell density fermentation technology, will be able to produce high yield and high purity carotenoid products within a short period. [0022] The object of the present invention is to provide a process of carotenoid production, which, through genetically engineered modification of Escherichia coil ( E. coli ) may produce high content carotenoids. [0023] Another object of the present invention is to provide a process of carotenoid production, which provides the high cell density fermentation process of E. coli for producing carotenoids. [0024] Yet another object of the present invention is to provide a process of carotenoid production, which provides the recovery purification method for carotenoids. [0025] The present invention is related to a process for the creation of genetically engineered bacteria, and in coordination with high cell density fermentation for the rapid mass production to attain high purity through recovery purification. [0026] The process described by the present invention involves the following steps: [0027] (a) host screening for the genetically engineered bacteria: using lycopene as the index, screen for a host with a high yield of carotenoids. First, JCL1613 (host for BCRC940321) is used as the host to produce lycopene; the genes for producing lycopene, including dxs, gps, crtB and crtI are created in plasmid PCL1920, this particular plasmid carrying multiple genes is named mp25, while the plasmid carrying gene idi and promoter glnAP2 is named p2IDI. mp25 and p2IDI is to be transformed within the JCL1613 host, to further employ physical (UV) mutation method to improve the strain, utilizing 50 mL shake flask for screening. A mutated strain can be obtained after JCL1613 goes through UV mutation screening, this mutated strain is called M2H, and it may produce a higher quantity of carotenoids. [0028] (b) creating plasmids for the production of zeaxanthin, β-cryptoxanthin, canthaxanthin and astaxanthin, such as FIG. 5A to FIG. 8B : wherein the genes crtY and crtZ are cloned within Erwinia uredovora ; crtW genes are cloned within Brevundimonas sp.; and genes for β-carotene hydroxyl enzymes with N terminal defects (code bh4; crtZde genes) are cloned within Arabidopsis thaliana . The crtY genes are constructed in mp25, forming mp25y or mpy; crtZ genes are constructed in mp25y, forming mp25yz; crtZ genes are constructed in p2IDI, forming pz16; crtW genes are constructed in p2IDI, forming w-p2IDI; crtZde(bh4) genes are constructed in p2IDI, forming pI12; crtW-idiglnAP2 genes are constructed in pz16, forming pwizI6, plasmids mp25yz and zI6, mp25y and pI12, mpy and w-p2IDI, mp25yz and pwizI6 are respectively transferred into host M2H, in order to obtain the production strains for producing zeaxanthin, β-cryptoxanthin, canthaxanthin and astaxanthin. [0029] (c) utilizing these carotenoids to produce strains for performing the optimization of high cell density fermentation. [0030] (d) using the centrifugal method in collaboration with spray drying for the recovery of cells. [0031] (e) using solvents or supercritical extraction method to recover and purify these carotenoids to obtain high yield and high purity lycopene, zeaxanthin, β-cryptoxanthin, canthaxanthin and astaxanthin. [0032] After performing the steps described above, the fermentation of lycopene bacteria may reach 1250 mg/L, and the lycopene purity may reach 96% and above after recovery and purification; the fermentation of zeaxanthin bacteria may reach 1020 mg/L, and the zeaxanthin purity may reach 96% and above after recovery and purification; the fermentation of β-cryptoxanthin bacteria may reach 610 mg/L, and the β-cryptoxanthin purity may reach 85% and above after recovery and purification; the fermentation of canthaxanthin bacteria may reach 1200 mg/L, and the canthaxanthin purity may reach 98% and above after recovery and purification; the fermentation of astaxanthin bacteria may reach 650 mg/L, and the astaxanthin purity may reach 90% and above after recovery and purification. [0033] The lycopene bacteria mp25/p2IDI (in E. coli . M2H), zeaxanthin bacteria mp25yz/pzI6 (in E. coli . M2H), β-cryptoxanthin mp25y/pI12 (in E. coli . M2H), canthaxanthin mpy/w-p2IDI (in E. coli . M2H) and astaxanthin mp25yz/pwizI6 (in E. coli . M2H) used for production in the present invention have been deposited into the Culture Collection Centre within the Food Industry Research and Development Institute in Taiwan on the 29 Apr. 2008, in compliance with the Taiwan Patent Law Article 30, and the deposit numbers are BCRC940542, BCRC940543, BCRC940540, BCRC940541 and BCRC940539 respectively. BRIEF DESCRIPTION OF THE DRAWINGS [0034] The foregoing aspects, and other features and advantages of the present invention will become more apparent by reference to the following detailed descriptions when taken in conjunction with the accompanying drawings, wherein: [0035] FIG. 1 illustrates the biosynthetic pathway diagram of the carotenoids in E. coli . according to the present invention; [0036] FIG. 2 illustrates the flow chart for the process of obtaining biosynthesized carotenoids from mutated bacteria or natural bacteria according to the present invention; [0037] FIG. 3 illustrates the yield comparison diagram for different hosts according to the present invention; [0038] FIGS. 4A to 4B illustrate the plasmid diagrams for lycopene production according to the present invention; [0039] FIGS. 5A to 5B illustrate the plasmid diagrams for zeaxanthin production according to the present invention; [0040] FIGS. 6A to 6B illustrate the plasmid diagrams for β-cryptoxanthin production according to the present invention; [0041] FIGS. 7A to 7B illustrate the plasmid diagrams for canthaxanthin production according to the present invention; [0042] FIGS. 8A to 8B illustrate the plasmid diagrams for astaxanthin production according to the present invention; [0043] FIG. 9 illustrates HPLC diagram for lycopene after fermentation and purification according to the present invention; [0044] FIG. 10 illustrates HPLC diagram for zeaxanthin after fermentation and purification according to the present invention; [0045] FIG. 11 illustrates HPLC diagram for β-cryptoxanthin after fermentation and purification according to the present invention; [0046] FIG. 12 illustrates HPLC diagram for canthaxanthin after fermentation and purification according to the present invention; [0047] FIG. 13 illustrates HPLC diagram for astaxanthin after fermentation and purification according to the present invention. DESCRIPTION OF THE PREFERRED EMBODIMENT [0048] In the following description, numerous specific details are provided in order to give a thorough understanding of the embodiments of the invention. The present invention is described in detail below, along with the preferred embodiments and accompanying drawings, it should be recognized that all the preferred embodiments are for the purpose of illustration only, and not for the purpose of limiting the present invention. Those skilled in the relevant art will recognize, however, that the invention may be practiced without one or more of the specific details, or with other methods, components, materials, etc. [0049] The present invention discloses a process for the rapid mass production of different carotenoids through the utilization of bacteria. The present invention utilizes the improved bacteria via UV mutation, and the improved bacteria are suitable hosts for E. coli producing high yield carotenoids. The process of producing carotenoids from E. coli utilizes the UV mutated, improved bacteria host in order to create genetically engineered bacteria that are able to produce carotenoids and are suitable for high cell density fermentation, then the genetically engineered bacteria are mass produced via high cell density fermentation followed by recovery and purification process in order to obtain high content carotenoids or different kinds of high purity carotenoid crystals. [0050] The present invention discloses a process for obtaining biosynthesized carotenoids via mutated bacteria, please refer to FIG. 2 for the process flow chart of the present invention, the process includes: step 10, screening for high yield biosynthesized carotenoid bacteria; step 12, creating carotenoid plasmids; step 14, carrying out high cell density fermentation to produce carotenoid cells; step 16, recovering the cells and performing purification to obtain carotenoid crystals. [0051] The steps involved in the method disclosed by the present invention are described in detail below: [0052] (1) Step 10, screening for high yield biosynthesized carotenoid bacteria: i.e. screening the host for genetically engineered bacteria. Using lycopene as an index, screening the host for high carotenoid yields, please refer to FIG. 3 . Firstly, the patented strain BCRC940321 for producing lycopene has been purchased from the Food Research Institute, and the host of this patented strain, JCL1613 is purified. The genes for biosynthesizing lycopene dxs, gps, crtB and crtI are created in plasmid PCL1920, this plasmid with multiple genes is called mp25. In addition, the patented strain BCRC940323 has been purchased from the Food Research Institute, wherein the plasmid with idi and glnAP2 genes is called p2IDI. mp25 and p2IDI is transformed in the JCL1613 host, physical (UV) mutation method is further utilized to improve the strain, then selecting the portion with 99% death rate, and use the 50 mL shake flask incubation to perform the screening. Through the screening of JCL1613 by ultraviolet (UV) light mutation, a second generation strain called M2H is obtained, and this strain is able to produce a higher yield of lycopene and carotenoids. [0053] (2) Step 12, creating carotenoid plasmids: i.e. creating the genetically engineered production bacteria for producing related carotenoids. Firstly, crty and crtz genes are cloned from Erwinia uredovora , crtw gene is cloned from Brevundimonas sp. and β-carotene hydroxyl enzymes with N terminal defects (bh4 genes) genes are cloned from Arabidopsis thaliana . By constructing these genes in suitable plasmids, and transformed in E. coli respectively, they may be able to biosynthesize genetic recombination strains such as lycopene, zeaxanthin, β-cryptoxanthin, canthaxanthin and astaxanthin etc., please refer FIG. 4A to FIG. 8B for the related plasmids diagrams of each production strain. [0054] (3) Step 14, carrying out high cell density fermentation to produce carotenoid cells: i.e. the fermentation of high cell density bacteria to produce the related carotenoids. After hundreds of researches and experiments regarding fermentation conditions have been carried out, the optimum fermentation conditions for the production bacteria that have been improved through genetic recombination are listed below: [0055] A: each liter of seed strain medium include 10 grams of yeast extract, 10 grams of peptone and 10 grams of glycerol; [0056] B: each liter of batch medium include 36 grams of yeast extract, 10.7 grams of dibasic potassium phosphate, 5.4 grams of monobasic potassium phosphate, 10 grams of glycerol, antibiotics Ampicillin (100 ppm) and Streptomycin (200 ppm); [0057] C: each liter of feeding medium include 60 grams of yeast extract, 90 grams of mixed amino acid powder, 10 grams of magnesium sulfate, 60 grams of monosodium glutamate (MSG), 650 grams of glycerol, antibiotics Ampicillin (200 ppm) and Streptomycin (400 ppm); [0058] Cultivation temperature of 28-32° C.; ventilation of 0.3-1.0 vvm; after approximately 96 hours of high cell density fermentation, the dry weight of the bacteria may reach 75-100 grams per liter, wherein the cell weight of lycopene content in the lycopene production strain is roughly 10-15 mg/g, the cell weight of zeaxanthin content in the zeaxanthin production strain is roughly 8-12 mg/g, the cell weight of β-cryptoxanthin content in the β-cryptoxanthin production strain is roughly 5-10 mg/g, the cell weight of canthaxanthin content in the canthaxanthin production strain is roughly 10-20 mg/g, and the cell weight of astaxanthin content in the astaxanthin production strain is roughly 5-10 mg/g. In order to obtain higher yields and higher purity products, minor parameter adjustments during the high cell density fermentation process to suit different production strains may be carried out. [0059] (4) Step 16, recovering the cells and performing purification to obtain carotenoid crystals: utilizing centrifugal method with spray drying to recover cells with carotenoid contents, and using the solvent purification method to extract high purity and high yield carotenoid crystals. The detailed steps are as follows: adding extraction solvent to extract cells with carotenoids; removing the solid state portion of carotenoid cells, and filtering the liquid state portion of carotenoid cells; condensing the carotenoid cells to obtain a crystalline substance; adding solvent to dissolve impurities so the crystalline substance suspends evenly, separating crystalline substance and impurities via filtering; performing drying process on the crystalline substance to obtain high purity carotenoids. The extraction solvent includes dichloromethane and acetone, and solvent includes methane and alcohol. Comparisons Between High Yield Gene Recombination Hosts [0060] At first, plasmids with biosynthesized lycopene genes are transformed within host JCL1613, creating a strain M1I that is able to produce lycopene. M1I uses the Luria Broth (LB) medium to process overnight cultivation, the bacterial broth is irradiated under UV for 10 minutes (death rate of 99%) and placed in the dark room for 1 hour, the bacterial broth, after being diluted under an appropriate ratio is applied onto the culture plate comprising antibiotics, it is then placed in the incubator at 37° C. for 48 hours, perform a preliminary screen for the bacterial colony with the redder color, and shake culture for 24 hours at 37° C. in the LB medium comprising 1% glycerol, then use OD600 to measure the cell biomass, and utilize acetone to extract lycopene from the cells and measure the content, the results have shown that the lycopene content in this cell is higher than M1I, thus the strain that has been improved by ultraviolet (UV) light is named M2I, and its host is known as M2H. At the same time, plasmids with biosynthesized lycopene genes are transformed within hosts JM109, JCL1613 and M2H (i.e. strains that may produce lycopene JM1091, M1I and M2I), shake culture for 24 hours at 37° C. in the LB medium comprising 1% glycerol, the results are shown in FIG. 3 , the lycopene yield of M2I is 38.8 mg/L (9.8 mg/g dry weight), which is higher than M1I, it is 3 times more than M1I and 13 times more than JM109. Embodiment 1—Lycopene High Cell Density Fermentation [0061] Lycopene seed strain (M2I) is connected into the 50 ml/250 ml shake flask via −80° C. holding tube, and placed in an incubator at 32° C., 150 rpm for activation. After 8 hours, take out the shake flask and reconnect the seed strain to a 2 L/5 L fermentor, and continue to culture at a temperature of 30° C., mixing speed of 400 rpm and ventilation of 2 L/min. When the bacteria count/OD600 in the fermentor reaches 15˜25, start to add feeding medium, continue to culture, and control the pH value to stay between 6.8˜7.2. The total fermentation time takes 96 hours and the yield is 1250 mg/L (HPLC purity is 96%). High Cell Density Fermentation and Recovery Purification [0062] Lycopene seed strain is connected into the 50 ml/250 ml shake flask via −80° C. holding tube, and placed in an incubator at 32° C., 150 rpm for activation. After 8 hours, take out the shake flask and reconnect the seed strain to a 4 L/5 L fermentor to continue culturing, the activation conditions are controlled at a temperature of 30° C., mixing speed of 400 rpm and ventilation of 2 L/min for culturing seed strain (II). After culturing seed strain (II) for approximately 14 hours (OD600 is 22.8 at this moment), connect the bacterial broth to the 400 L/1 KL fermentor to continue culturing, the fermentation conditions are controlled at a temperature of 30° C., mixing speed of 120 rpm and ventilation of 400 L/min for culturing; when the bacteria count/OD600 reaches 14.5, start to add feeding medium to culture, and control the pH value to stay between 6.8˜7.5. The total fermentation time takes 96 hours and the yield is 880 mg/L (HPLC purity is 96%). After washing, spray drying and using the solvent to extract and purify the fermentation broth, lycopene crystalline powder with the purity of 97% (refer to FIG. 9 ) and weighing 320 g may be obtained. Embodiment 2—Zeaxanthin High Cell Density Fermentation [0063] Zeaxanthin seed strain is connected into the 50 ml/250 ml shake flask via −80° C. holding tube, and placed in an incubator at 32° C., 150 rpm for activation. After 8 hours, take out the shake flask and reconnect the seed strain to a 2 L/5 L fermentor, and continue to culture at a temperature of 30° C., mixing speed of 400 rpm and ventilation of 2 L/min. When the bacteria count/OD600 in the fermentor reaches 20, start to add feeding medium, continue to culture, and control the pH value to stay between 7.0˜7.5. The total fermentation time takes 100 hours and the yield is 1020 mg/L (HPLC purity is 82%). High Cell Density Fermentation and Recovery Purification [0064] Zeaxanthin seed strain is connected into the 50 ml/250 ml shake flask via −80° C. holding tube, and placed in an incubator at 32° C., 150 rpm for activation. After 10 hours, take out the shake flask and reconnect the seed strain to a 4 L/5 L fermentor to continue culturing, the activation conditions are controlled at a temperature of 30° C., mixing speed of 400 rpm and ventilation of 2 L/min for culturing seed strain (II). After culturing seed strain (II) for approximately 14 hours (where OD600 is 25 at this moment), connect the bacterial broth to the 400 L/1 KL fermentor to continue culturing, the fermentation conditions are controlled at a temperature of 30° C., mixing speed of 120 rpm and ventilation of 400 L/min for culturing; when the bacteria count/OD600 reaches 15, start to add feeding medium to culture, and control the pH value to stay between 7.0˜7.5. The total fermentation time takes 98 hours and the yield is 850 mg/L (HPLC purity is 81%). After washing, spray drying and using the solvent to extract and purify the fermentation broth, zeaxanthin crystalline powder with the purity of 98% (refer to FIG. 10 ) and weighing 250 g may be obtained. Embodiment 3—β-cryptoxanthin High Cell Density Fermentation [0065] β-cryptoxanthin seed strain is connected into the 50 ml/250 ml shake flask via −80° C. holding tube, and placed in an incubator at 32° C., 150 rpm for activation. After 8 hours, take out the shake flask and reconnect the seed strain to a 2 L/5 L fermentor, and continue to culture at a temperature of 30° C., mixing speed of 400 rpm and ventilation of 2 L/min. When the bacteria count/OD600 in the fermentor reaches 20, start to add feeding medium, continue to culture, and control the pH value to stay between 7.0˜7.5. The total fermentation time takes 96 hours and the yield is 610 mg/L (HPLC purity is 68.1%), refer to FIG. 11 . Embodiment 4—Canthaxanthin High Cell Density Fermentation [0066] Canthaxanthin seed strain is connected into the 50 ml/250 ml shake flask via −80° C. holding tube, and placed in an incubator at 32° C., 150 rpm for activation. After 8 hours, take out the shake flask and reconnect the seed strain to a 2 L/5 L fermentor, and continue to culture at a temperature of 30° C., mixing speed of 400 rpm and ventilation of 2 L/min. When the bacteria count/OD600 in the fermentor reaches 25.3, start to add feeding medium, continue to culture, and control the pH value to stay between 6.8˜7.2. The total fermentation time takes 96 hours and the yield is 1178.6 mg/L (HPLC purity is 78.1%). High Cell Density Fermentation and Recovery Purification [0067] Canthaxanthin seed strain (I) is connected into the 50 ml/250 ml shake flask via −80° C. holding tube, and placed in an incubator at 32° C., 150 rpm for activation. After 8 hours, take out the shake flask and reconnect the seed strain to a 4 L/5 L fermentor to continue culturing, the activation conditions are controlled at a temperature of 30° C., mixing speed of 400 rpm and ventilation of 2 L/min for culturing seed strain (II). After culturing seed strain (II) for approximately 14 hours (where OD600 is 22.8 at this moment), connect the bacterial broth to the 400 L/1 KL fermentor to continue culturing, the fermentation conditions are controlled at a temperature of 30° C., mixing speed of 120 rpm and ventilation of 400 L/min for culturing; when the bacteria count/OD600 reaches 14.5, start to add feeding medium to culture, and control the pH value to stay between 6.8˜7.5. The total fermentation time takes 69 hours and the yield is 866.3 mg/L (HPLC purity is 68.8%). After washing and spray drying of the fermentation broth, dried bacterial powder with water content of 8.2% and canthaxanthin content of 5.94 mg/g may be obtained. Then, through solvent extraction, canthaxanthin crystalline powder with the purity of 98% and weighing 220 g may be obtained, refer to FIG. 12 . Embodiment 5—Astaxanthin Creating and Culturing of Production Strains [0068] Utilizing M2H as the host, further create strains that may be biosynthesized as astaxanthin. crty and crtz genes are cloned from Erwinia uredovora , crty is first created at the sac I position of mp25, and crtz is created at the apaI position, this new plasmid is called mp25yz ( FIG. 8A ), at the same time crtz gene is connected into the HindIII position of p2IDI, this new plasmid is called pzI6; on the other hand, crtw gene is cloned from Brevundimonas aurantiaca , this gene is created in pzI6 along with idi and glnAP2, this new plasmid is called pwizI6 ( FIG. 8B ); plasmids mp25yz and pwizI6 are transformed in the M2H host together, forming a new bacteria Ast6 that is able to produce astaxanthin. Ast6 is cultured in the LB comprising AP and SP at 32° C. and shake culture for 24 hours, resulting in an astaxanthin content of 3.7 mg/g DCW and HPLC purity of 59%. High Cell Density Fermentation [0069] Astaxanthin seed strain is connected into the 50 ml/250 ml shake flask via −80° C. holding tube, and placed in an incubator at 32° C., 150 rpm for activation. After 8 hours, take out the shake flask and reconnect the seed strain to a 2 L/5 L fermentor, and continue to culture at a temperature of 30° C., mixing speed of 400 rpm and ventilation of 2 L/min. When the bacteria count/OD600 in the fermentor reaches 15, start to add feeding medium, continue to culture, and control the pH value to stay between 6.8˜7.2. The total fermentation time takes 99 hours and the yield is 1100 mg/L (HPLC purity is 40%). High Cell Density Fermentation and Recovery Purification [0070] Astaxanthin seed strain is connected into the 50 ml/250 ml shake flask via −80° C. holding tube, and placed in an incubator at 32° C., 150 rpm for activation. After 8 hours, take out the shake flask and reconnect the seed strain to a 4 L/5 L fermentor to continue culturing, the activation conditions are controlled at a temperature of 30° C., mixing speed of 400 rpm and ventilation of 2 L/min for culturing seed strain (II). After culturing seed strain (II) for approximately 14 hours (where OD600 is 24.8 at this moment), connect the bacterial broth to the 350 L/1 KL fermentor to continue culturing, the fermentation conditions are controlled at a temperature of 30° C., mixing speed of 120 rpm and ventilation of 400 L/min for culturing; when the bacteria count/OD600 reaches 13.1, start to add feeding medium to culture, and the control conditions is that the pH value needs to be less than or equal to 7.1, when the pH value is greater than 7.1, the system automatically adds the feeding medium into the fermentor. The total fermentation time takes 100 hours and the yield is 411.1 mg/L (HPLC purity is 65.5%). After washing and spray drying of the fermentation broth, dried bacterial powder with water content of 11% and astaxanthin content of 5.24 mg/g (HPLC purity of 52.3%) may be obtained. Then, through solvent extraction, astaxanthin crystalline powder with purity greater than 85% may be obtained, refer to FIG. 13 . Deposit of Microorganisms [0071] The lycopene bacteria mp25/p2IDI (in E. coli . M2H), zeaxanthin bacteria mp25yz/pzI6 (in E. coli . M2H), β-cryptoxanthin mp25y/pI12 (in E. coli . M2H), canthaxanthin mpy/w-p2IDI (in E. coli . M2H) and astaxanthin mp25yz/pwizI6 (in E. coli . M2H) used for production in the present invention have been deposited into the Culture Collection Centre within the Food Industry Research and Development Institute in Taiwan on the 29 Apr. 2008, in compliance with the Taiwan Patent Law Article 30, and the deposit numbers are BCRC940542, BCRC940543, BCRC940540, BCRC940541 and BCRC940539 respectively. [0072] The advantages of the present invention are that it provides a process of obtaining biosynthesized carotenoids from transformed bacteria, provides E. coli that has been modified through genetic engineering processes and is able to produce high content carotenoids, and provides high density culture methods and recovery purification methods for carotenoids. The present invention is able to make use of the improvements in bacteria and constructions of gene combinations and plasmids, utilizing high cell density fermentation production methods to biosynthesize carotenoids, recover and dry so that high content carotenoids may be obtained, thus achieving the goal of effective and rapid production of the required carotenoids via the biological cell factory mode. [0073] An advantage of the present invention is that it utilizes metabolic engineering control method as the basis for proceeding with conventional bacteria improvement, obtains a higher yield lycopene production strain, and further develops this strain into a biological platform for producing large volumes of carotenoids. By building the biosynthetic pathway of carotenoids onto this biological platform, bacteria for producing various types of carotenoids may be formed, such as zeaxanthin, β-cryptoxanthin, canthaxanthin and astaxanthin, etc., accompanied by high cell density fermentation technology, and recovery purification technology. Therefore, the present invention may be able to overcome the existing biotechnology problems for producing carotenoids, and achieve the target of commercial production [0074] As is understood by a person skilled in the art, the foregoing preferred embodiments of the present invention are illustrative of the present invention rather than limiting the present invention. The present invention is intended to cover various modifications and similar arrangements included within the spirit and scope of the appended claims, the scope of which should be accorded the broadest interpretation so as to encompass all such modifications and similar structures.
The present invention relates to a strain of Escherichia coli ( E. coli M2H) for biosynthesis of high yield carotenoids, the steps for obtaining E. coli M2H comprises: purifying the host strain JCL1613 for pCW9/P2IDI; create plasmids for producing carotenoid genes; transform the plasmids into JCL1613; utilizing physical method (UV) to induce and improve JCL1613; select the portions with 99% death rate; utilizing 50 mL shake flask incubation; and go through UV screening to obtain the mutated strain of E. coli M2H.
2
CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of priority from Provisional Patent Application No. 60/720,308 “Combination Cleaning Tool and Plunger” filed Sep. 23, 2005, which is incorporated herein by reference in its entirety. STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH AND DEVELOPMENT Not Applicable. REFERENCE TO A MICROFICHE APPENDIX Not Applicable. BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a dual-use tool for plumbing maintenance in which a cleaning tool and plunger are operably contained in a single shafted tool. The cleaning tool is used to remove unwanted deposits from the surface of a plumbing fixture. The plunger is used to apply pressure to the drain of a plumbing fixture in order to force a collection of debris down the drain that is preventing free flow through the drain. 2. Description of Related Art A combination toilet brush/plunger apparatus is disclosed in U.S. Pat. No. 6,804,839 (McMaster). This combination tool provides a bell-shaped plunger attached to the lower portion of a housing. An upper portion of the housing contains a brush protective guard cylinder with a seal to prevent water ingress to the brush chamber, also located in the upper portion of the housing. The brush is attached to the tool handle and bolted to the housing so the brush handle may be used to operate the plunger. In order to use the brush, the user reaches inside the plunger internal cavity and removes the brush protective guard cylinder and seal. The bolt nuts, which attach the brush to the housing, are then removed from the bolts and the brush and handle may then be removed through the opening of the plunger. The reverse order is required to reattach the brush so as to use the plunger. This is a long and tedious procedure that requires the use of hand tools. This defeats the purpose of a dual-purpose tool by making it very tedious to convert from one use to the other. Also, to many users the act of having to reach inside a potentially contaminated plunger cavity to remove a cylinder and seal is repugnant. Another disadvantage is the device also is prone to loss or damage to the cylinder and seal, which are loose parts when the brush is in use. Another invention claiming to be a combination toilet brush/plunger apparatus is disclosed in US patent application US2005/0125922 (Szarawarski). This combination provides a resilient sponge diaphragm imbedded in a brush assembly. The application claims the sponge diaphragm operates as a toilet plunger. The present applicant's evaluation indicates such a device provides at best a weak plunging action compared to the force available from the conventional bell-shaped resilient plunger, and thus only useful on minor flow impediments. In addition, the use of such a device as a plunger with brush bristles in sewage-contaminated water appears to pose a significant contamination hazard to the user. SUMMARY OF THE INVENTION This invention is a combination-cleaning tool and plunger on a single shaft comprising the shaft, a cleaning tool, a plunger seal, a plunger, a plunger handle and a main handle. The shaft has an upper end and a lower end. The upper end is arranged with a main handle attachment adjacent to an upper plunger handle attachment and the lower end is arranged with a lower plunger handle attachment adjacent to a cleaning tool and plunger seal attachment. The cleaning tool has a body with a cleaning surface, examples are brush bristles or looped fabric strips, and a body attachment arranged to connect to the shaft cleaning tool and plunger seal attachment. The plunger seal is disk-shaped with a central attachment opening and fits around the shaft between the shaft cleaning tool body attachment and the shaft cleaning tool and plunger seal attachment. The plunger has an upper end and a lower end. The upper end has an elastic attachment opening containing an elastic attachment and the lower end has an opening mouth providing a lower end of an internal cavity. The internal cavity upper end connects to the elastic attachment opening and provides a seating surface for the plunger seal to close the elastic attachment opening to the internal cavity contents when using the plunger. The plunger opening mouth is arranged to allow entry of the cleaning tool into the plunger internal cavity. The plunger handle has an upper end, a lower end, an external surface, and a through-hole connecting the upper and lower ends. The through-hole is larger than the shaft outer surface so the plunger handle is movable on the shaft between the shaft upper plunger handle attachment and the lower plunger handle attachment. This provides the means for moving the plunger between the handle and the cleaning tool. The plunger handle upper end through-hole has a shaft connection end attachment to allow the plunger handle to removably connect to the shaft upper plunger handle attachment. This provides the means for removably connecting the plunger to the shaft adjacent to the handle. The plunger handle lower end external surface has an adjacent elastic attachment mate to allow the plunger handle to connect to the plunger elastic attachment. The plunger handle lower end through-hole also has a plunger connection end attachment so the plunger handle removably connects to the shaft lower plunger handle attachment. This connection places the plunger seal in contact with the plunger elastic attachment opening at the plunger cavity upper end, sealing the opening. This also provides the means for removably connecting the plunger to surround the cleaning tool, as the cleaning tool is located within the plunger internal cavity when the plunger is in this position. The plunger elastic attachment is connected to the plunger handle elastic attachment mate. Then the plunger handle, when connected to the shaft upper plunger handle attachment, retains the plunger near the main handle, which exposes the cleaning tool for use. Also when the plunger handle is connected to the shaft lower plunger handle attachment it places the plunger in position for use. The main handle has an upper end and a lower end, the lower end arranged with an attachment opening to attach to the shaft. The assembled handle and plunger is grasped by the plunger handle and removably attached to the shaft upper plunger handle attachment adjacent to the main handle so the cleaning tool is exposed and may be used for cleaning purposes. Then the assembled handle and plunger is grasped by the plunger handle, detached from the shaft upper plunger handle attachment adjacent to the main handle, and removably attached to the shaft lower plunger handle attachment adjacent to the shaft second end, such that the cleaning tool is contained within the plunger cavity, thus allowing the plunger to be used as a drain blockage removal tool. OBJECTS AND ADVANTAGES An object of this invention is to provide a compact tool that minimizes storage space required. A second object of this invention is to provide the tools required for non-invasive plumbing maintenance in one convenient tool assembly. A third object of this invention is to provide a combination-cleaning tool and plunger that is converted from one tool to the other without the user being required to contact the potentially contaminated working surfaces of the cleaning tool or the plunger. BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS A more complete understanding of the present invention can be obtained by considering the detailed description in conjunction with the accompanying drawings, in which: FIG. 1 is a side view of a disassembled combination-cleaning tool and plunger showing the component parts. FIG. 2 is a side view of the main handle. This view shows the location on the handle for the cut-away view in FIG. 4 . FIG. 3 is a bottom view of the main handle. FIG. 4 is a cut-away view of the main handle assembled on the shaft. FIG. 5 is a side view of the shaft. FIG. 6 is a top view of the shaft. FIG. 7 is a bottom view of the shaft. FIG. 8 is a side view of the plunger handle. FIG. 9 is a top view of the plunger handle. FIG. 10 is a bottom view of the plunger handle. FIG. 11 is a side view of the assembled plunger, plunger handle, and shaft with the plunger handle attached to the shaft lower plunger handle attachment to retain the plunger in the lower position. This view shows the location of the cut-away view in FIG. 12 and the expanded view in FIG. 13 . FIG. 12 is a cut-away side view of the assembled plunger, plunger handle, plunger seal, cleaning tool, and shaft with the plunger handle attached to the shaft lower plunger handle attachment to retain the plunger in the lower position. FIG. 13 is an expanded cut-away view of the assembled plunger, plunger handle, plunger seal, cleaning tool, and shaft as shown in FIG. 12 . FIG. 14 is a side view of the assembled combination cleaning tool and plunger with the plunger handle attached to the shaft upper plunger handle attachment to retain the plunger in the upper position. This view shows the location of the cut-away view in FIG. 15 . FIG. 15 is a cut-away side view of the assembled main handle, shaft, and plunger handle with the plunger handle attached to the shaft upper plunger handle attachment to retain the plunger in the upper position. FIG. 16 is a side view of a disassembled combination-cleaning tool and plunger showing an embodiment using a two-pin bayonet for the shaft upper and lower plunger handle attachment. FIG. 17 is a perspective view of the plunger handle in an embodiment using a two-pin bayonet for the shaft connection end and plunger connection end attachment, showing the shaft connection end female bayonet connection. FIG. 18 is a side view of an embodiment of the shaft with an integral main handle. The figure also shows the separate plunger seal used in this embodiment. FIG. 19 is a bottom view of a separate plunger seal consisting of two part, the plunger seal and a brush body seal. The location of the cross-section of FIG. 21 is also shown. FIG. 20 is a top view of the two-piece plunger seal brush body seal. FIG. 21 is a central cross-section of the two-piece plunger seal assembled. The location of the cross-section is shown in FIG. 19 . FIG. 22 is a perspective view of an embodiment of the plunger handle with a double elastic attachment mate using pins to guide the plunger handle in a bayonet slot in the shaft. FIG. 23 is a side view of the embodiment of the plunger handle with a double elastic attachment mate and using pins to guide the plunger handle in a bayonet slots in the shaft. FIG. 24 is a perspective view of an embodiment of the shaft with bayonet slots in the shaft. FIG. 25 is a cut-away side view of the shaft embodiment shown in FIG. 24 with an assembled plunger, plunger handle, plunger seal, cleaning tool, and shaft with the plunger handle attached to the shaft lower plunger handle attachment to retain the plunger in the lower position. REFERENCE NUMERALS IN DRAWINGS These reference numbers are used in the drawings to refer to areas or features of the invention. 30 Shaft 32 Shaft Main Handle Attachment 34 Shaft Upper Plunger Handle Attachment 36 Shaft Lower Plunger Handle Attachment 38 Shaft Cleaning Tool and Plunger Seal Attachment 40 Shaft Upper Bayonet Attachment 50 Cleaning Tool 52 Cleaning Tool Body 54 Cleaning Tool Body Attachment 56 Cleaning Tool Cleaning Surface 70 Plunger Seal 72 Plunger Seal Attachment Opening 74 Plunger Handle Bayonet Attachment 76 Plunger Handle Bayonet Guide Pin 77 Plunger Seal Brush Body Seal 80 Plunger 82 Plunger Elastic Attachment Opening 84 Plunger Elastic Attachment 86 Plunger Internal Cavity 88 Plunger Opening Mouth 90 Plunger Handle 92 Plunger Handle Elastic Attachment Mate 94 Plunger Handle Plunger Connection End Attachment 96 Plunger Handle Shaft Connection End Attachment 98 Plunger Handle Plunger Connection End Shaft Bayonet Attachment 99 Plunger Handle Through-Hole 100 Plunger Handle Shaft Connection End Shaft Bayonet Attachment 102 Plunger Handle Bayonet Guide Pin 110 Main Handle 112 Main Handle Attachment Opening DETAILED DESCRIPTION OF THE INVENTION The combination cleaning tool and plunger provides for cleaning plumbing fixtures, and clearing drain blockage in one compact tool. The tool provides these multiple functions by arranging the cleaning tool at the end of a shaft, and arranging the plunger slidably on the shaft, with attachments near each end of the shaft so it may be attached to the shaft in a lower position, surrounding the cleaning tool, for plunger use, or the plunger may be slid upwards and attached to the shaft in an upper position, near the handle and remote from the cleaning tool, for cleaning tool use. FIG. 1 shows a disassembled combination cleaning tool and plunger. The tool comprises the main handle ( 110 ), the shaft ( 30 ), the cleaning tool ( 50 ), the plunger seal ( 70 ), the plunger ( 80 ) and the plunger handle ( 90 ). Each of these parts and their assembly to allow use of the tool as a combination cleaning tool and plunger is described in detail in the following. FIG. 2 shows a side view of the main handle ( 110 ) with a threaded internal main handle attachment opening ( 112 ) shown in dotted lines. FIG. 3 shows a bottom view of the main handle ( 110 ) with the threaded main handle attachment opening ( 112 ) shown extending into the handle from the bottom. FIG. 4 shows a cut-away view of the main handle ( 110 ) and shaft ( 30 ) assembled. The cut-away is at the location shown in FIG. 2 . The shaft ( 30 ) has a main handle attachment ( 32 ), and an upper plunger attachment ( 34 ) formed by screw threads on the upper first end of the main shaft ( 30 ). The threads are longer than the main handle attachment opening ( 112 ) to form the main handle attachment ( 32 ) and the upper plunger attachment ( 34 ). The main handle may be constructed of plastic, wood-based materials, metal, real or synthetic stone, ceramic, or covered with materials pleasing to the décor and touch of the user. A side view of the shaft ( 30 ) is shown in FIG. 5 . FIG. 6 shows a top view of the shaft ( 30 ) and FIG. 7 shows a bottom view of the shaft ( 30 ). FIG. 5 illustrates the position of the main handle attachment ( 32 ), and the upper plunger attachment ( 36 ) near the upper end of the shaft ( 30 ). The opposite end of the shaft ( 30 ), the second end, has a lower plunger handle attachment ( 36 ) and cleaning tool and shaft plunger seal attachment ( 38 ), both comprising screw threads. FIG. 6 shows a top view of the shaft ( 30 ) and FIG. 7 shows a bottom view of the shaft ( 30 ). The connections described previous are shown in dotted lines. The shaft ( 30 ) may be constructed of plastic, wood-based materials, metal, real or synthetic stone, ceramic as long as the material provides a diameter consistent with sliding the plunger and plunger handle between the upper and lower plunger handle attachments ( 34 and 36 ). The plunger handle ( 90 ) side view is shown in FIG. 8 and the top and bottom view, respectively, is shown in FIG. 9 and FIG. 10 . The plunger handle ( 90 ) is substantially cylindrical in shape with the outside surface of the cylinder having a ridge called the elastic attachment mate ( 92 ). This elastic attachment mate ( 92 ) is arranged to secure the plunger handle ( 90 ) to the plunger as described in detail in the description of the plunger, which follows below. The plunger handle ( 90 ) has a through hole ( 99 ) providing an inner surface arranged with an upper shaft connection end attachment ( 96 ) and a lower plunger connection end attachment ( 94 ) comprising common screw threads. The plunger handle ( 90 ) may be constructed of plastic, wood-based materials, metal, real or synthetic stone, ceramic, or other material which provides a smooth external surface for attachment to the plunger and a consistent internal diameter arranged to allow the plunger handle ( 90 ) to slide on the shaft ( 30 ) between the shaft upper and lower plunger handle attachments ( 34 and 36 ). The assembled plunger ( 80 ), plunger handle ( 90 ) and shaft ( 30 ) are shown in FIG. 11 . In this view the plunger handle plunger connection end attachment ( 94 ), as shown in FIGS. 8 , 9 , and 10 is attached to the shaft lower plunger handle attachment ( 36 ) as shown in FIGS. 1 , 4 and 5 . A cut-away view of the assembly of FIG. 11 is shown in FIG. 12 at the location indicated in FIG. 11 . The cleaning tool ( 50 ) has a body ( 52 ) with an attachment ( 54 ) that screws on the shaft cleaning tool and shaft plunger seal attachment ( 38 ). An expanded view of the cut-away location shown by the broken line circle in FIG. 11 is shown in FIG. 13 to better show the details. The cleaning tool cleaning surface ( 56 ) is made up of a multitude of bristles that form a brush, or looped fabric that form a small mop, or other cleaning materials suitable for a wet environment. The cleaning tool body ( 52 ) is preferably of a material (example plastic) that is non-corrosive in a wet environment. FIGS. 12 and 13 show the positioning of the plunger seal ( 70 ) on the shaft ( 30 ) is arranged so the plunger seal may engage the plunger ( 80 ) at the plunger elastic attachment ( 84 ) lower opening. This seals the openings at the attachment to the plunger handle ( 90 ) and the attachment of the plunger handle to the shaft ( 30 ) during plunger use to prevent water leakage between the plunger handle ( 90 ) and shaft ( 30 ) that could pose a contamination hazard to the user. The plunger handle ( 90 ) is assembled on the plunger ( 80 ) by pressing the handle ( 90 ) into the plunger elastic attachment opening ( 82 ) until the plunger handle elastic attachment mate ( 92 ) engages the plunger elastic attachment ( 84 ). The plunger is made of an elastic material (example rubber). Such materials are well known in the art. This assembly, consisting of the plunger ( 80 ) and plunger handle ( 90 ) is shown in FIGS. 12 and 13 with the plunger handle plunger connection end attachment ( 94 ) attached to the shaft lower plunger handle attachment ( 36 ). This attachment of the plunger ( 80 ) and plunger handle ( 90 ) to the shaft lower plunger handle attachment ( 36 ) places the cleaning tool ( 50 ) within the plunger internal cavity ( 86 ) and also brings the plunger seal ( 70 ) into contact with the plunger elastic attachment ( 84 ) lower opening. In this position the tool is ready for use of the plunger. The plunger ( 80 ) and plunger handle ( 90 ) is shown in FIGS. 14 and 15 with the plunger handle shaft connection end shaft attachment ( 96 ) attached to the shaft upper plunger handle attachment ( 34 ). In FIG. 14 the shaft upper plunger handle attachment is hidden by the plunger handle. FIG. 15 shows a cut-away view of this connection at the location indicated in FIG. 14 . This attachment of the plunger ( 80 ) and plunger handle ( 90 ) to the shaft upper plunger handle attachment ( 34 ) is accomplished by disengaging the plunger ( 80 ) and plunger handle ( 90 ) assembly from the shaft lower plunger handle attachment ( 36 ), sliding the plunger and plunger handle assembly up the shaft and engaging the shaft upper plunger handle attachment ( 34 ) with the plunger handle shaft connection end attachment ( 96 ). With the plunger and plunger handle assembly moved to this upper position the cleaning tool is exposed for use as shown in FIG. 14 . Alternate Embodiments Another embodiment of the combination cleaning tool and plunger is shown in FIGS. 16 and 17 . In this embodiment fastening is accomplished by a two-pin bayonet attachment. Other bayonet attachment arrangements well known to those familiar with the art may also be used. The shaft upper plunger handle attachment ( 34 ) in this embodiment is a round male bayonet ( 40 ) arranged with two pins on opposing sides. The male bayonet attachment slides into a female bayonet, shown in FIG. 17 , with the pins entering the bayonet grooves ( 100 ). When fully inserted, the female bayonet allows rotary motion in a clockwise direction to complete the attachment. The lower plunger handle bayonet attachment ( 74 ) is arranged as a male two-pin bayonet attachment adjacent to, or part of, a plunger seal ( 70 ), separate from the shaft ( 30 ). This part, or parts, attach to the shaft ( 30 ) with the attachment of the cleaning tool ( 50 ) that is previously described. The engagement of the plunger handle plunger connection end bayonet attachment ( 98 ) to the lower plunger handle bayonet attachment ( 74 ) is similar to the upper attachment. In the embodiment shown, the main handle ( 110 ) may be formed continuous with the shaft ( 30 ), or made separate and joined to the shaft ( 30 ) by connection means, or by adhesive, or by a welding technique. Another equivalent embodiment of the combination cleaning tool and plunger using threaded attachments is shown in FIG. 18 . The shaft ( 30 ) in this embodiment has a separate plunger seal ( 70 ) rather than an integral one, so the main handle ( 110 ) may be formed continuous with the shaft ( 30 ), or made separate and joined to the shaft ( 30 ) by connection means, or by adhesive, or by a welding technique. An embodiment of the combination cleaning tool and plunger seal ( 70 ) using a brush body seal ( 77 ) is shown in FIGS. 19 , 20 and 21 . FIG. 19 shows a bottom view of the plunger seal ( 70 ). FIG. 20 shows a bottom view of the brush body seal ( 77 ), which is made of a resilient material such as rubber. The brush body seal ( 77 ) is connected to the plunger seal by stretching the resilient material around the raised surface on the bottom of the plunger seal ( 70 ). This connection is shown in the cross-section shown in FIG. 21 . An embodiment of the combination cleaning tool and plunger using a two-pin bayonet is shown in FIGS. 22 , 23 , 24 and 25 . FIGS. 22 and 23 show an embodiment of the plunger handle ( 90 ) with multiple elastic attachment mates ( 92 ). This embodiment also has openings for bayonet guide pins ( 102 ). The pins are spring pins or sized for a force fit in the handle openings. FIG. 24 shows the shaft ( 30 ) used with this embodiment. It contains two axially oriented bayonet slots on opposing sides of the shaft with the bayonet shaft upper plunger handle attachment ( 34 ) at the upper end of the slots and the shaft lower plunger handle attachment ( 36 ) at the lower end of the slots. The engagement of this embodiment of the plunger handle ( 90 ) with the plunger ( 80 ) and the shaft lower plunger handle attachment ( 36 ) is shown in FIG. 25 . This figure also shows the use of the plunger seal ( 70 ) with a brush body seal ( 77 ). Those skilled in the art will recognize the combination cleaning tool and plunger may be made with a variety of construction details changed, depending on materials chosen, or on the attachment type, or combinations of attachment types chosen. It is intended this invention is not limited by the exact construction shown and described, but that suitable modifications and equivalents are also encompassed by this invention. It is intended that the preferred and other embodiments of the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents. Operation The combination cleaning tool and plunger, as shown in FIGS. 1 through 15 , is assembled by attaching the plunger handle ( 90 ) to the plunger ( 80 ) as previously described. The plunger ( 80 ) and plunger handle ( 90 ) are then positioned on the shaft ( 30 ) by threading the plunger handle shaft connection ends past the shaft upper plunger handle attachment ( 34 ) so the plunger handle ( 90 ) and plunger ( 80 ) may slide on the shaft between the upper and lower plunger handle connections ( 34 and 36 ). The handle ( 110 ) is then attached to the shaft ( 30 ). The plunger ( 80 ) and plunger handle ( 90 ) are then positioned on the shaft ( 30 ) upper plunger handle attachment ( 34 ). This positioning allows the cleaning tool ( 50 ) to be attached to the shaft cleaning tool and plunger seal attachment ( 38 ) by the cleaning tool body attachment ( 54 ). The combination cleaning tool and plunger is now assembled as shown in FIG. 14 . The embodiment shown in FIGS. 16 and 17 is assembled in a similar manner. The plunger ( 80 ) and plunger handle ( 90 ) assembly is positioned on the shaft ( 30 ) without threading, but simply by sliding them on the shaft ( 30 ) second end, which does not have an integral plunger seal in these embodiments. The lower plunger handle attachment ( 74 ) and the plunger seal ( 70 ) are attached to the shaft by attaching the cleaning tool ( 50 ) as described previously. The embodiment shown in FIG. 18 is also assembled in a similar manner. The plunger ( 80 ) and plunger handle ( 90 ) assembly is positioned on the shaft ( 30 ) by threading them on the shaft ( 30 ) second end, which does not have an integral plunger seal in this embodiment. The lower plunger handle attachment ( 74 ) and the plunger seal ( 70 ) are attached to the shaft by attaching the cleaning tool ( 50 ) as described previously. The embodiment shown in FIGS. 23 through 25 is assembled by sliding the plunger handle ( 90 ) on the shaft ( 30 ) and then installing the bayonet guide pins ( 102 ) in the openings in the plunger handle ( 90 ). The pins are installed a sufficient distance so the ends of the pins are inserted in the slot in the handle connecting the upper plunger handle attachment ( 34 ) and the lower plunger handle attachment ( 36 ). The plunger handle ( 90 ) then is captured on the shaft, but free to be rotated in or out of the upper plunger handle attachment ( 34 ) and the lower plunger handle attachment ( 36 ) and then along the shaft to the opposite attachment. Once assembled, the combination cleaning tool and plunger may be used as a cleaning tool with the plunger ( 80 ) and plunger handle ( 90 ) fastened to the upper plunger handle attachment ( 34 ) or in an alternate embodiment to the upper bayonet attachment ( 40 ). This lifts the plunger ( 80 ) above the cleaning tool ( 50 ). The tool may then be grasped by the handle and the cleaning tool ( 50 ) used to clean the plumbing fixture. Alternately, the combination cleaning tool and plunger may be used as a plunger with the plunger ( 80 ) and plunger handle ( 90 ) fastened to the lower plunger handle attachment ( 36 ) or an alternate embodiment to the lower plunger handle bayonet attachment ( 74 ). This places the cleaning tool ( 50 ) inside the plunger internal cavity ( 86 ). The tool may then be grasped by the handle and the plunger opening mouth ( 88 ) applied to the plumbing fixture drain opening. The tool is then vigorously moved in an up and down motion to apply hydraulic force from the plunger opening mouth ( 88 ) to the drain opening to clear the blockage. Changing between the use of the cleaning tool and the use of the plunger is accomplished by holding the shaft ( 30 ) by the handle ( 110 ) and grasping the plunger handle ( 90 ) to disengage the plunger handle from the shaft upper plunger handle attachment ( 34 ). The plunger handle is slide down the shaft until the plunger handle can be connected to the shaft lower plunger handle attachment ( 36 ). The tool is then configured for use of the plunger.
A combination cleaning tool and plunger integrates a cleaning tool and plunger in a single shafted tool to save storage space and provide the tools required for non-invasive plumbing maintenance in one convenient tool assembly. The plunger portion of the tool may be attached in a position near the lower end of the shaft for use in plunging a drain, or slidably moved to be attached in a position near the shaft handle at the upper end of the shaft, exposing the cleaning tool at the lower end of the shaft for use. No disassembly of parts or handling of the working parts is required to use either tool.
4
CROSS-REFERENCE TO RELATED APPLICATION [0001] This application claims the benefit of U.S. Provisional Application No. 60/811,057, Filed Jun. 5, 2006, which is incorporated herein by reference. FIELD OF THE INVENTION [0002] The present invention is directed to orally disintegrating dosage forms comprising lipid coated substrates and silicified excipients. In particular the silicified excipient is silicified microcrystalline cellulose. Use of silicified microcrystalline cellulose in the orally disintegrating dosage from along with lipid coating of active agents, allows for improvements in the ability of the protective coating to prevent unpleasant taste or aftertaste and provide better chemical and mechanical stability of the coated substrate. Further, immediate and modified release profiles are possible. This formulation also provides a practical method of preparing durable orally disintegrating dosage forms. BACKGROUND OF THE INVENTION [0003] Oral administration is the preferred route for numerous pharmaceuticals and nutraceuticals. Orally disintegrating dosage forms offer advantages in terms of convenience and ease of use. However, for many actives, problems such as instability, rapid degradation [0004] To overcome many of the problems listed above, a variety of methods have been used in attempts to effectively protect active agents by controlling release rates and/or masking unpleasant tastes or aftertastes. One common method is to coat the active agent with layers of various polymeric coatings. An alternative approach involves coating the active agent with layers of hydrophobic materials such as lipids or waxes. [0005] Although many orally disintegrating dosage forms exist, some of which use approaches where active substrates are coated, these dosage forms often do not provide a satisfactory level of taste masking within a durable dosage form. There exists a need to optimize both the type of active agent coating along with the dosage form excipients to maximize the level of taste masking, release characteristics and dosage form physical properties such as disintegration and tablet durability. SUMMARY OF THE INVENTION [0006] It is an object of the invention to provide an orally disintegrating dosage form that comprises a plurality of lipid coated active substrates, and a silicified excipient. This combination results in an orally disintegrating dosage form that has excellent taste masking properties as well as providing a commercially viable dosage form. [0007] It is an object of the invention to provide a method of preparing an orally disintegrating dosage form that comprises a plurality of lipid coated active substrates, and a silicified excipient. and unpleasant taste or aftertaste can make oral administration less than favorable. [0008] It is an object of the invention to provide an oral disintegrating dosage form that comprise a plurality of lipid coated active substrates, and a silicified excipient, where the coated active substrate is taste masked and has immediate release. [0009] It is an object of the invention to provide an oral disintegrating dosage form that comprise a plurality of lipid coated active substrates, and a silicified excipient, where the coated active substrate is taste masked and has modified release. [0010] It is further an object of the invention to provide an oral disintegrating dosage form that comprises a plurality of lipid coated active substrates, and a silicified excipient, where the combination of lipid coated active substrates and silicified excipient contributes to the mechanical strength and stability of the dosage form, and the chemical and physical stability of the active ingredient. [0011] In accordance with the above objects and others, the present invention is directed in part to a method for preparing lipid coated active substrates comprising an active agent. In certain embodiments, the method comprises melting a lipid to a temperature above its melting point to obtain a coating solution and then applying the coating solution to the substrates at a temperature such that the coating solidifies to form uniformly coated substrates. In certain embodiments, the coating may be applied to be substrates via various spraying techniques, e.g., utilizing a fluidized bed type encapsulation process. [0012] The substrates of the present invention may comprise a pharmaceutically acceptable bead, granule, spheroid, pellet, slab, rod and the like. [0013] In certain embodiments, the substrates may comprise a mixture of an active agent and an excipient. [0014] In order that the invention describe herein may be further understood, the following definitions are provided for the purposes of the disclosure: [0015] The term “oral disintegrating dosage form” is defined as a tablet, caplet, rod, spheroid, film strip or any other dosage form that disintegrates/disperses in the buccal cavity with the help of saliva, i.e., without the need of additional water. The time of disintegration should be less than two minutes, preferably less than one minute, and even more preferably less than 30 seconds. [0016] The term “active agent” or “active ingredient” is defined as any compound that provides an effect in an environment of use. In certain embodiments, the effect is a therapeutic effect. An active agent may be active pharmaceutical ingredient (API) such as a drug or biological agent, a nutraceutical agent, an herbal remedy, a vaccine, or a bactericidal agent. [0017] The term “excipient” is defined as any pharmaceutically acceptable excipient suitable for animal, e.g., human, consumption. [0018] The term “substrate” is defined as the active agent itself, the active agent combined together with at least one pharmaceutically acceptable excipient. The substrate may be in the form of a pharmaceutically acceptably bead, granule, pellet, spheroid, and the like with the active agent contained therein or thereon. [0019] For purposes of the present invention, the term “patient” is defined as a human or animal inflicted with a disease or condition that requires treatment with a pharmaceutically active agent. [0020] The term “object” is defined as a human or animal that does not have any disease or condition that requires treatment with a pharmaceutically active agent, e.g., a normal volunteer. [0021] The term “protective coating” is defined as a coating that may have a positive effect on the processability of the substrate (e.g., taste-making, improvement in flow, binding, friability, hardness, etc). [0022] The term “lipid” is defined as any lipid known in the art, including fatty acid glycerol esters, hydrogenated vegetable oils or animal fats, waxes, fatty acids, fatty alcohols, sterols, and phospholipids, or combinations thereof. [0023] The term “hydrophobic material” is defined as material that is acceptable for the active defined herein, that has a sufficient level of hydrophobicity that is dissolvable in a lipid. [0024] The term “polymer” is defined as a chemical with greater than 5 monomer units. [0025] There term “silicified excipient” is defined as any inactive or active that is combined or impregnated with silicon, silica, silicates or its derivatives. [0026] For purposes of the present invention, the term “immediate release” is defined as a release of substantially all of the active agent contained in a dosage form within about 1 hour (and preferably faster)after being exposed to an environment of use (e.g., an in-vitro dissolution bath, or the stomach of a human patient). [0027] For purposes of the present invention, the term “modified release” is defined as delayed, controlled, extended, site specific, slow or pulsatile release, i.e., different from immediate release, of the active agent from a dosage form. DETAILED DESCRIPTION [0028] The combination of a coated substrate with a silicified excipient in an orally disintegrating dosage form, where the coated substrate is coated with a lipid protective coating, provides improved properties. These improved properties include preventing unpleasant taste or after taste and contribute to the mechanical strength, chemical protection and stability of the coated substrate, the to the processability of the dosage form and to a modified release of the active agent. In addition, the silicified excipient aids in the preparation of a pre-mix that is subsequently tableted, as well as providing an orally disintegrating dosage form that has favorable mechanical properties. [0029] It is well known that a coated substrate, where the protective coating is lipid, can mask taste. However, the taste masking and level of protection of the protective coating is compromised owing to mechanical pressures, when it is included in an orally disintegrating dosage form. In the present invention, by using a silicified excipient as part of the orally disintegrating dosage form, the lipid coated substrate retains beneficial properties. [0030] It has been found that upon blending lipid coated substrates with conventional flow aids such as silica in a tablet blend formulation, the efficiency of sieving the blend is severely compromised. This leads to long times to sieve which can be costly in a manufacturing environment. Conversely, by using a co-processed silicified excipient, with lipid coated substrates, the sieving process is very efficient. [0031] The formulations of the present invention allow for a superior performance orally disintegrating dosage form, both in terms of ease and time of manufacture, and final properties such as taste masking, stability, release and physical properties of the dosage form. [0000] Protective Coating—Microencapsulation [0032] The protective coating is lipid, composed of a lipid with optionally other coating additives. Not limiting to this property, any lipid that exhibits acceptable properties for use in hot-melt processes can be used in the protective coatings of the present invention. Lipids suitable for use as a protective coating in the oral disintegrating dosage forms of the invention are well known to those skilled in the art, and basically are fat and fat-like substances which are derived from plants, animals or synthetically. A variety of materials having varied chemical structure are generally classified as lipids, and are considered to be useful in the formulations and methods of the present invention. [0033] One type of lipid suitable for use in the invention is generally classified as fatty acid glycerol esters. Such materials, also known as glycerides, and may be simple (where all fatty acid groups are identical) or mixed, saturated or unsaturated. Examples of suitable glycerides include those derived from higher-molecular weight fatty (aliphatic) acids, such as palmitic, stearic and oleic acids. For example, the lipid may be a fatty acid glycerol ester, such as, but not limited to, mono-,di-, tri-glycerides and any combinations or mixtures thereof. Another type of lipid suitable suitable for use in the invention is generally classified as waxes, which are esters of high molecular weight, even-numbered monohydric alcohols (C 16 to C 36 ) and fatty acids (C 14 to C 36 ). Further detail and explanation concerning acceptable lipids useful in the invention may be gleaned from Remington's 20 th Edition ©2000 by the University of the Sciences in Philadelphia, pages 415-419, hereby incorporated by reference. [0034] In particular, hydrogenated vegetables oils and animal oils may be used in the protective coating in the present invention. Hydrogenated vegetable oils may include, but are not limited to, cashew, castor bean, linseed, grape seed, hemp seed, mustard seed, poppy seed, rape seed (canola oil), safflower, sesame seed, sunflower, almond, algae, apricot, argan, avacodo, corn oil, cotton seed, coconut, fusarium, hazelnut, neem oil, palm, palm kernel, peanut, pumpkin, rice bran, walnut, soybean oil and any combinations or mixtures thereof. [0035] The protective coating may also be comprised of a wax such as, but not limited to, paraffin wax; a petroleum wax; a mineral wax such as ozokerite, ceresin, utah wax or montan wax; a vegetable wax such as, for example, carnauba wax, japan wax, bayberry wax or flax wax; an animal wax such as, for example, spermaceti; or an insect wax such as beeswax, Chinese wax or shellac wax. [0036] The choice of lipid for preparing the protective coatings of the present invention may have varying effects on the methods of preparation as well on the dissolution of the active agent from the coated substrate. [0037] The amount of protective coating is at least about 1% to not more than 90% by weight of the microencapsulated substrate. In certain embodiments, the coating is at least about 1% to about 60% by weight of the microencapsulated substrate, preferably at least about 1% to 35% by weight, and even more preferably at least about 1% to about 20% by weight, and even more preferably at least about 1% to about 10% by weight of the microencapsulated substrate. [0038] Coating additives can be included or dissolved in the lipid. Optional additives for use in the present invention include, but are not limited to, flavoring agents, taste-making agents, bitter blockers, plasticizers, binders, sensory masking agents, flavors, pH triggers, antioxidants, cellulose and cellulose derivatives, and the like. Other excipients suitable for use in the present invention are described in the Handbook of Pharmaceutical Excipients, American Pharmaceutical Association (2005), incorporated by reference herein. [0039] The protective coating may comprise from about 0 to about 25 percent by weight coating additives (in addition to the lipid and the optional hydrophobic material), and preferably such additives comprise up to about 10 percent by weight of the protective coating. [0040] In certain embodiments of the invention, an effective amount of a hydrophobic material is incorporated into the protective coating. The hydrophobic material, preferably a cellulose derivative (e.g., ethylcellulose), is dispersed or (preferably) dissolved in the lipid prior to coating may range from about 1% to about 25%, from about 1% to about 15% or from about 1% to about 10%. The addition of cellulose derivative(s) to the protective coating may improve the tableting properties of the coated substrate. Improved tableting properties include, but are not limited to increased mechanical strength stability, binding, friability and hardness of the dosage form, as well as providing consistent properties from tablet to tablet, as described in Applicants' co-pending Provisional Patent Application No. 60/810,983, entitled “Protective Coating for Active Agent Substrate”, filed Jun. 5, 2006, disclosure of which is hereby incorporated by reference. [0041] The protective coating is applied by any known coating method. These include but are not limited to spray chilling, spinning disk, pan coating, fluidized bed coating. In particular fluidized bed type microencapsulation processes known in the art may be utilized such as those described in U.S. Pat. Nos. 4,511,584; 4,537,784; 4,511,592; and 4,497,845, the disclosures of which are hereby incorporated by reference. plurality of substrates may be delivered into a chamber (fluidized bed) and the protective coating uniformly sprayed onto the substrates. It is contemplated that temperatures inside the fluidized bed will be less than about 150° F., but not limited to. In certain embodiments, the temperature may be less than 120° F. or less than 100° F. The temperatures utilized inside the fluidized bed will be dependent upon the crystallization properties of the particular lipid to be applied, with relatively higher temperatures being preferred where the melting point of the particular lipid material utilized is relatively higher. [0042] Fluidized-bed apparatuses suitable for microencapsulating the substrates in accordance with the methods of the present invention may be any known fluidized bed apparatus such as, but not limited to, the GPCG series of batch fluidized bed apparatus, the GF series of continuous fluidized bed apparatuses and the ProCell series of spouted bed systems manufactured by the Glatt® Group. [0043] Preferably, the protective coating is applied in a single step process and in the absence of any required solvents. [0044] The potential functions of the protective coatings of the present invention include, but are not limited to, high dissolution of the substrate, modified release characteristics of the substrate, enhancing the bioavailability of the active agent, improving flow, compactibility, etc. for the processing of solid dosage forms. [0000] Substrates [0045] The substrate to be microencapsulated may be the active agent itself, the active agent combined together with one or more acceptable excipients into suitably sized particles (granules), shaped into pellets, or manufactured as spheroids. In certain embodiments, the active agent itself is a granulate of acceptable size such that the protective coating can be directly applied onto its surface in an even manner to create a desirable microencapsulate. In other embodiments of the invention, the active agent is granulated (e.g., wet granulated) together with an excipient(s) to make desirable granules which can be coated. In such embodiments, the active agent is typically wet granulated with a diluent (e.g., lactose, sucrose, starch, and the like). Generally, the resultant granulated has a particle size ranging from about 0.01 mm to about 3 mm, and preferably from about 0.1 mm to about 1 mm. In certain preferred embodiments, the active agent granulate is about 800 microns to about 200 microns in diameter (and in certain embodiments about 400 microns) is then separated and further processed via microencapsulation. Alternatively, the substrates used in the invention may comprise a pharmaceutically acceptable sugar sphere (bead) coated with the active agent. Sugar spheres are solid excipients which are composed of one or more sugar, starch, cellulose, etc. and typically have a size ranging about 300 microns to about 1400 microns. Pellets are generally considered in the art to comprise small, sterile cylinders (e.g., about 3 mm in diameter by about 8 mm in length), which are formed from compression from a mass comprising active agent and one or more excipients. On the other hand, the substrate may comprise a matrix spheroid in which the active agent is incorporated together with the excipient(s) a substantially uniform fashion. One skilled in the art will also appreciate that excipients may be utilized in the preparation of such substrates without changing the basic character of the invention. [0046] The load of the active agent contained in the coated substrates may be at least about 10%. In certain embodiments, the load may be at least about 40%. In certain embodiments, the load may be at least 65%. In certain embodiments, the load may be at least about 75%. In certain embodiments, the load may be at least 95%. When the present invention contemplates lipid coated acetaminophen substrates, the load of acetaminophen ranges from about 85% to about 97%. [0000] Active Agents [0047] Active agents suitable for use in the present invention may include, but are not limited to, water soluble and water insoluble agents. Active agents include drugs, nutrients, biologicals, vaccines and herbal agents. [0048] Combinations of active agents may be included within the dosage form. In this manner, the active agents can be combined within the coated active substrate and/or included with the excipients of the dosage form. [0000] Drugs [0049] Examples of active agents that are suitable for incorporation in the present invention include: antihistamines (e.g., azatadine maleate, brompheniramine maleate, carbinoxamine maleate, chlorpheniramine maleate, dexchlorpheniramine maleate, diphenhydramine hydrochloride, doxylamine succinate, methdilazine hydrochloride, promethazine, trimeprazine tartrate, tripelennamine citrate, tripelennamine hydrochloride and triprolidine hydrochloride);antibiotics (e.g., penicillin V potassium, cloxacillin sodium,dicloxacillin sodium, nafacillin sodium, oxacillin sodium, carbenicillin indanyl sodium, oxytetracycline hydrochloride, tetracycline hydrochloride, clinamycin phosphate, clindamycin hydrochloride, clindamycin palmitate HCL, lincomycin HCL, novobiocin sodium, nitrofurantonin sodium, metronodazle hydrochloride); antituberculosis agents (e.g., isoniazed); cholinergic agents(e.g., ambenonium chloride, bethanecol methylbromide, clindinium bromide, dicyclomine hydrochloride,glyopyrrolate, hexocyclium methylsulfate, homatropine methylbromide, hyoscyamine sulfate, methantheline bromide, hyoscine hydrobromide, oxyphenonium bromide, propantheline bromide, tridihexethyl chloride); sympathomimetics (e.g., bitolterol mesylate, ephedrine, ephedrine hydrochloride, ephedrine sulphate, orciprenaline sulphate, phenylpropanolamine hydrochloride, pseudoephedrine hydrochloride, ritodrine hydrochloride, salbutamol sulphate, terbutaline sulphate); sympatholytic agents (e.g., phenoxybenzamine hydrochloride); miscellaneous autonomic drugs (e.g., nicotine); iron preperations (e.g., ferrous gluconate, ferrous sulphate); haemostatics (e.g., aminocaproic acid); cardiac drugs (e.g., acebutolol hydrochloride, disopyramide phosphate, flecainide acetate, procainamide hydrochloride, propranolol hydrochloride, quinidine gluconate, timolol maleate, tocainide hydrochloride, verapamil hydrochloride); antihypertensive agents (e.g., captopril, clonidine hydrochloride, hydralazine hydrochloride, mecamylamine hydrochloride, metoprolol tartrate); vasodilators (e.g., papaverine hydrochloride);non-steroidal anti-inflammatory agents (e.g., choline salicylate, ibuprofren , ketoprofen, magnesium salicylate, meclofenamate sodium, naproxen sodium, tolmetin sodium); opiate agonists (e.g., codeine hydrochloride, codeine phosphate, codeine sulphate, dextromoramide tartrate, hydrocodone bitartrate, hydromorphone hydrochloride, pethidine hydrochloride, methadone hydrochloride, morphine sulphate, morphine acetate, morphine lactate, morphine meconate, morphine nitrate, morphine monobasic phosphate, morphine tartrate, morphine valerate, morphine hydrobromide, morphine hydrochloride, propoxyphene hydrochloride); anticonvulsants (e.g., phenobarbital sodium, phenytoin sodium, troxidone, ethosuximide, valproate sodium); tranquilizers (e.g., acetophenazine maleate, chlorpromazine hydrochloride, fluphenazine hydrochloride, prochlorperazine edisylate, promethazine hydrochloride, thioridazine hydrochloride, trifluoroperazine hydrochloride, lithium citrate, molindone hydrochloride, thiothixine hydrochloride); chemotherapeutic agents (e.g., doxorubicin, cisplatin, floxuridine, methotrexate, combinations thereof, etc); lipid lowering agents (e.g., gemfibrozil, clofibrate, HMG-CoA reductase inhibitors, such as for example, atorastatin, cerivastatin, fluvastatin, lovastatin, pravastatin, simvstatin, etc.); H 2 -antagonists (e.g., cimetidine, famotidine, nizatidine, ranidine HCl, etc); anti-coagulant and anti-platelet agents (e.g., warfarin, cipyridamole, ticlopidine,etc.); bronchodilators (e.g., albuterol, isoproterenol, metaproterenol, terbutaline, etc.); stimulants (e.g., benzamphetamine hydrochloride, dextroamphetamine sulphate, dextroamphetamine phosphate, diethylpropion hydrochloride, fenfluramine sulphate, methamphetamine hydrochloride, methylphenidate hydrochloride, phendimetrazine tartrate, phenmetrazine hydrochloride, caffeine citrate); barbituates (e.g., amylobarbital sodium, butabarbital sodium, secoarbital sodium);sedatives (e.g., hydroxydize hydrochloride, methprylon); expectorants (e.g., potassium iodide); antiemetics (e.g., benzaquinamide hydrochloride, metoclopropamide hydrochloride, trimethobenzamide hydrochloride); gastro-intestinal drugs (e.g., ranitidine hydrochloride); heavy metal antagonists (e.g., penicillamine, penicillimine hydrochloride); antithyroid agents (e.g., methimazole); genitourinary smooth muscle relaxants (e.g., flavoxate hydrochloride, oxybutynin hydrochloride); vitamins (e.g., thiamine hydrochloride, ascorbic acid); unclassified agents (e.g., amantadine hydrochloride, colchicine, etidronate disodium, leucovorin calcium, methylene blue, potassium chloride, pralidoxime chloride; steroids, particularly glucocorticoids (e.g., prednisolone, prednisone, cortisone, hydrocortisone, methylprednisolone, betamethasone, dexamethasone, triamcinolone), and any combinations or mixtures of the foregoing. [0050] In other embodiments, the subtrates may comprise a combination of active agents. For example, the substrates may comprise a combination of acetaminophen and an opoid analgesic, such as but not limited to, alfentanil, allylprodine, alphaprodine, anileridine, bezylmorphine, buprenorphine, butorphanol, clonitazene, codeine, desomorphine, dextromoramide, dezocine, diampromide, diamorphone, dihydrocodeine, dihydromorphine, dimenoxadol, dimepheptanol, dimethylthiambutene, dioxaphetyl butyrate, dipipanone, eptazocine, ethoheptazine, ethylmethylthiambutene ethylmorphine, etonitazene, fentanyl,heroin,hydrocodone, hydromorphone, hydroxypethidine, isomethadone, ketobemidone, levorphanol, levophenacylmorphan, lofentanil, meperidine, meptazinol, metazocine, methadone, metopon, morphine, myrophine, narceine, nicomorphine, norlevorphanol, normethadone, nalorphine, nalbuphene, normorphine, norpipanone, opium, oxycodone, oxymorphone, papaveretum, pentazocine, phenadoxone, phenomorphan, phenazocine, phenoperidine, piminodine, piritramide, propheptazine, promedol, properidine, propoxyphene, sufentanil, tilidine, tramadol, mixtures thereof and pharmaceutically acceptable salts thereof. [0051] In certain embodiments, the active agent is ranitidine HCl, caffeine, vitamin C, acetaminophen, or guaifenesin. [0000] Biologicals and Vaccines [0052] Biologicals suitable for use in the present invention include, but are not limited to, immune serums (e.g., immune globulins), antitoxins, antivenins, toxoids (e.g., tetanus toxoid), allergenic extracts, in-vivo diagnostic biologicals, interferon and the like. [0053] Suitable vaccines include, but are not limited to, bacterial vaccines and viral vaccines. Bacterial vaccines include, but are not limited to, BCG vaccine, mixed respiratory vaccines, meningococcal vaccine, cholera vaccine, plague vaccine, pneumococcal vaccine, hemophilus vaccine and the like. Viral vaccines include, but are not limited to, measles, mumps, rubella, poliovirus, influenza, encephalitis, yellow fever, hepatitis A, hepatitus B, varicella vaccines and the like. [0000] Herbal Agents [0054] Herbal compositions may include, but are not limited to agrimony, alfalfa, allspice, angelica, anise, basil, bayberry, boneset, borage, caraway, cayenne, chamomile, dandelion, dill, Echinacea, evening primrose, fennel, garlic, ginger. ginko balboa, jasmine, juniper, lavendar, lemon balm, rosemary, rue, thyme, valerian, yarrow and any other herbal that is suitable for administration to a subject/patient in need thereof. Other herbal agents suitable for use in the present invention include, but are not limited to thos described in The Complete Guide to Herbal Medicines, Fetrow, Charles A., et al. (September 2000), the disclosure of which is hereby incorporated by reference. [0000] Nutrients [0055] Other ingredients which may be employed as the active agent(s) in the present invention include nutritional supplements, dietary supplements and combinations thereof. The compounds meeting this criteria may have varying degrees of solubility in water ranging from highly soluble to insoluble. These compounds generally include vitamins, minerals, amino acids, herbal and botanical products and the like. Vitamins generally refer to organic substances that are required in the diet and include thiamin, riboflavin, nicotinic acid, pantothenic acid, pyrodoxine, biotin, folic acid, vitamin B12, as well as enzymes and coenzymes thereof. Minerals include inorganic substances which are required in the human diet and include calcium, iron, zinc, selenium, copper, iodine, magnesium, phosphorous, chromium, and the like and mixtures thereof. [0056] Dietary supplements which may employed as the active agent(s) of the invention include, for example, B pollen, bran, wheat germ, kelp, cod liver oil, ginseng, fish oils, amino acids, protein and the like and mixtures thereof. A non-limiting example of a final formulation comprising multi-vitamin and mineral supplements is described e.g., in U.S. Pat. 6,987,098, hereby incorporated by reference. The supplement described therein is useful for human consumption and comprises, e.g., from about 5000 I,U to about 10,000 I.U. of vitamin A; from about 1000 mg to about 2000 mg of vitamin C; about 800 I.U. of vitamin D; from about 800 I.U. to about 1200 I.U. of vitamin E; about 25 mcg of vitamin K; about 3 mg of vitamin B6; about 800 mcg of folic acid; about 400 mcg of vitamin B12; about 300 mcg of biotin; about 10 mg of pantothenic acid; up to about 18 mg of iron dosed in the form of an acceptable iodine compound; about 150 mcg of iodine dosed in the form of an acceptable zinc compound; from about 100 mcg to 200 mcg of selenium; about 2 mg of copper dosed in the form of an acceptable copper compound; about 100 mcg of chromium dosed in the form of an acceptable chromium compound; about 400 mg of potassium dosed in the form of an acceptable potassium compound; about 500 mg of choline dosed in the form of an acceptable choline compound; about 10 mg of lycopene; and about 50 mg co-enzyme Q-10 dosed in the form of an acceptable co-enzyme Q-10 compound. [0000] Preparation of Final Dosage Form [0057] The lipid coated active substrates may be incorporated into an orally disintegrating dosage form. The dosage form preferably disintegrates/disperses in the buccal cavity with the help of saliva, i.e., without the need of additional water, generating for more readily swallowable residual. The time of disintegration should be less than two minutes, preferably less than one minute, and even more preferably less than 30 seconds. [0058] There are a number of technologies that generate tablets which satisfy the above requirements: Zydis® (Cardinal Health) and Quicksolv® (Janssen Pharmaceutica) use lyophilization; OraSov® (Cima Labs), Wowtab® (Yamanouchi), Flashtab® (Ethypharm) and Frosta® (Akins) are made on regular tablet presses; while FlashDose® (Biovail) uses the so-called Fuisz technology, also known as the “cotton candy process.” Examples of the actice pharmaceutical ingredients that have been commercially available in rapid-dissolve tablet form are lortadine, acetaminophen, fluoxetine, diphenydramine, famotidine, etc. [0059] In certain embodiments, the lipid coated active substrates utilized in the present invention may be directly compressed together with or without additional pharmaceutical excipients, as described in Applicants' co-pending Provisional Patent Application No. 60/811,056, entitled “Directly Compressed Dosage Forms and Methods for Producing the Same”, filed Jun. 5, 2006, the disclosure of which is hereby incorporated by reference. [0060] In certain embodiments, the lipid coated substrates are directly compressed together with a silicified excipient, such as ProSolv R (silicified microcrystalline cellulose). ProSolv® is a high functionally ingredient as it is multifunctional, requires less complex processing (direct compression), has high inherent functionality and imparts that functionality to the drug formula. Various grades of ProSolv® (98% microcrystalline cellulose and 2% colloidal silicon dioxide) are available from JRS Pharma Inc., Petterson, N.Y. ProSolv SMCC® 50, ProSolv SMCC® 90 and SMCC® HD (high density) 90. ProSolv SMCC® 50 has a median particle size (by sieve analysis) in the region of 50 μm while ProSolv SMCC® 90 and SMCC® HD 90 have median particle size (by sieve analysis) in the region of 90 μm. ProSolv® and the process for its manufacture are protected by U.S. Pat. Nos. 5,585,115; 5,725,884; 6,103,219; 6,217,909; 6,358,533; 6,521,261; 6,858,231; 5,725,883; 5,866,166; 6,106,865; 6,936,277; 5,741,524; 5,858,412, the disclosures of which are hereby incorporated by reference. ProSolv is an excipient comprising a particulate agglomerate of coprocessed microcrystalline cellulose and from about 0.1% to about 20% silicon dioxide, by weight of the microcrystalline cellulose, the microcrystalline cellulose and silicon dioxide being in intimate association with each other, and the silicon dioxide portion of the agglomerate being derived from a silicon dioxide having a particle size from about 1 nanometer (nm) to about 100 microns (.mu.m), based on average primary particle size. [0061] ProSolv® is free-flowing excipient that posses excellent disintegration properties, and importantly, improved compressibility relative to normal “off-the-shelf” commercially available microcrystalline cellulose when directly compressed. The advantages of ProSolv® are especially realized in pharmaceutical formulations prepared using wet granulation techniques. When utilized in wet granulation techniques, the ProSolv® provides a compressibility of normal “off-the-shelf” commercially available microcrystalline cellulose used in direct compression techniques. ProSolv® provides a compressibility which is substantially superior to the compressibility of normal “off-the-shelf” commercially available microcrystalline cellulose used in direct compression techniques. [0062] The amount of silicified excipient present in the dosage forms described herein ranges from about 0.1% to about 50%, preferably from about 0.1% to about 20%. [0063] In addition to the inclusion of a silicified excipient, the dosage forms may also contain an optional excipient such as, but not limited to, binder/fillers, disintegrants and superdisintegrants, lubricants, and antiadherents. Examples of suitable excipients include sucrose, dextrose, lactose, mannitol, starches, silicas, clays, microcrystalline cellulose, xylitol, fructose, sorbitol, disintegrants and superdisintergrants, such as crospovidone, croscarmellose and sodium starch glycolate, flavoring agents, acidifiers, sweeteners, taste-maskers, lubricants (e.g., magnesium stearate, stearic acid) and any combinations or mixtures of the foregoing. [0064] Other suitable compression excipients for use in the dosage forms of the present invention may also pre-manufactured direct-compression excipients in place of part or all of the silicified excipients (e.g., ProSolv). Examples of such pre-manufactured direct compression excipients includ Emcocel® (microcrystalline cellulose, N.F.), Emdex® (dextrates, N.F.), and Tab-Fine® (a number of direct-compression sugars including sucrose, fructose, and dexrtose), all of which are commercially available from JRS Pharma Inc., Patterson, N.Y.). Other direct compression diluents include Anhydrous lactose (Lactose N.F., anhydrous direct tableting) from Sheffield Chemical, Union, N.J. 07083; Elcems® G-250 (Powered cellulose, N.F.) from Degussa, D-600 Frankfurt (Main) Germany; Fast-Flo Lactose® (Lactose, N.F., spray dried) from Foremost Whey Products, Banaboo, Wis. 53913; Maltrin® (Agglomerated maltrodextrin) from Grain Processing Corp., Muscatine, Iowa 52761; Neosorb 60® (Sorbital, N.F., direct-compression) from Roquette Corp., 645 5th Ave., New York, N.Y. 10022; Nu-Tab® (Compressible sugar, N.F.) from Ingredient Technology, Inc., Pennsauken, N.J. 08110; Poly plasdone XL® (Crospovidone N.F., cross-linked polyvinylpyrrolidone) from ISP Corp, Wayne N.J. 07470; Primojel® (Sodium starch glycolate, N.F., carboxymethyl starch) from Generichem Corp., Little Falls, N.J. 07424; Spray-dried lactose® (Lactose N.F., spray dried) from Foremost Whey Products, Baraboo, Wis. 53913 and DMV Corp., Vehgel, Holland; and Sta-Rx 1500® (Starch 1500) (Pregelatinized starch, N.F., compressible) from Colorcon, Inc., West Point, Pa. 19486, calcium silicate (RxCIPIENTS FM1000) from Huber Materials, Germany. Pre-manufactured directed compression excipients may also comprise all or a portion of the inert diluent. [0000] Rate of Release [0065] Release properties of the active agent from the lipid coated substrate in the final dosage form may be altered depending on the lipid(s) chosen for a particular protective coating. The release properties of the active agent from the coated substrate in the final dosage form may further be altered by controlling the amount (thickness) of the lipid coating. The release properties may further be altered by the inclusion and amount of hydrophobic material incorporated into the protective coating. Any combination of the foregoing may be used together to achieve a desired release of active agent from the microencapsulated substrates. [0066] For example, certain lipids, such as, but not limited to, monoglycerides, may provide a faster release of the active agent from the coated substrate. Other lipids, such as, but not limited to, triglycerides may provide a relatively slower, modified release of the active agent from the coated substrate. For purposes of the present invention, the term “modified release” is defined as a delayed release, a controlled release, a bi-phasic or multi-phasic release and pulsatiled release. [0067] In addition to controlling the releasing rate by factors described herein, in embodiments of the invention where a modified release is desired, it is further contemplated that one or more modified release carriers may be incorporated into the dosage form. This may be accomplished, e.g., (i) by admixing one or more modified release carriers with a plurality of lipid coated active substrates;(ii) by applying a further coating comprising one or more modified release carriers onto the surface of the coated substrates (either with or without any additional admixed excipients); and (iii) any combination of the foregoing. [0068] Suitable materials which may be included as the modified release carrier in such applications include hydrophilic and hydrophobic materials which are either pH-independent or pH-dependent in the environment of use (e.g., a dissolution media or in the gastro-intestinal tract when administered in-vivo). Such material include pharmaceutically acceptable polymers and copolymers, including cellulosics and acrylic and methacrylic acid polymers and copolymers, polysaccharides, gums, lipids (such as those set forth for use in encapsulation of the substrates in the invention), etc. This list is not meant to be exclusive. Examples of suitable materials include cellulose ethers and cellulose esters acrylic and methacrylic acid polymers and copolymers. Further specific examples of suitable modified release materials include alginates, xantham gum, guar gum, pectin, carageenan, gum Arabic, locust bean gum, carob gum, modified starch, methylhydroxyethylcellulose, carboxymethylcellulose, sodium carboxymethylcellulose, calcium carboxymethylcellulose, hydroxypropycellulose, hydroxypropylmethylcellulose, methyl hydroxyethylcellulose, ethylcellulose, poly(vinylpyrrolidone), polyacrylates, polylysines, poly (N-vinyl lactams), poly(ethylene oxide), poly (propylene oxide), polyacrylamides, polyacrylic acids, polyvinyl alcohols, polyvinyl ethers, polylactide, a polyglycolide, a poly (lactide-co-glycolide),a polyanhydride, a polyorthoester, polycaprolactones, polyphosphazenes, polysaccharides, proteinaceous polymers, soluble derivatives of polysaccharides, soluble derivatives of proteinaceous polymers, polypeptides, polyesters, polyorthoesters, poly-1,4-glucans (e.g., starch glycogen, amylose, amylopectin, and mixtures thereof), hydroxyalkyl derivatives of hydrolyzed amylopectin such as hydroxyethyl starch (HES), hydroxyethyl amylose, dialdehyde starch, methyl methacrylate, methyl methacrylate copolymers, ammonio methacrylate copolymers, ethoxyethyl methacrylates, cynaoethyl methacrylate, aminoalkyl methacrylate copolymer, poly(acrylic acid), poly(methacrylic acid), methacrylic acid alkylamine copolymer, poly(methyl methacrylate), poly (methacrylic acid)(anhydride), polymethacrylate. polyacrylamide, poly(methacrylic acid anhydride), and glycidyl methacrylate copolymers, mixtures of any of the foregoing, and the like. Ammonio merhacrylate copolymers are well known in the art, and are described in NF XVII as fully polymerized copolymers of acrylic and methacrylic acid esters with a low content of quaternary ammonium groups. One commercially-available aqueous dispersion of ammoniomethacrylate copolymers is sold under the tradename Eudragit R (Rohm Pharma). One comercially-available aqueous dispersion of ethylcellulose is sold under the tradename Aquacoat® (FMC Corp.). [0069] In certain embodiments, the orally disintegrating dosage forms of this invention, the active is taste masked and the release of the active agent has immediate release. In certain embodiments, the release of the active agent from the lipid coated active substrate does not have immediate release characteristics until it has been included in the dosage form. In the dosage form, the release is immediate whilst unexpectedly taste masking the active agent and/or providing stability. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [0070] The present invention will be firther appreciated in view of the following examples: [0071] In the following examples soy or HSO is hydrogenated soybean oil, soy/EC is 90% hydrogenated soybean oil (Sterotex® HM NF, from Abitec) and 10% ethylcellulose (Ethylcellulose, Standard 4, from Dow Chemical). Castorwax/EC is 90% or 80% hydrogenated castor oil (HSO) (Casterwax® NF, from Caschem) and 10% or 20% ethylcellulose. ProSolv SMCC® 50, ProvSolv SMCC® 90, ProSolv SMCC® HD90 are all microcrystalline cellulose coprocessed with amorphous fumed silica, from JRS Pharma; Perlitol® is mannitol from Roquette; and Polyplasdone® XL is crospovidone from ISP Technologies; caffiene from Pharmline; acetaminophin (APAP)from Kangle; Ibuprofen from AnMar International Ltd. EXAMPLE I Process for Making Lipid Coated Active Substrates [0072] As a representative example, acetaminophen was used as the active substrate. Twenty pounds (20 lbs) of acetaminophen was coated (microencapsuledated) using a solution of ethylcellulose in hydrogenated soybean oil (1.74 lbs), 1 : 9 ratio (EC/HSO). The solution, at 300° F. was top sprayed at a rate of about 0.34 lb/min onto a bed of acetaminophen in a modified fluid bed process. The bed temperature of about 115° F. was maintained, to achieve an even coating of the particles. A 92% load of the active agent was achieved. Other active substrates in the following examples were coated in a similar fashion. At 50% activity, 15 lbs of active substrate was coated with 15 lbs of coating. [0073] The solution of lipid (for example hydrogenated soybean oil) and ethylcellulose were prepared by heating hydrogenated soybean oil (13.5 lbs) to a temperature of about 180° F. Ethylcellulose was added. By heating to 380° F., ethylcellulose (1.5 lbs) was then dissolved in the hydrogenated soybean oil to form a protective coating solution, at a 1:9 ratio. [0074] Lipids that do not contain dissolved ethylcellulose are typically applied as a coating at lower temperatures, approx. 220° F. EXAMPLE II Orally Disintegrating Tablets Containing Soy Coated Acetaminophen [0075] Soy coated acetaminophen at 92% activity was prepared as in Example I. The coated acetaminophen was mixed with excipients using a Turbula blender according to the following formula: 41 g coated APAP (92% active, soy coating) 40 g Pearlitol 200SD 14 g ProSolv SMCC90 3 g Polyplasdone 1 g Splenda 1 g Mg stearate [0082] The powder blend was compressed into acceptable tablets on a K-International press. The tablet weight was about 505 mg, the hardness ranged from 0.8 to 1.1 kP. The acetaminophen in the orally disintegrating tablets were taste masked. [0083] The tablets were tested for releases using a Dissolution Tester (Model VK 7000, Varian, Inc.) following USP 27/NF 22 with Apparatus 2. Dissolution vessels were filled with 900 ml pH 5.8 phosphate buffer at 37.0° C. The paddles were at 50 rpm. 5 ml samples were withdrawn from dissolution vessel at 30 min. Immediate release of the active was achieved with 96% release in 30 min. EXAMPLE III Orally Disintegrating Tablets Containing Soy/EC Coated Acetaminophen [0084] Soy/EC coated acetaminophen at 92% activity was prepared as in Example I. The coated acetaminophen was mixed excipients using a Turbula blender according to the following formula: 110 g coated APAP (92% active) 50 g Pearlitol 200SD 30 g ProSolv 50 6 g Polyplasdone XL 2 g tartaric acid 1 g Mg-stearate [0091] Tableting was done the same way as in the previous examples. The average weight of the tablets was 515 mg, the hardness range 0.6-0.8 kP. The tablets did not taste bitter. The tablets were tested for releases using a Dissolution Tester (Model VK 7000, Varian, Inc.) following USP 27/NF 22 with Apparatus 2. Dissolution vessels were filled with 900 ml pH 5.8 phosphate buffer at 37.0° C. The paddles were set at 50 rpm. 5 ml samples were withdrawn from dissolution vessel at 45 min. Immediate release of the active was achieved with 98% release in 45 min. EXAMPLE IV Orally Disintegrating Tablets Containing Soy Coated Ibuprofen [0092] Soy coated ibuprofen at 80% activity was prepared as in Example I. The coated ibuprofen was mixed with excipients using a Turbula blender according to the following formula: 50 g coated ibuprofen (80% active) 50 g Peralitol 200SD 20 g ProSolv HD90 3 g Polyplasdone 1 g Splenda 1 g Mg-stearate [0099] Pharmaceutically acceptable tablets were made on a K-International single-action tableting press. The tablet hardness (Dr. Schleusinger Tablet Tester 8M) ranged from 0.8-1.0 kP. The weight (Mettler) of a tablet was 500 mg on average. The tablets were found to be palatable, i.e., no bitterness or after-taste or throat-bite was noticable. A Varian VK7000 dissolution tester was used to measure the aqueous release of the active ingredient, following the USP #2 method. 900 ml pH 7.2 phosphate buffer was used as the medium. Based upon an average of two tablets, which resulted in 93% release after 60 minutes at 37° C. EXAMPLE V Orally Disintegrating Dosage Forms Containing the Coated Active Substrate, Caffeine (Soy/10% Ethylcellulose Coating) [0100] Soy/EC coated caffeine at 70% activity was prepared as in Example I. Fifteen pounds of caffeine was coated with 6.4 lbs of HSO/EC, yielding particles with 70% activity. The lipid coated caffeine substrate was mixed with excipients using a Patterson-Kelly V-blender according to the following formula: 70 g coated caffeine (70% active, soy/EC coating) 70 g Pearlitol 200SD 20 g ProSolv 50 6 g Polyplasdone XL 2 g tartaric acid 2 g Ca-stearate [0107] The powder blend was successfully compressed into tablets on a K-International press. Acceptable tablets were prepared; average weight: 730 mg; hardness range: 1.0-1.5 kP; no bitterness was detected. EXAMPLE VI Orally Disintegrating Dosage Forms Containing the Coated Active Substrate, Caffeine (Castorwax/10% Ethylcellulose Coating) [0108] Castorwax/EC coated caffeine at 70% and 60% activities were prepared as in Example I. Each coated caffeine was mixed with excipients using a Patterson-Kelly V-blender according to the following formulas: Formula I: 70 g coated Caffeine (70% active) 70 g Pearlitol 200SD 20 g ProSolv 50 6 g Polyplasdone XL 2 g tartaric acid 2 g Ca-stearate Formula II: 70 g coated Caffeine (60% active) 70 g Pearlitol 200SD 20 g ProSolv 50 6 g Polyplasdone XL 2 g tartaric acid 2 g Ca-stearate [0123] Blending and tableting were done the same way as in previous Examples. Acceptable tablets were prepared. The tablet weight was about 525 mg, the hardness ranged from 1.1 to 1.4 kP. The tablets were taste masked in each case. [0124] The tablets were tested for releases using a Dissolution Tester (Model VK 7000, Varian, Inc.) following USP 27/NF 22 with Apparatus 2. Dissolution vessels were filled with 900 ml distilled water at 37.0° C. The paddles were set at 50 rpm. 5 ml samples were withdrawn from dissolution vessel at 60 min. Immediate release of the active achieved with 94.0% release for tablets made from 70% active caffeine microencapsulates and 76.4% release for caffeine tablet made from 60% active microencapsulates in 60 min. EXAMPLE VII Orally Disintegrating Dosage Forms Containing the Coated Active Substrate, Caffeine (Castorwax/20% Ethylcellulose Coating) [0125] Castorwax/EC (80:20) coated caffeine at 60% activity was prepared as in Example I. The coated caffeine was mixed with excipients using a Petterson-Kelly V-blender according to the following formula: 70 g coated Caffeine (60% active) 70 g Pearlitol 200SD 20 g ProSolv 50 6 g Polyplasdone XL 2 g tartaric acid 2 g Ca-stearate [0132] Blending and ableting were done the same way as in previous Examples. Acceptable tablets were prepared. The tablet weight was about 513 mg, the hardness ranged from 1.0 to 1.4 kP. The tablets were taste masked. The tablets were tested for releases using a Dissolution Tester (Model VK 7000, Varian, Inc.) as described in Example VI. Immediate release of the active was achieved with 84.1% release in 60 min. EXAMPLE VIII Sieving of Lipid Coated Substrate with Silicified Excipient [0133] 4.0 kg of soy-coated APAP (92% active)was bag mixed with 200 g CabOSil. The blend was sieved through a USSS 40-mesh screen by one person. After about an hour, the sieving completely stopped due to clogging. Weighing showed that only 2.3 kg of the 4.2 kg blend gad gone through the screen. [0134] The test was repeated with ProSolv in place of CabOSil. Since silica constitutes only about 2% of ProSolv, a comparativly large amount of the latter was elected to be used. 2.0 kg of soy coated APAP (92% active) was bag mixed with 2.0 kg of ProSolv SMCC90. The blend was sieved through a USSS 40-mesh screen by the same person. The entire four-kg blend went through in about ten minutes, and there was no observable clogging on the screen. EXAMPLE IX Orally Disintegrating Tablets Containing Soy/EC Coated Acetaminophen [0135] Acetaminophen (APAP) was coated with soy/EC to 92% active, as described in Example I. The following compression mix was made: Ingredient Weight (kg) Percent (% w/w) Coated APAP 14.0 33.7 Pearlitol 200SD 18.0 43.3 Avicel PH102 3.0 7.2 Starch 1500 3.0 7.2 Polyplasdone 2.2 5.3 Orange 0.46 1.1 CabOSil 0.60 1.4 Mg-stearate 0.30 0.7 [0136] To include the flow-aid CabOSil, the common practice is to co-sieve it with the other ingredients, preferably with the active ingredient. In this case, the co-sieving with the lipid coated active substrates proved to be difficult and extremely time-consuming, as in Example VIII. It took about three hours for three individuals, i.e., about nine man-hours to accomplish. [0137] When CabOSil and Avicel were replaced with ProSolv SMCC 90, the ProSolv provided sufficient flow aid properties and the co-sieving time was reduced to 10 minutes. Once again, a similar result as in Example VIII. [0138] In the preceding specification, the invention has been described with reference to specific exemplary embodiments and examples 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 as set forth in the claims that follow. The specifications are accordingly to be regarded in an illustrative manner rather than a restrictive sense.
The present invention is directed to orally disintegrating dosage forms comprising lipid coated substrates and silicified excipients. The use of silicified excipients in the orally disintegrating dosage form along with lipid coating of active agents, allows for improvements in the ability to prepare these dosage forms. Further, the dosage form can prevent unpleasant taste or aftertaste and provide better chemical and mechanical stability of the coated active substrate. This present invention also provides the possibility of harder more durable tablets, along with targeted immediate or modified release profiles for the active agent.
0
[0001] The present invention relates to photostable cosmetic compositions comprising sunscreens, more particularly to cosmetic compositions comprising dibenzoylmethane sunscreens. [0002] It is generally known that UV-A rays having wavelengths between 320 and 400 nm cause tanning of the skin, localized irritation, sun-burn and melanoma. It is also known that UV-B radiation, having wavelength between 280 nm and 320 nm also promotes tanning of the human epidermis, in addition to causing various other short and long-term damages, such as photoaging of skin, dryness, deep wrinkle formation, mottled pigmentation and the breakdown of elastic tissues and collagen. Therefore, it is desirable to protect the skin from the harmful effects of ultraviolet radiation. [0003] Various cosmetic preparations have been reported for preventing and/or protecting the skin from harmful effects of ultraviolet radiation. Numerous organic sunscreen agents capable of absorbing harmful UV-A rays are also reported in the field of cosmetics amongst which a particularly advantageous organic sunscreen agent is dibenzoylmethane and its derivatives. This is because they exhibit high intrinsic absorption power. On the other hand p-methoxycinnamic acid and its derivatives are also used extensively as they are highly effective UV-B sunscreens. It is essential that cosmetic compositions contain both UV-A and UV-B sunscreens so as to provide protection over the entire range of UV radiation. [0004] It is known that dibenzoylmethane and its derivatives are relatively sensitive to ultraviolet radiation and they decompose rapidly under the effect of sunlight. This decomposition is accelerated in the presence of UV-B sunscreens, especially p-methoxycinnamic acid and its derivatives. Owing to photochemical instability of dibenzoylmethane and its derivatives in the presence of UV-B sunscreens, especially p-methoxycinnamic acid and its derivatives, one cannot guarantee constant protection during prolonged exposure to the sun. This therefore warrants repeated applications at regular and frequent intervals by the user in order to maintain effective protection against UV rays. [0005] On the other hand, it is also known that the protection afforded by cosmetic sunscreen compositions reduces over a period of time and typically by the end of 1 hour from application, the protection is almost negligible. Stabilization of dibenzoylmethane and its derivatives therefore becomes important so that the user achieves complete advantage of its efficacy and he does not have to resort to frequent applications. [0006] Various methods have been reported for stabilization of dibenzoylmethane and its derivatives in cosmetic formulations, which include the use of stabilizers such as thickening copolymers, amphiphilic copolymers and micronized insoluble organic UV sunscreen agents. [0007] In an alternative approach, U.S. Pat. No. 5,985,251 (Roche Vitamins, 1999) describes light screening cosmetics wherein compositions comprising dibenzoylmethane derivatives and p-methoxycinnamic acid derivatives are stabilized by incorporating 0.5 to 12% by weight 3,3-diphenylacrylate derivatives or benzylidene camphor derivatives. It can be readily seen that the formulation must necessarily contain an additional UV-B sunscreen of the diphenylacrylate class to stabilize UV-A sunscreens, a large part of which ends up getting utilized for stabilizing the UV-A sunscreen, without providing protection, which is its primary role. Incorporation of the additional sunscreen would also add to the cost of the formulation. [0008] Therefore there exists the need for cosmetic compositions comprising dibenzoylmethane or its derivatives, which are stabilized, especially in the presence of p-methoxycinnamic acid or its derivatives, wherein specialty polymers and/or additional sunscreen stabilizers are not essentially required. It is highly desirable to have cosmetic compositions, which are stabilized with ingredients that are conventionally used in cosmetics, thereby reducing the complexities of formulation and substantially reduce costs. The present inventors have surprisingly found that cosmetic compositions comprising dibenzoylmethane or its derivative and p-methoxycinnamic acid or its derivative, can be stabilized by incorporating a combination of fatty alcohol ethoxylates and polyalkyleneglycol. [0009] It is therefore an object of the present invention to obviate at least some drawbacks of the prior art and provide photostable cosmetic compositions having sunscreens. [0010] Another object of the present invention is to provide photostable compositions comprising dibenzoylmethane sunscreens, wherein the stabilization is brought about by using conventionally used ingredients. SUMMARY OF THE INVENTION [0011] According to one aspect, the present invention relates to a photostable cosmetic composition comprising [0000] 0.1% to 10% by weight dibenzoylmethane or its derivative; 0.1% to 10% by weight p-methoxy cinnamic acid or its derivative, wherein said composition comprises from 0.5% to 8% by weight C8-C18 fatty alcohol ethoxylate and 0.5% to 8% by weight polyalkyleneglycol. [0012] Preferably dibenzoylmethane or its derivative is present from 0.1% to 5% by weight, more preferably from 0.1% to 2% by weight of the composition. [0013] It is also preferred that p-methoxy cinnamic acid or its derivative is present from 0.1% to 5% by weight, more preferably from 0.1% to 2% by weight of the composition. [0014] According to a most preferred aspect, the dibenzoylmethane derivative is 4-tert-butyl-4′-methoxydibenzoylmethane and p-methoxycinnamic acid derivative is 2-ethyl-hexyl-p-methoxycinnamate. [0015] It is preferred that the fatty alcohol ethoxylate is present from 0.5% to 4% by weight of the composition. [0016] According to a preferred aspect, the polyalkyleneglycol is present from 0.5 to 4% by weight. [0017] According to a preferred aspect, the molecular weight of polyethyleneglycol is between 200 to 100000 Daltons, more preferably between 200 to 10000 Daltons. [0018] As used herein, the term “cosmetic composition” is intended to describe compositions for topical application to human skin, including leave-on and wash-off products. The term “skin” as used herein includes the skin on the face, neck, chest, back, arms, hands, legs, and scalp. [0019] For the avoidance of doubt the word “comprising” is intended to mean including but not necessarily consisting of or composed of. In other words the listed options need not be exhaustive. [0020] Other characteristics, aspects and advantages of the invention and the essential, preferred and optional features of the invention will emerge on reading the detailed description that follows. DETAILED DESCRIPTION OF THE INVENTION [0021] Preferred dibenzoylmethane derivative are selected from 4-tert-butyl-4′-methoxydibenzoylmethane, 2-methyldibenzoylmethane, 4-methyl-dibenzoyl-ethane, 4-isopropyldibenzoyl-methane, 4-tert-butyldibenzoylmethane, 2,4-dimethyldibenzoylmethane, 2,5-dimethyldibenzoylmethane, 4,4′-diisopropyl-dibenzoylmethane, 2-methyl-5-isopropyl-4′-methoxydibenzoylmethane, 2-methyl-5-tert-butyl-4′-methoxy-dibenzoylmethane, 2,4-dimethyl-4′-methoxydibenzoylmethane or 2,6-dimethyl-4-tert-butyl-4′-methoxy-dibenzoylmethane. The most preferred dibenzoylmethane derivative is 4-tert.-butyl-4′-methoxydibenzoylmethane. [0022] The preferred p-methoxycinnamic acid derivative are selected from 2-ethylhexyl-p-methoxycinnamate, ammonium-p-methoxycinnamate, sodium-p-methoxycinnamate, potassium-p-methoxycinnamate, or salts of primary, secondary or tertiary amines of p-methoxycinnamic acid and more preferably it is 2-ethylhexyl-p-methoxy cinnamate. [0023] Fatty alcohol ethoxylates (also known as ethoxylated fatty alcohols) have the general formula: [0000] R—O—(CH2-CH2-O) n H [0000] where R is a saturated or unsaturated, linear or branched hydrocarbon-based chain having from 10 to 24 carbon atoms, and n is an integer ranging from 8 to 50. [0024] Fatty alcohol ethoxylates are products of the addition of ethylene oxide onto primary alcohols. The ethoxylates are produced by known methods and are basically mixtures. Depending on their production, they may have a conventional broad homolog distribution or a narrow homolog distribution. The degree of ethoxylation (EO: number of ethylene oxide units added on) represents a Gauss distribution, the maximum of the Gauss curve being referred to here as the average degree of ethoxylation “n”. [0025] Preferred are products of the addition of ethylene oxide onto caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and technical mixtures thereof. Representative examples of ethoxylated fatty alcohols are the addition products of ethylene oxide with lauryl alcohol, in particular those containing from 9 to 50 oxyethylenated groups (having CTFA names Laureth-9 to Laureth-50); the addition products of ethylene oxide with behenyl alcohol, in particular those containing from 9 to 50 oxyethylenated groups (having CTFA names Beheneth-9 to Beheneth-50); the addition products of ethylene oxide with cetearyl alcohol (mixture of cetyl alcohol and of stearyl alcohol) in particular those containing from 9 to 30 oxyethylenated groups (having CTFA names Ceteareth-9 to Ceteareth-30); the addition products of ethylene oxide with cetyl alcohol, in particular those containing from 9 to 30 oxyethylenated groups (having CTFA names Ceteth-9 to Ceteth-30); the addition products of ethylene oxide with stearyl alcohol, in particular those containing from 9 to 30 oxyethylenated groups (having CTFA names Steareth-9 to Steareth-30; the addition products of ethylene oxide with isostearyl alcohol, in particular those containing from 9 to 50 oxyethylenated groups (having CTFA names Isosteareth-9 to Isosteareth-50); and mixtures thereof. [0026] The more preferred alcohol ethoxylates are addition products of ethylene oxide onto fatty alcohol having 8 to 18 carbon atoms, i.e. C8-C18 fatty alcohol ethoxylates, and in a highly preferred aspect; it is lauryl alcohol, which has 12 carbon atoms. It is marketed under the name Brij® 35 (laureth-35, lauryl alcohol with 35 EO units). Several grades of Brij are available, depending upon the degree of ethoxylation. [0027] A suitable polyalkyleneglycol is selected from polyethyleneglycol, polypropyleneglycol or polybutyleneglycol and preferably it is polyethyleneglycol. [0028] The present composition can include any cosmetic vehicle/carrier known in the art. Suitable vehicles include, but are not limited to, one or more of the following: vegetable oils; esters such as octyl palmitate, isopropyl myristate and isopropyl palmitate; ethers such as dicapryl ether and dimethyl isosorbide; alcohols such as ethanol and isopropanol; fatty alcohols such as cetyl alcohol, stearyl alcohol and behenyl alcohol; isoparaffins such as isooctane, isododecane and isohexadecane; silicone oils such as dimethicones, cyclic silicones, and polysiloxanes; hydrocarbon oils such as mineral oil, petrolatum, isoeicosane and polyisobutene; polyols such as propylene glycol, ethoxydiglycol, glycerin, butylene glycol, pentylene glycol and hexylene glycol; as well as water, or any combinations of the above. Fatty acids having from 10 to 30 carbon atoms may also be included as cosmetically acceptable carriers for compositions of this invention. Illustrative of this category are pelargonic, lauric, myristic, palmitic, stearic, isostearic, hydroxystearic, oleic, linoleic, ricinoleic, arachidic, behenic and erucic acids. [0029] Humectants of the polyhydric alcohol-type may also be employed as cosmetically acceptable carriers in compositions of this invention. The humectant aids in increasing the effectiveness of the emollient, reduces skin dryness and improves skin feel. Typical polyhydric alcohols include glycerol, polyalkylene glycols and more preferably alkylene polyols and their derivatives, including propylene glycol, dipropylene glycol, polypropylene glycol, polyethylene glycol and derivatives thereof, sorbitol, hydroxypropyl sorbitol, hexylene glycol, 1,3-butylene glycol, 1,2,6-hexanetriol, ethoxylated glycerol, propoxylated glycerol and mixtures thereof. The amount of humectant may range anywhere from 0.5% to 30%, preferably between 1% and 15% by weight of the composition. [0030] The amount of cosmetically acceptable vehicle in the present composition will vary considerably based upon product form, but typically will range from about 20 wt % to about 70 wt % and preferably from about 20 wt % to about 40 wt %, based upon the total weight of the composition. The cosmetically acceptable vehicle acts as a dilutent, dispersant or carrier for the in the composition, so as to facilitate the distribution of the sunscreens when the composition is applied to the skin. [0031] The present composition, when in emulsion form, could optionally have one or more additional emulsifiers, without deviating from the scope of the invention, which are preferably selected from sorbitan esters dimethicone copolyols; polyglyceryl-3-diisostearate; such as sorbitan monooleate and sorbitan monostearate; glycerol esters such as glycerol monostearate and glycerol monooleate; polyoxyethylene phenols such as polyoxyethylene octyl phenol and polyoxyethylene nonyl phenol; polyoxyethylene ethers such as polyoxyethylene cetyl ether and polyoxyethylene stearyl ether; polyoxyethylene glycol esters; polyoxyethylene sorbitan esters; dimethicone copolyols; polyglyceryl-3-diisostearate; or any combinations thereof. An oil or oily material may be present, together with an emulsifier to provide either a water-in-oil emulsion or an oil-in-water emulsion, depending largely on the average hydrophilic-lipophilic balance (HLB) of the emulsifier employed. Preferred anionic surfactants include soap, alkyl ether sulfate and sulfonates, alkyl sulfates and sulfonates, alkylbenzene sulfonates, alkyl and dialkyl sulfosuccinates, C9-C20 acyl isethionates, acyl glutamates, C8-C20 alkyl ether phosphates and combinations thereof. Typically, the additional emulsifier could be present from 1 wt % to about 12 wt %, based upon the total weight of the composition. Water when present will be in amounts which could range from 5% to 75%, preferably from 20% to 70%, optimally between 40% and 70% by weight of said composition. [0032] Besides water, relatively volatile solvents may also serve as carriers within compositions of the present invention. Most preferred are monohydric C1-C3 alkanols. These include ethyl alcohol and isopropyl alcohol. [0033] Preferred cream bases are, for example, beeswax, cetyl alcohol, stearic acid, glycerine, propylene glycol, propylene glycol monostearate, polyoxyethylene cetyl ether and the like. Preferred lotion bases include, for example, oleyl alcohol, ethanol, propylene glycol, glycerine, lauryl ether, sorbitan monolaurate and the like. [0034] When the composition of the present invention is in the form of film-forming skin packs or masks it could comprise film formers known in the art. These include acrylate copolymers, acrylates C12-22 alkyl methacrylate copolymer, acrylate/octylacrylamide copolymers, acrylate/VA copolymer, amodimethicone, AMP/acrylate copolymers, behenyl beeswax, behenyl/isostearyl, beeswax, butylated PVP, butyl ester of PVM/MA copolymers, calcium/sodium PVM/MA copolymers, dimethicone, dimethicone copolyol, dimethicone/mercaptopropyl methicone copolymer, dimethicone propylethylenediamine behenate, dimethicolnol ethylcellulose, ethylene/acrylic acid copolymer, ethylene/MA copolymer, ethylene/VA copolymer, fluoro C2-8 alkyldimethicone, hexanediol beeswax, C30-38 olefin/isopropyl maleate/MA copolymer, hydrogenated styrene/butadiene copolymer, hydroxyethyl ethylcellulose, isobutylene/MA copolymer, laurylmethicone copolyol, methyl methacrylate crosspolymer, methylacryloyl ethyl betaine/acrylates copolymer, microcrystalline wax, nitrocellulose, octadecene/MA copolymer, octadecene/maleic anhydride copolymer, octylacrylamide/acrylate/butylaminoethyl methacrylate copolymer, oxidized polyethylene, perfluoropolymethylisopropyl ether, polyacrylic acid, polyethylene, polymethyl methacrylate, polypropylene, polyquaternium-10, polyquaternium-11, polyquaternium-28, polyquaternium-4, PVM/MA decadiene crosspolymer, PVM/MA copolymer, PVP, PVP/decene copolymer, PVP/eicosene copolymer, PVP/hexadecene copolymer, PVP/MA copolymer, PVP/VA copolymer, silica, silica dimethyl silylate, sodium acrylate/vinyl alcohol copolymer, stearoxy dimethicone, stearoxytrimethylsilane, stearyl alcohol, stearylvinyl ether/MA copolymer, styrene/DVB copolymer, styrene/MA copolymer, tetramethyl tetraphenyl trisiloxane, tricontanyl trimethyl pentaphenyl trisiloxane, trimethylsiloxysilicate, VA/crotonates copolymer, VA/crotonates/vinyl proprionate copolymer, VA/butyl maleate/isobornyl acrylate copolymer, vinyl caprolactam/PVP/dimethylaminoethyl methacrylate copolymer, and vinyldimethicone. [0035] The film former is preferably present in an amount from about 0.5 wt % to about 5 wt %, and more preferably from about 1 wt % to about 5 wt %, based upon the total weight of the composition. More preferably, the film former is present in an amount about 3 wt % of the total weight of the composition. [0036] Optionally, the present composition may include one or more ingredients selected from chelating agents, botanical extracts, colorants, depigmenting agents, emollients, exfollients, fragrances, humectants, moisturizers, preservatives, skin protectants, skin penetration enhancers, stabilizers, thickeners, viscosity modifiers, vitamins, anti-aging, wrinkle-reducing, skin whitening, anti-acne, and sebum reduction agents or any combinations thereof. Examples of these include alpha-hydroxy acids and esters, beta-hydroxy acids and ester, polyhydroxy acids and esters, kojic acid and esters, ferulic acid and ferulate derivatives, vanillic acid and esters, dioic acids (such as sebacid and azoleic acids) and esters, retinol, retinal, retinyl esters, hydroquinone, t-butyl hydroquinone, mulberry extract, licorice extract, and resorcinol derivatives such as 4-substituted resorcinol derivatives, as well as additional sunscreens such UV diffusing agents, typical of which is finely divided titanium oxide and zinc oxide which generally are between 5 nm and 100 nm and preferably between 10 and 50 nm) of coated or uncoated metal oxides, for instance nanopigments of titanium oxide (amorphous or crystallized in rutile and/or anatase form), of iron oxide, of zinc oxide, of zirconium oxide or of cerium oxide, which are all photoprotective agents that are well-known per se, acting by physically blocking out (reflection and/or scattering) UV radiation. Standard coating agents are, moreover, alumina and/or aluminum stearate. The compositions according to the invention may also contain agents for artificially tanning and/or browning the skin (self-tanning agents), for instance dihydroxy-acetone (DHA). [0037] Thickeners may also be utilized as part of the cosmetically acceptable carrier of compositions according to the present invention, without deviating from the scope of the present invention. Typical thickeners include crosslinked acrylates (e.g. Carbopol 982), hydrophobically-modified acrylates (e.g. Carbopol 1382), cellulosic derivatives and natural gums. Among useful cellulosic derivatives are sodium carboxymethylcellulose, hydroxypropyl methylcellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, ethyl cellulose and hydroxymethyl cellulose. Natural gums suitable for the present invention include guar, xanthan, sclerotium, carrageenan, pectin and combinations of these gums. Amounts of the thickener may range from 0.0001% to 0.5%, usually from 0.001% to 1%, optimally from 0.01% to 0.5% by weight. [0038] The inventive cosmetic composition could also optionally contain lathering surfactant. By “lathering surfactant” is meant a surfactant which, when combined with water and mechanically agitated, generates a foam or lather. Preferably, the lathering surfactant should be mild, meaning that it must provide sufficient cleansing or detergent benefits but not overly dry the skin, and yet meet the lathering criteria described above. The cosmetic compositions of the present invention may contain a lathering surfactant in a concentration of about 0.01% to about 50%. This is typically needed, in wash-off products, such as face-washes. [0039] The cosmetic compositions according to the invention may also contain, besides the essential elements, one or more additional sunscreens that are different from the preceding sunscreens, which are water-soluble, liposoluble or insoluble in the cosmetic solvents commonly used. These screening agents may be suitably chosen from salicylic derivatives, benzylidenecamphor derivatives, triazine derivatives, benzophenone derivatives, [β], [β]′-diphenylacrylate derivatives, phenyl-benzimidazole derivatives, anthranilic derivatives, imidazoline derivatives, methylenebis(hydroxyphenyl-benzotriazole) derivatives, p-aminobenzoic acid derivatives, and screening hydrocarbon-based polymers and screening silicones derivatives. [0040] The preferred organic UV-screening agents are chosen from the following compounds: Ethylhexyl salicylate, Octocrylene, Phenylbenzimidazolesulphonic acid, Terephthalylidenedicamphorsulphonic acid, Benzophenone-3, Benzophenone-4, Benzophenone-5, 4-Methylbenzylidene, Benzimidazilate, Anisotriazine, 2,4,6-Tris(diisobutyl 4′-aminobenzalmalonate)-s-triazine, Ethylhexyltriazone, Diethylhexylbutamidotriazone, Methylenebis(benzotriazolyl)tetramethylbutyl-phenol, Drometrizole trisiloxane, and mixtures thereof. [0041] Specific preparations of the cosmetics to which the present invention is applicable include creams, ointments, emulsions, lotions, oils and face-packs, balm, gel, mousse, stick or hair-gels, hair-creams and the like. The emulsion could be, for example, anhydrous, water-in-oil, oil-in-water, water-in-silicone, or multiple emulsions. In case of protection of the hairs, the suitable formulations are shampoos, conditioners, lotions, gels, emulsions, dispersions, lacquers, and the like. [0042] The cosmetic composition of the invention can be formulated as a lotion having a viscosity of from 4,000 to 10,000 mPas, a fluid cream having a viscosity of from 10,000 to 20,000 mPas or a cream having a viscosity of from 20,000 to 100,000 mPas or above, all measured at 25° C. [0043] The composition according to the invention is intended primarily as a personal care product for topical application to human skin, as well as to protect exposed skin from the harmful effects of excessive exposure to sunlight. [0044] In use, a small quantity of the composition, for example about 0.1 ml to about 5 ml, is applied to exposed areas of the skin, from a suitable container or applicator and, if necessary, it is then spread over and/or rubbed into the skin using the hand or fingers or a suitable device. [0045] In order to further illustrate the present invention and the advantages thereof, the following specific examples are given, it being understood that same are intended only as illustrative and in no way limitative. In said examples to follow, all parts and percentages are given by weight, unless otherwise indicated. EXAMPLES Example 1 [0046] Demonstration of stabilization of dibenzoylmethane derivative using combination of fatty alcohol ethoxylate and polyethyleneglycol, according to the invention. [0047] Various cosmetic cream compositions were prepared as per formulation details given in table 1 below. [0000] TABLE 1 Ingredients % wt Control Form 1 Form 2 Form 3 Form 4 Form 5 Stearic acid 18 18 18 18 18 18 Potassium 0.67 0.67 0.67 0.67 0.67 0.67 hydroxide Cetyl alcohol 0.53 0.53 0.53 0.53 0.53 0.53 Isopropyl 0.75 0.75 0.75 0.75 0.75 0.75 myristate Dimethicone 0.5 0.5 0.5 0.5 0.5 0.5 200 Niacinamide 1 1 1 1 1 1 Parsol 1789 0.8 0.8 0.8 0.8 0.8 0.8 Parsol MCX 0.75 0.75 0.75 0.75 0.75 0.75 Brij-35 — — 4 4 — — Tween 80 — — — — 4 — Span 80 — — — — 4 Polyethylene — 4 — 4 4 4 glycol 200 Water and 100 100 100 100 100 100 other minors upto Tween 80 Polyoxythylene sorbitan monooleate (Uniquema) Span 80 Sorbitan monooleate (Uniquema) Brij-35 Polyoxyethylene lauryl ether (Uniquema) Parsol 1789 4-tert.-butyl-4′-methoxydibenzoylmethane (Merck) Parsol MCX 2-ethylhexyl methoxycinnamate (Merck) Processing [0000] 1. Weighed quantities of water, potassium hydroxide, EDTA, p-casitose, and glycerin were taken in a 100 ml beaker (vessel A). 2. Weighed quantities of isopropyl myristate, diemthicone 200, Parsol 1789, Parsol MCX, propylparaben, methylparaben, cetyl alcohol, and phenoxyethanol were taken in another beaker (vessel B) 3. Stearic acid was melted by heating to 70° C. in a separate vessel. 4. Contents of vessel B were melted at 70° C. 5. Vessel B was heated to 75° C. under continuous homogenization at low shear (500-700 rpm). 6. After attaining 70° C., molten stearic acid was added to vessel A, slowly and under continuous stirring. 7. After 1-2 min of stirring Brij 35/Tween 80/Span 80 was added, followed by the addition of PEG-200 in above rotating mixture, followed by the addition of TiO2. 8. Molten mass of vessel B was added to it. 9. Shear rate of homogenization was increased to 1000-1200 rpm and was continued for 5 min. 10. The hot mixture was thereafter allowed to cool at room temperature with continuous stirring at low speed (500-700 rpm). 11. At 60° C., niacinamide was added. 12. Mixture was allowed to cool to room temperature. [0060] Test Method [0061] The following test method was used for determining the stability of dibenzoylmethane sunscreens in the compositions of the present invention as well as for all the comparative examples described below. 1. A clean glass slide was taken and its weight was recorded (A). 2. About 10 mg of cream was applied and spread on about 2 cm 2 . 3. The weight of slide with cream was recorded as (B). 4. Subtraction of B from A gave the weight of cream applied (C). 5. The above-mentioned process was repeated six times for each test formulation. 6. These glass slides were exposed to sun simultaneously for various time intervals: 0 min, 15 min, 30 min and 60 min respectively. 7. After exposure to sunlight the creams were extracted in methanol and the volume was made up to 25 ml. 8. The UV-absorbance of each of the samples was recorded on a UV spectrophotometer. 9. Absorbance per unit weight of the sample was calculated by dividing the absorbance at λ max (i.e. 357 nm, which is λ max of dibenzoylmethanes) by weight of the cream (C). 10. The percentage absorbance remaining which is an indicator of the stability of the sample was calculated as follows: [0073] Percentage absorbance remaining=[A n /A 0 ×100] where A 0 is “absorbance per unit weight” of 0 min sample, and A n is “absorbance per unit weight” of nth min sample. The results of the experiment conducted in example 1 are summarized in table 2 below. It is to be noted that the intensity of sunlight was found to vary from 20-40 mW/Cm 2 at the time of exposure of the slides to sun and the experiments were conducted on different days. Therefore, the absolute values of % absorbance for the same/similar experiments conducted over the entire period, e.g. experiments using control samples are different across the tables. [0000] TABLE 2 Sunlight % Absorbance of Parsol 1789 remaining after exposure, Exposure when measured by the procedure given above. time/min Control Form 1 Form 2 Form 3  0 (T 0 ) 100 100 100 100 15 (T 15 ) 79 91 78 97 30 (T 30 ) 68 91 69 93 45 (T 45 ) 60 80 60 91 60 (T 60 ) 42 69 57 88 [0074] The above table indicates that in the formulation containing both PEG 200 and Brij-35, a significantly higher activity of dibenzoylmethane sunscreen is available after 1 hour of application, as evident from the absorbance value. Example 2 [0075] To study the effect of combination of polyethyleneglycol with other surfactants on the stability of dibenzoylmethane sunscreen and its comparison with the combination of polyethyleneglycol with Brij 35 according to the invention. [0076] The results are summarized in table 3 below. [0000] TABLE 3 Sunlight % Absorbance of Parsol 1789 remaining after exposure, Exposure when measured by the procedure given above. time/min Control Form 4 Form 5 Form 3  0 (T 0 ) 100 100 100 100 15 (T 15 ) 66 73 96 97 30 (T 30 ) 66 71 78 94 45 (T 45 ) 47 63 78 85 60 (T 60 ) 40 64 75 83 [0077] Thus it can be readily seen that a combination of polyethylene glycol and fatty alcohol ethoxylate gives better stability as compared to combination of polyethylene glycol and other surfactants/emulsifiers. Example 3 [0078] The present inventors have also determined the effect of varying the molecular weight of polyethyleneglycol on the stability of dibenzoylmethane. The results of this experiment are summarized in table 4 below. [0000] TABLE 4 % Absorbance of Parsol 1789 remaining after exposure, when measured by the procedure given above. Form 3 with Form 3 with 4% PEG Form 3 with 4% PEG 20000 4% PEG Sunlight 6000 instead instead 100000 Exposure of 4% PEG of 4% instead of 4% time/min Control Form 3 200 PEG 200 PEG 200  0 (T 0 ) 100 100 100 100 100 15 (T 15 ) 74 86 91 86 96 30 (T 30 ) 57 81 87 80 81 45 (T 45 ) 50 78 78 68 76 60 (T 60 ) 47 72 71 70 72 [0079] The above table indicates that with various molecular weights of polyethylene glycol, greater than 70% of the dibenzoylmethane derivative remains available, even after 1 hour from application. This demonstrates that any molecular weight of PEG from 200 to 100000 can be used, without departing from the scope of the invention. Example 4 [0080] In yet another set of experiments, the effect of 2 grades of fatty alcohol ethoxylates (Brij) on the stability of dibenzoylmethane sunscreen was studied in cosmetic creams, the results of which are summarized in table 5 below. [0000] TABLE 5 % Absorbance of Parsol 1789 remaining after exposure, when measured by the procedure given below. Sunlight Form-3 with 4% Exposure Brij 56 instead of time/min Control Form 1 Form 3 4% Brij 35.  0 (T 0 ) 100 100 100 98 15 (T 15 ) 81 81 99 84 30 (T 30 ) 70 69 95 78 45 (T 45 ) 45 68 84 74 60 (T 60 ) 43 59 83 74 (Note: Brij 56 is polyethylene glycol hexadecyl ether or polyoxyethylene 10 cetyl ether(CAS number 9004-95-9) (Uniquema or Sigma-Aldrich)) [0081] Thus, it can be readily seen that different grades of fatty alcohol ethoxylates provide a high degree of stability to the dibenzoylmethane sunscreen in the composition. Example 5 [0082] The stability of dibenzoylmethane derivative was also studied in the case of cosmetic lotions, to test the invention in a different carrier/vehicle. The details of the formulation are present in table 6 below. The processing details are also given below. The Results are summarized in the table 7 below. [0000] TABLE 6 Percentage Control Ingredient lotion Lotion A Lotion B Lotion C Part A Water 84 84 84 84 Part B Brij 35 — 4.00 — 4.00 Peg-200 — — 4.00 4.00 Part C Titanium Dioxide 1.00 1.00 1.00 1.00 Part D Isopropyl Myristate 0.75 0.75 0.75 0.75 Dimethicone DC 200 0.50 0.50 0.50 0.50 Stearic acid 2.00 2.00 2.00 2.00 Cetyl alcohol 0.53 0.53 0.53 0.53 Parsol 1789 0.80 0.80 0.80 0.80 Parsol MCX 0.75 0.75 0.75 0.75 Part E Triethanolamine (99%) 0.50 0.50 0.50 0.50 Total with other minors 100 100 100 100 [0083] Processing 1. Disodium EDTA was added to the water and was mixed until dissolution. 2. Carbopol Ultrez™ was dispersed in the water and was mixed at low speed. 3. The ingredients of Part B were added to the water. 4. The ingredients of Part C were added to the water and mixed after moderate heating. The TiO2 was mixed until it dispersed. 5. The combined Parts A, B and C were heated to 65° C. 6. The ingredients of Part D were heated to 65° C. and mixed until all the solids dissolved. 7. This part D was then added to combined Parts A, B and C. While the temperature was at 65° C., the Part E ingredients were added. 8. The emulsion was mixed under moderate agitation until the temperature reached 40° C. It was later cooled to room temperature and was used as such for analysis. [0000] TABLE 7 Sunlight % Absorbance of Parsol 1789 remaining after exposure, Exposure when measured by the procedure given above. time/min Control lotion Lotion A Lotion B Lotion C  0 (T 0 ) 100 100 100 100 15 (T 15 ) 81 96 81 86 30 (T 30 ) 70 91 69 78 45 (T 45 ) 46 70 68 75 60 (T 60 ) 43 68 59 76 [0092] Thus it can be readily seen that the inventive combination of polyethylene glycol and fatty alcohol ethoxylate stabilizes the dibenzoylmethane derivative, even in a lotion based cosmetic composition. [0093] Thus it can be seen from the foregoing description and examples that the invention provides for a composition comprising stable sunscreens. The invention also provides for compositions comprising stabilized dibenzoylmethane sunscreens, wherein the stabilization is brought about by using ingredients, which are conventionally used in cosmetic compositions. [0094] While the invention has been described in terms of various specific and preferred embodiments, the skilled artisan will appreciate that various modifications, substitutions, omissions, and changes may be made without departing from the spirit thereof.
Photostable cosmetic compositions comprising sunscreens, more particularly to cosmetic compositions comprising dibenzoylmethane sunscreens are provided. It is known that dibenzoylmethane and its derivatives are relatively sensitive to ultraviolet radiation and they decompose rapidly under the effect of sunlight. This decomposition is accelerated in the presence of UV-B sunscreens, especially p-methoxycinnamic acid and its derivatives. The present inventors have surprisingly found that cosmetic compositions comprising dibenzoylmethane or its derivative and p-methoxycinnamic acid or its derivative, can be stabilized by incorporating a combination of fatty alcohol ethoxylates and polyalkyleneglycol.
0
CROSS RELATED APPLICATION This application is a divisional application claiming the benefits of U.S. Non-provisional patent application Ser. No. 13/747,976 filed Jan. 23, 2013, now U.S. Pat. No. 9,103,070, the entirety of which is incorporated herein by reference; the Ser. No. 13/747,976 application in turn claims the benefit of U.S. Provisional Patent Application Ser. No. 61/598,112 filed Feb. 13, 2012, the entirety of which is incorporated herein by reference. BACKGROUND OF THE INVENTION The present invention relates to flashing fluids extracted from pressurized reactor vessels and particularly to flash tanks for flashing black liquor from a pressurized reactor vessel in a pulping or biomass treatment system. Flash tanks are generally used to flash a high pressure fluid liquor stream including steam and condensate. A flash tank typically has a high pressure inlet port, an interior chamber, an upper steam or gas discharge port and a lower condensate or liquid discharge port. Flash tanks safely and efficiently reduce pressure in a pressurized fluid stream, allow recovery of heat energy from the stream, and collect chemicals from the stream in condensate. Flash tanks may be used to recover chemicals from chemical pulping systems, such as Kraft cooking systems. Flash tanks are also used in other types of cooking systems for chemical and mechanical-chemical pulping systems. To pulp wood chips or other comminuted cellulosic fibrous organic material (collectively referred to herein as “cellulosic material”), the cellulosic material is mixed with liquors, e.g., water and cooking chemicals, and pumped in a pressurized treatment vessel. Sodium hydroxide, sodium sulfite and other alkali chemicals are used to “cook” the cellulosic material such as in a Kraft cooking process. These chemicals degrade lignins and other hemicellulose compounds in the cellulosic material. The Kraft cooking process is typically performed at temperatures in a range of 100 degrees Celsius (100° C.) to 170° C. and at pressures at or substantially greater than atmospheric. The cooking (reactor) vessels may be batch or continuous flow vessels. The cooking vessels are generally vertically oriented and may be sufficiently large to process 1,000 tons or more of cellulosic material per day. The material continuously enters and leaves the vessel, and remains in the vessel for several hours. In addition to the cooking vessel, a conventional pulping system may include other reactor vessels (such as vessels operating at or near atmospheric pressure or pressurized above atmospheric pressure) such as for impregnating the cellulosic material with liquors prior to the cooking vessel. In view of the large amount cellulosic material in the impregnation and cooking vessels, a large volume of black liquor is typically extracted from these vessels. The black liquor includes the cooking chemicals and organic chemicals or compounds, e.g., hydrolysate, residual alkali, lignin, hemicellulose and other dissolved organic substances, dissolved from the cellulosic materials. The black liquor is flashed in a flash tank to generate steam and condensate. The cooking chemicals and organic compounds are included with the liquid condensate formed when the liquor is flashed. The steam formed from flashing is generally free of the chemicals and organic compounds. The condensate is processed to, for example, recover and recausticize the cooking chemical. The steam may be used as heat energy in the pulping system. In conventional flash tanks, the black liquor enters flash tanks through an inlet pipe having a fixed inlet diameter. The inlet is not variable or otherwise controllable to adjust the size of the black liquor flow passage. Changes to the flow passage at the inlet to a conventional flash tank for black liquor have been made by changing the inlet piping to the flash tank. Conventional flash tanks do not have a means for adjusting the flow passage; controlling of the volume or the velocity of the black liquor flow into the flash tank, pressure drop in the flash tank, or regulating the pressure in the conduits containing black liquor connected to the inlets to the flash tanks. BRIEF DESCRIPTION OF THE INVENTION An inlet for a flash tank has been conceived where the flow passage area of the inlet to the flash tank is varied to allow for control of the flow passage area of the inlet to the flash tank without changing of physical or mechanical components of the inlet or flash tank. The flow passage area is adjusted by a pivoting hinged plate in the inlet to the flash tank. This movable, hinged plate may be located at, near or after the junction between piping and the inlet to the flash tank. At this junction, the piping typically transitions from piping having a rectangular cross-section to piping circular in cross-section. The movable, hinged plate changes of the cross-sectional area of the inlet to adjust the flow passage area through which hot black liquor flows from fully open to smaller area or from a smaller area to a larger area. This adjustment of the inlet opening size provides a means to control the velocity of the fluid into the tank. The movable, hinged plate may be operated by a pneumatic or electro-mechanical actuator. A formable seal may be provided on either the movable hinged plate or the interior of the pipe to prevent leaking of hot black liquor out of the pipe or past the side edges of the plate. A flash tank has been conceived including: a closed interior chamber; a gas exhaust port coupled to an upper portion of the chamber; a liquid discharge port coupled to a lower portion of the chamber; an inlet nozzle attached to an inlet port of the chamber, wherein the inlet nozzle includes a flow passage having a throat, and a movable valve plate in the flow passage, wherein the valve plate has a first position which defines a first throat area in the flow passage and a second position which defines a second throat area having a smaller cross-sectional area than the first throat area. The valve plate may be a rectangular plate having planar surfaces bounded by edges and the flow passage may have a rectangular cross-section. The rectangular plate may be attached to a hinge attached to a sidewall of the flow passage. The hinge may be attached to an upstream end of the valve plate and creates a pivoting axis for the valve plate. The valve plate may have an actuator connected to the valve plate, wherein the actuator moves the valve plate between the first and second positions. The valve plate may be moved by an actuator having an extendible shaft connected to the valve plate, wherein the actuator moves the valve plate between the first and second positions. A method has been conceived to flash a pressurized liquor comprising: feeding a pressurized liquor to an inlet nozzle of a flash tank; flashing the pressurized liquor as the liquor flows from the inlet nozzle into an interior chamber of the flash tank; exhausting a gas exhaust formed by the flashing through an upper portion of the chamber; discharging a liquid formed by the flashing from a lower portion of the chamber, and adjusting a cross-sectional area of a flow passage in the inlet nozzle by moving a valve plate in the flow passage. The step of feeding may include a first feeding step in which the pressurized liquor flows through the flow passage while the valve plate is at a first position which defines a first throat area in the flow passage and a second feeding step in which the pressurized liquor flows through the flow passage while the valve plate is in a second position which defines a second throat area having a smaller cross-sectional area than the first throat area. Additional valve plate positions may also exist where the valve plate in multiple positions along the flow passage define multiple throats having smaller cross-sectional areas than the first throat area. The method may include adjusting the cross-sectional area of the flow passage in the inlet nozzle allows for control of the volume of flow of black liquor entering the flash tank. Adjusting of the cross-sectional area of the flow passage inlet nozzle may also allow for control of the flow velocity of the black liquor entering the flash tank. Additionally, adjusting the cross-sectional area of the flow passage in the inlet nozzle allows for a degree of control over the pressure drop in the flash tank. Adjusting the cross-sectional area of the flow passage in the inlet nozzle may also ensure sufficient pressure in the conduits upstream of the inlet nozzle to the flash tank. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram of a conventional flash tank receiving black liquor extracted from a pressurized reactor vessel. FIG. 2 is cross-sectional view of the flash tank taken along a horizontal line, wherein the inlet nozzle is attached to the tank along a tangent to tank. FIG. 3 shows a perspective and partially cut-away view of the inlet nozzle to illustrate the valve plate and the connection of the nozzle to the sidewall of the flash tank. FIG. 4 is a cross-sectional schematic view of the inlet nozzle taken along a vertical plane to illustrate the valve plate. DETAILED DESCRIPTION OF THE INVENTION FIG. 1 is a schematic diagram of a pulping system including a flash tank 10 coupled to a vessel 12 , e.g., an impregnation vessel or a cooking vessel. A slurry of cellulosic material 14 and liquor flow to an upper inlet 15 of the vessel 12 . White liquor 16 may be added to the vessel 12 such as through center inlet pipes 18 . Screen assemblies 20 at various elevations in the vessel 12 extract black liquor from the cellulosic material moving down through the vessel 12 . The material is discharged as pulp 22 from the bottom 24 of the vessel. The black liquor extracted from the vessel 12 may flow to the flash tank 10 through conduits 26 fluidly coupling the screen assemblies 20 to a respective flash tank 10 . The number of flash tanks 10 and whether one flash tank 10 receives black liquor from multiple screen assemblies 20 are design choices. The number, size and arrangement of flash tanks 10 may also depend on the design choice of whether to have heat exchange equipment in the conduits 26 leading to the flash tanks 10 . Black liquor flashes in the flash tank 10 to form steam 28 and condensate 30 . The steam 28 flows out upper outlets 17 of the flash tanks 10 . The condensate 30 flows as a liquid from bottom discharges 19 of the flash tanks 10 . FIG. 2 is a cross-sectional view of the flash tank 10 , wherein the cross-section is along a horizontal plane bisecting the inlet piping system to the flash tank 10 . The conduits 26 transporting the black liquor to be flashed may be cylindrical pipes. The inlet nozzle 34 to the flash tank 10 may be rectangular in cross-section. An end outlet 32 of the conduits 26 connects to the inlet nozzle 34 attached to the flash tank 10 . The inlet nozzle 34 may be tangential to a cylindrical portion 38 of the flash tank 10 . The flash tank 10 need not be cylindrical and the inlet nozzle 34 need not be tangential to the flash tank 10 . The flash tank 10 may have planar sections in its sidewall. Other suitable configurations of the inlet nozzle 34 may be oriented vertically and attached to the top of the flash tank 10 or to the side of the flash tank 10 without being tangential to the sidewall of the flash tank 10 . The flow passage 40 through inlet nozzle 34 may be rectangular, e.g., square, in cross-section. The rectangular cross section allows a valve plate 42 in the flow passage 40 to move, e.g., pivot, within the flow passage 40 . The valve plate 42 regulates the velocity of the flow stream of black liquor to the flash tank 10 . A transition section 44 at the upstream end of the inlet nozzle 34 may convert a round inlet to a rectangular cross section of the remainder of the flow passage 40 through the inlet nozzle 34 . The inlet of the transition section 44 connects to the end of the conduit 26 . The outlet of the transition section 44 connects to the inlet nozzle 34 . The transition section 44 may include a flange coupling 31 to attach to an end outlet 32 of the conduit 26 . FIG. 3 illustrates an exemplary valve plate 42 in the inlet nozzle 34 . The inlet nozzle 34 extends tangentially to the cylindrical portion 38 of the flash tank 10 . The valve plate 42 may be attached to a hinge 46 fixed to a sidewall 48 of the flow passage 40 through the inlet nozzle 34 . An upstream end 50 end of the valve plate 42 is fixed to the hinge 46 and may be adjacent the sidewall 48 . Pressurized black liquor flows through the flow passage 40 and, specifically, between the valve plate 42 and an opposite sidewall 52 of the inlet nozzle 34 . The valve plate 42 may extend downstream such that the downstream edge 54 of the valve plate 42 is proximate to an opening 56 in the side of the cylindrical portion 38 of the flash tank 10 . The valve plate 42 pivots, see arrow 58 , about the vertical axis of the hinge 46 . The range of angles through which the valve plate 42 pivots is a design parameter to be selected during the design of the inlet nozzle 34 . The range of angles may swing the valve plate 42 from being adjacent to the sidewall 48 (a zero angle position) to a maximum angle position where the downstream edge 54 abuts the end of the opposite sidewall 52 . The downstream edge 54 of the valve plate 42 will form an edge of the throat area (T in FIGS. 2 and 4 ) of the flow passage 40 . The throat area T is the narrowest cross-sectional area of the flow passage 40 . The throat area T is directly related to the capacity, quantity of black liquor the flow passage 40 is capable of passing to the flash tank 10 . The throat area T of the flow passage 40 is widest and has a maximum capacity when the angle of the valve plate 42 is zero and the valve plate 42 is adjacent the sidewall 48 . The throat area T of the flow passage 40 is narrowest and has a minimum capacity, which may be a zero flow rate, when the valve plate 42 is at a maximum angle the downstream edge 54 nearest the opposite sidewall 52 of the flash tank 10 . The downstream edge 54 of the valve plate 42 may have a replaceable or hardened strip 60 , e.g., soft metal such as copper or a plastic material capable of withstanding the abrasive conditions such as those from the black liquor, which may be available to act as a seal between the downstream edge 54 of the valve plate 42 and the opposite sidewall 52 or interior wall of the flash tank 10 . A similar strip 60 may be along the upper and lower side edges of the valve plate 42 . FIG. 4 is a cross-sectional schematic diagram of the inlet nozzle 34 taken along a vertical plane and showing a side of the flash tank 10 . FIG. 4 shows a view looking directly into the inlet nozzle 34 in a downstream direction of the flow passage 40 . The rectangular cross-sectional shape of the flow passage 40 is evident as is the oval or circular shape of the opening 56 to the flash tank 10 . The valve plate 42 is shown extending partially across the flow passage 40 and forming a rectangular throat area (T). The valve plate also extends across and blocks a portion of the opening 56 to the flash tank 10 . The area of the flow passage 40 and portion of the opening 56 blocked or closed off by the valve plate 42 depends on the position of the valve plate 42 and particularly on the position of the downstream edge 54 (see FIG. 3 ) of the valve plate 42 . The valve plate 42 may extend completely across the flow passage 40 and cover the entire flow passage 40 , from top to bottom and side to side. On the other hand, the valve plate 42 may be positioned to be parallel and adjacent the sidewall 48 and thereby open the flow passage 40 and opening 56 . The motion of the movable, hinged valve plate 42 is controlled by a pneumatic or electro-mechanical actuator 62 , such as a pneumatic piston pump. The actuator 62 may have a cylindrical body 64 attached to the side of the flash tank 10 and a reciprocating shaft 66 driven by a piston in the cylindrical body 64 . A distal end of the shaft 66 is pivotable and is attached to the backside of the valve plate 42 . The actuator 62 may extend and retract the shaft 66 to move the valve plate 42 to open the throat area T or close the throat area T of the flow passage 40 . The shaft 66 extends through a port 67 in the sidewall 48 of the inlet nozzle 34 . The port 67 may include a seal to prevent leakage of black liquor. A controller 68 , e.g., a computer or manual adjustment, determines the extension of the shaft 66 and the position of the valve plate 42 . The controller 68 may extend the shaft 66 to set the position of the valve plate 42 and achieve a desired throat area T for the flow passage 40 . The controller 68 may be adjusted manually to change or adjust the position of the valve plate 42 . Alternatively, the controller 68 may adjust the position of the valve plate 42 by computer, manual adjustment or other suitable means based on, for example, comparison between a desired pressure in the flow passage 40 and a sensed pressure in the flow passage 40 . Hot black liquor extracted from the screens 20 of a vessel 12 flows through the inlet nozzle 34 and enters the flash tank 10 . The throat area T of the inlet nozzle 34 determines volume of flow or flow velocity using backpressure in the flow passage 40 which restricts the flow of black liquor entering the flash tank 10 . Because the throat area T is determined by the position of the valve plate 42 , the controller 68 can move the valve plate 42 to adjust the throat area T and consequently the velocity or volume of flow through the flow passage 40 . Controlling the volume of flow or flow velocity in the inlet nozzle 34 allows for the velocity and volume of black liquor entering the flash tank 10 to be regulated, provides a degree of control over the pressure drop in the flash tank 10 and ensures a sufficient pressure in the conduits 26 upstream of the inlet nozzle 34 . As the black liquor enters the flash tank 10 , the liquor flashes to produce steam 28 and condensate 30 . The steam 28 may be used as heat energy in the vessel 12 , in an impregnation vessel (not shown), in a chip feed bin (not shown), in a chip steaming vessel (not shown), in a tank holding fresh cooking liquor, e.g., white liquor, or other locations in the mill where steam is needed. The condensate 30 may flow to additional flash tanks 10 or other chemical recovery equipment (not shown), e.g., a recovery boiler, an evaporation system or other chemical recovery system. The orientation of the valve plate 42 in the inlet nozzle 34 is a design choice. The hinge 66 for the valve plate 42 may be attached to either sidewall 48 or the top or bottom walls of the flash tank 10 . 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 appended claims.
A flash tank including: a closed interior chamber; a gas exhaust port coupled to an upper portion of the chamber; a liquid discharge port coupled to a lower portion of the chamber; an inlet nozzle attached to an inlet port of the chamber, wherein the inlet nozzle includes a flow passage, and a movable valve plate in the flow passage, wherein the valve plate has a first position which defines a first throat in the flow passage and a second position which defines a second throat having a smaller cross-sectional area than the first throat.
3
BACKGROUND OF THE INVENTION [0001] 1 Field of the Invention [0002] The present invention relates to an automatic tent frame having an extension spring extended when an automatic tent is folded, and more particularly, to an automatic tent frame that is capable of preventing an upper coupler and a lower coupler from being rotated with respect to each other or preventing given gaps from being generated on the coupled portions of the upper coupler and the lower coupler even in a case where an automatic tent is not unfolded to its original shape by the reduction of the restoring force of an extension spring and thus falls down due to external impacts like wind, thus preventing support poles supporting main poles from being damaged to extend the life span of the automatic tent frame, and that is capable of reducing the length of a pipe module, while allowing the pipe module to have the same functions as in conventional one, thus upwardly lifting an outer surface of the automatic tent by the reduced length to increase the interior of the automatic tent by a maximum height and providing very pleasant camping in the relatively extended internal space of the automatic tent. [0003] 2. Background of the Related Art [0004] Modern people, who want to live comfortably in nature like mountains and river, away from busy schedules, have enjoyed their camping as one of their endevours to improve their quality of life. [0005] Camping means with modern facilities such as a camping car, a forest park, a bungalow and the like have been developed, but among them, one of the best camping means is an automatic tent capable of realizing the real value of nature and learning the wisdom of life in nature. [0006] However, it is not easy to find an appropriate area for camping, install the automatic tent, and remove the automatic tent, and particularly, it is very hard for women or children to do such works. Accordingly, various developments for an automatic tent frame capable of easily installing and removing the automatic tent have been dynamically made as will be mentioned below. [0007] In this case, an automatic tent is a new tent capable of being installed and removed in a rapid and convenient way, and as shown in FIG. 6 , the automatic tent T includes an automatic tent frame 1 forming a frame structure thereof and an outer surface 2 fitted to the outside of the automatic tent frame 1 to shield the automatic tent from rain and wind. The automatic tent T is installed by pulling outer surface loops 21 locked onto the automatic tent frame 1 through momentary unfolding of the automatic tent frame 1 and by unfolding the outer surface 2 . The automatic tent is also called foldable tent or one touch tent, and one of the main features of the automatic tent T is the completion of installation and removal with a short period of time through just folding or unfolding, thus improving the convenience in use. [0008] Of course, the outer surface 2 of the automatic tent T basically needs a water proofing function according to the exposure to ultraviolet rays and a flame resistance treatment for protecting a user from fire, but the automatic tent frame 1 basically should improve the easiness in the installation and removal of the automatic tent, maintain the stability of the installed tent, and enhance the conveniences in living in the automatic tent. [0009] Recently, there has been proposed Korean Patent No. 10-1191046 entitled ‘automatic tent frame’, issued on Oct. 9, 2012 to the same inventor as the present invention, wherein the conventional automatic tent frame has an extension spring extended when an automatic tent is folded. [0010] Referring to FIGS. 7 to 9 , the above-mentioned conventional automatic tent frame will be in detail explained below. The automatic tent frame 500 includes: a pipe module 510 having two pipes having different diameters from each other, the small diameter pipe being insertedly fitted to the large diameter pipe in such a manner as to slidingly move therein; an upper coupler 520 located on top of the pipe module 510 in such a manner as to be coupled to any one of the two pipes of the pipe module 510 ; a lower coupler 530 located on the underside of the pipe module 100 in such a manner as to be coupled to the other pipe of the pipe module 510 ; an extension spring T inserted into the pipe module 510 in such a manner as to be fixed on the upper end periphery thereof to the pipe to which the upper coupler 520 is fixed and on the lower end periphery to the pipe to which the lower coupler 530 is fixed, the extension spring T being fixed in a state of being extended by a given length; a plurality of main poles F 9 hinge-coupled to the upper coupler 520 ; and a plurality of support poles F 10 each having one end hinge-coupled to the main pole F 9 and the other end hinge-coupled to the lower coupler 530 , wherein the extension spring T has an upper coupling end U and a lower coupling end L on which fastening holes H are formed, the upper end periphery of the extension spring T being fixed to the pipe to which the upper coupler 520 is fixed by means of a fastening member M passing through the upper coupler 520 and the pipe to which the upper coupler 520 is fixed in such a manner as to be inserted into the fastening hole H of the upper coupling end U, and the lower end periphery of the extension spring T being fixed to the pipe to which the lower coupler 530 is fixed by means of a fastening member M passing through the lower coupler 530 and the pipe to which the lower coupler 530 is fixed in such a manner as to be inserted into the fastening hole H of the lower coupling end U, and the lower coupler 530 has a through hole P formed on the underside thereof, the lower coupling end L of the extension spring T having an extension piece E exposed to the outside through the through hole P in such a manner as to allow the extension spring T to be extended by a given length L 5 in an arrow direction C when the lower coupling end L of the extension spring T is fixed. [0011] According to the above-mentioned conventional automatic tent frame, in the state where the extension spring is extended while the automatic tent frame is being not used for a long period of time, even if the automatic tent is unfolded, it can be completely unfolded to its initial expected shape. [0012] As the time has passed, however, the extension force of the extension spring becomes weak, and further, the restoring force of the extension spring becomes reduced, so that the automatic tent is not unfolded to its initial shape and thus falls down due to the external impacts like wind. Furthermore, the upper coupler and the lower coupler are rotated with respect to each other, and given gaps are undesirably generated on the coupling portions of the upper coupler and the lower coupler, thus causing the support poles supporting the main poles to be turned and damaged to shorten the life span of the automatic tent frame. Accordingly, separate locking means should be needed. [0013] Additionally, the height of the head portion formed by coupling the upper coupler, the pipe module and the lower coupler with each other is relatively high in the whole height of the installed automatic tent, but the height of the internal space of the automatic tent is not relatively high, which causes many inconveniences in standing or moving in the interior of the automatic tent. SUMMARY OF THE INVENTION [0014] Accordingly, the present invention has been made in view of the above-mentioned problems occurring in the prior art, and it is an object of the present invention to provide an automatic tent frame that is capable of preventing an upper coupler and a lower coupler from being rotated with respect to each other or preventing given gaps from being generated on the coupled portions of the upper coupler and the lower coupler, without having any separate locking means, even in a case where an automatic tent is not unfolded to its original shape by the reduction of the restoring force of an extension spring and thus falls down due to external impacts like wind, thus preventing support poles supporting main poles from being damaged to extend the life span of the automatic tent frame, and that is capable of reducing the length of a pipe module, while allowing the pipe module to have the same functions as in conventional one, thus upwardly lifting an outer surface of the automatic tent by the reduced length to increase the interior of the automatic tent by a maximum height and providing very pleasant camping in the relatively extended internal space of the automatic tent. [0015] To accomplish the above-mentioned object, according to the present invention, there is provided an automatic tent frame including: a pipe module having a small diameter pipe and a large diameter pipe having different diameters from each other, the small diameter pipe being insertedly fitted to the large diameter pipe in such a manner as to be slidingly moved therein; an upper coupler having a small diameter pipe coupling groove formed at the center of the underside thereof in such a manner as to be located on top of the pipe module and coupled to the upper end periphery of the small diameter pipe by means of a first fastening member; a lower coupler having a large diameter pipe coupling groove formed at the center of the top thereof and a through hole formed at the center of the underside thereof in such a manner as to be located on the underside of the pipe module and coupled to the lower end periphery of the large diameter pipe by means of a second fastening member; an extension spring having an upper coupling end and a lower coupling end on which fastening holes are formed, an extension piece exposed to the outside through the through hole of the lower coupler in such a manner as to be pulled by a given length when the extension spring is fixed, the upper end periphery of the extension spring being insertedly fitted to the pipe module in such a manner as to be fixed to the small diameter pipe by means of the first fastening member passed through the upper coupler and the small diameter pipe to which the upper coupler is fixed and inserted into the fastening hole of the upper coupling end, and the lower end periphery of the extension spring being insertedly fitted to the pipe module in such a manner as to be fixed to the large diameter pipe by means of the second fastening member passed through the lower coupler and the large diameter pipe to which the lower coupler is fixed and inserted into the fastening hole of the lower coupling end; a plurality of main poles hinge-coupled to the upper coupler; and a plurality of support poles each having one end hinge-coupled to the main pole and the other end hinge-coupled to the lower coupler, wherein the small diameter pipe is open on the top and bottom thereof and has coupling holes formed facingly on the upper periphery thereof and long slots formed facingly on the lower end periphery thereof in a perpendicular direction to the coupling holes. [0016] According to the present invention, desirably, each long slot has a given width through which the second fastening member is passed and a given length extended from the underside of the small diameter pipe to a higher position than the position where coupling holes are formed on the lower coupler to face the long slots when the small diameter pipe is coupled to the lower coupler. [0017] According to the present invention, desirably, the extension piece exposed to the outside through the through hole of the lower coupler is coupled to an upper loop disposed on top of an outer surface of an automatic tent in such a manner as to be pulled together when the extension spring is contracted to increase a height of the automatic tent. BRIEF DESCRIPTION OF THE DRAWINGS [0018] The above and other objects, features and advantages of the present invention will be apparent from the following detailed description of the preferred embodiments of the invention in conjunction with the accompanying drawings, in which: [0019] FIG. 1 is a perspective view showing an automatic tent frame according to the present invention; [0020] FIG. 2 is an exploded perspective view showing the automatic tent frame according to the present invention; [0021] FIG. 3 is a sectional view showing the folded state of the automatic tent frame according to the present invention; [0022] FIG. 4 is a sectional view showing the unfolded state of the automatic tent frame according to the present invention; [0023] FIG. 5 is a perspective view showing a lower coupler of the automatic tent frame according to the present invention; [0024] FIG. 6 is a schematic view showing an automatic tent mounted with the automatic tent frame according to the present invention; [0025] FIG. 7 is a sectional view showing the folded state of a conventional automatic tent frame; [0026] FIG. 8 is a sectional view showing the unfolded state of the conventional automatic tent frame; and [0027] FIG. 9 is a sectional view showing the extended state of the conventional automatic tent frame. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [0028] Hereinafter, an explanation on an automatic tent frame according to the present invention will be in detail given with reference to the attached drawings. [0029] In the description, the terms as will be discussed later are defined in accordance with the functions of the present invention, but may be varied under the intention or regulation of a user or operator. Therefore, they should be defined on the basis of the whole scope of the present invention. Before the present invention is disclosed and described, it is to be understood that the disclosed embodiments are merely exemplary of the invention, which can be embodied in various forms. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one of ordinary skill n the art to variously employ the present invention in virtually any appropriately detailed structure. The present invention is disclosed with reference to the attached drawings wherein the corresponding parts in the embodiments of the present invention are indicated by corresponding reference numerals and the repeated explanation on the corresponding parts will be avoided. If it is determined that the detailed explanation on the well known technology related to the present invention makes the scope of the present invention not clear, the explanation will be avoided for the brevity of the description. [0030] FIG. 1 is a perspective view showing an automatic tent frame according to the present invention, FIG. 2 is an exploded perspective view showing the automatic tent frame according to the present invention, FIG. 3 is a sectional view showing the folded state of the automatic tent frame according to the present invention, FIG. 4 is a sectional view showing the unfolded state of the automatic tent frame according to the present invention, FIG. 5 is a perspective view showing a lower coupler of the automatic tent frame according to the present invention, and FIG. 6 is a schematic view showing an automatic tent mounted with the automatic tent frame according to the present invention. [0031] As shown in FIGS. 1 to 6 , an automatic tent frame 1 according to the present invention includes: a pipe module 100 having a small diameter pipe 110 and a large diameter pipe 120 having different diameters from each other, the small diameter pipe 110 being insertedly fitted to the large diameter pipe 120 in such a manner as to be slidingly moved therein; an upper coupler 200 having a small diameter pipe coupling groove 220 formed at the center of the underside thereof in such a manner as to be located on top of the pipe module 100 and coupled to the upper end periphery of the small diameter pipe 110 by means of a first fastening member p; a lower coupler 300 having a large diameter pipe coupling groove 340 formed at the center of the top thereof and a through hole 330 formed at the center of the underside thereof in such a manner as to be located on the underside of the pipe module 100 and coupled to the lower end periphery of the large diameter pipe 120 by means of a second fastening member p; an extension spring 400 having an upper coupling end 410 and a lower coupling end 420 on which fastening holes 411 and 421 are formed, an extension piece 423 exposed to the outside through the through hole 330 of the lower coupler 300 in such a manner as to be pulled by a given length when the extension spring 400 is fixed, the upper end periphery of the extension spring 400 being insertedly fitted to the pipe module 100 in such a manner as to be fixed to the small diameter pipe 110 by means of the first fastening member p passed through the upper coupler 200 and the small diameter pipe 110 to which the upper coupler 200 is fixed and inserted into the fastening hole 411 of the upper coupling end 410 , and the lower end periphery of the extension spring 400 being insertedly fitted to the pipe module 100 in such a manner as to be fixed to the large diameter pipe 120 by means of the second fastening member p passed through the lower coupler 300 and the large diameter pipe 120 to which the lower coupler 300 is fixed and inserted into the fastening hole 421 of the lower coupling end 420 ; a plurality of main poles 500 hinge-coupled to the upper coupler 200 ; and a plurality of support poles 600 each having one end hinge-coupled to the main pole 500 and the other end hinge-coupled to the lower coupler 300 , wherein the small diameter pipe 110 is open on the top and bottom thereof and has coupling holes 111 formed facingly on the upper periphery thereof and long slots h formed facingly on the lower end periphery thereof in a perpendicular direction to the coupling holes 111 . [0032] Further, each long slot h has a given width through which the second fastening member p is passed and a given length extended from the underside of the small diameter pipe 110 to a higher position than the position where coupling holes 311 are formed on the lower coupler 300 to face the long slots h when the small diameter pipe 110 is coupled to the lower coupler 300 . [0033] The extension piece 423 exposed to the outside through the through hole 330 of the lower coupler 300 is coupled to an upper loop 22 disposed on top of an outer surface 2 of an automatic tent in such a manner as to be pulled together when the extension spring 400 is contracted to increase a height of the automatic tent. [0034] Hereinafter, the automatic tent frame 1 according to the present invention will be in detail explained. [0035] As shown in FIG. 2 , first, the pipe module 100 has the small diameter pipe 110 and the large diameter pipe 120 having different diameters from each other, and the small diameter pipe 110 is insertedly fitted to the large diameter pipe 120 in such a manner as to slidingly move therein. That is, the extension spring 400 is inserted into the small diameter pipe 110 , and the open end portion of the small diameter pipe 110 coupled to the upper coupler 200 is movably inserted into the open end portion of the large diameter pipe 120 coupled to the lower coupler 300 . [0036] The small diameter pipe 110 is open on the top and bottom thereof and has the coupling holes 111 formed facingly on the upper periphery thereof and the long slots h formed facingly on the lower end periphery thereof. [0037] Each long slot h has a larger width than the second fastening member p to pass the second fastening member p therethrough and the length extended from the underside of the small diameter pipe 110 to a higher position than the position where coupling holes 311 are formed on the lower coupler 300 to face the long slots h when the small diameter pipe 110 is coupled to the lower coupler 300 . When the small diameter pipe 110 is insertedly fitted to the large diameter pipe 120 , as a result, the second fastening member p is completely inserted into the long slots h of the small diameter pipe 110 . [0038] At this time, the long slots h are formed in the perpendicular direction to the coupling holes 111 facingly formed on the upper periphery of the small diameter pipe 110 , so that the rotating gaps with respect to the upper coupler 200 and the lower coupler 300 can be even a little reduced desirably. [0039] The upper end periphery of the small diameter pipe 110 is inserted into the small diameter pipe coupling groove 220 of the upper coupler 200 and coupled thereto by means of the first fastening member p passing sequentially through coupling holes 231 formed facingly on the outer peripheral surface of a small diameter pipe coupler 230 of the upper coupler 200 , the coupling holes 111 formed on the upper periphery of the small diameter pipe 110 , and the fastening hole 411 of the upper coupling end 410 of the extension spring 400 . [0040] At this time, the first fastening member p is a bolt finished by means of nut coupling, but it is not limited thereto. According to the present invention, the first and second fastening members p have the same kind and size as each other, which is advantageous in the assembling process. [0041] The large diameter pipe 120 is open on the top and bottom thereof and has coupling holes 121 formed facingly on the lower periphery thereof. [0042] The lower end periphery of the large diameter pipe 120 is inserted into the large diameter pipe coupling groove 340 of the lower coupler 300 and fastened thereto by means of the second fastening member p passing sequentially through the coupling holes 311 of the lower coupler 300 , the coupling holes 121 of the large diameter pipe 120 , the long slots h of the lower end periphery of the small diameter pipe 110 , and the fastening hole 421 of the lower coupling end 420 of the extension spring 400 . [0043] Further, the upper coupler 200 has a shape of a disc having a plurality of main pole coupling grooves 210 formed along the outer periphery thereof and includes a pipe type small diameter pipe coupler 230 protruding unitarily from the center of the underside thereof, the small diameter pipe coupling groove 220 formed at the center of the underside of the small diameter pipe coupler 230 , and the coupling holes 231 formed facingly on the outer peripheral surface of the small diameter pipe coupler 230 . [0044] The upper coupler 200 is located on top of the pipe module 100 in such a manner as to be coupled to the upper end periphery of the small diameter pipe 110 by means of the first fastening member p passing sequentially through the coupling holes 231 formed facingly on the outer peripheral surface of the small diameter pipe coupler 230 , the coupling holes 111 formed on the upper periphery of the small diameter pipe 110 , and the fastening hole 411 of the upper coupling end 410 of the extension spring 400 inserted into the small diameter pipe 110 . [0045] Further, the lower coupler 300 has a flange-shaped upper portion having a plurality of support pole coupling grooves 320 formed along the outer periphery thereof and a cylindrical large diameter pipe receiver 310 formed unitarily from the underside thereof in such a manner as to be open on top thereof, and the large diameter pipe receiver 320 has a “+”-shaped through hole 330 formed at the center of the underside thereof in such a manner as to allow the extension piece 423 of the extension spring 400 to be exposed to the outside therethrough. [0046] The coupling holes 311 are formed facingly on the outer peripheral surface of the large diameter pipe receiver 320 . [0047] The lower coupler 300 is located on the underside of the pipe module 100 in such a manner as to be coupled to the lower end periphery of the large diameter pipe 120 by means of the second fastening member p passing sequentially through the coupling holes 311 formed on the outer peripheral surface of the large diameter pipe receiver 320 of the lower coupler 300 , the coupling holes 121 formed on the lower periphery of the large diameter pipe 120 , the long slots h of the lower end periphery of the small diameter pipe 110 , and the fastening hole 421 of the lower coupling end 420 of the extension spring 400 inserted into the small diameter pipe 110 . [0048] At this time, the fastening is achieved by outwardly pulling the extension piece 423 exposed to the outside through the through hole 330 of the lower coupler 300 to allow the fastening hole 421 formed on the lower end of the extension spring 400 to be located correspondingly on the coupling holes 311 formed on the outer periphery of the large diameter pipe receiver 310 and the coupling holes 121 formed on the lower periphery of the large diameter pipe 120 and next by insertedly passing the second fastening member p therethrough. That is, the extension spring 400 becomes fixed in the state of being extended by a given length. [0049] Of course, the small diameter pipe 110 and the large diameter pipe 120 may be changeably coupled to the upper coupler 200 and the lower coupler 300 . [0050] Further, the small diameter pipe 110 , the large diameter pipe 120 , the upper coupler 200 and the lower coupler 300 are made of any one selected from a metal material and a synthetic resin material, and particularly, only if the small diameter pipe 110 and the large diameter pipe 120 have the sectional shapes corresponding to each other, they have various sections such as circular, oval, and polygonal sections. [0051] According to the present invention, the small diameter pipe 110 , the large diameter pipe 120 , the upper coupler 200 and the lower coupler 300 are disposed independently of each other, as respective components, but the small diameter pipe 110 and the upper coupler 200 may be formed unitarily with each other, while the large diameter pipe 120 and the lower coupler 300 being formed unitarily with each other. Of course, the small diameter pipe 110 and the large diameter pipe 120 may be changeably formed unitarily with the upper coupler 200 and the lower coupler 300 . [0052] The extension spring 400 has the upper coupling end 410 and the lower coupling end 420 on which the fastening holes 411 and 421 are formed. [0053] The extension spring 400 further has the extension piece 423 disposed on the lower end thereof in such a manner as to be exposed to the outside through the through hole 330 of the lower coupler 300 , so that the extension piece 423 is pulled by a given length to allow the extension spring 400 to be easily fixed. [0054] The upper end periphery of the extension spring 400 is insertedly fitted to the pipe module 100 and fixed to the small diameter pipe 110 by means of the first fastening member p passed through the upper coupler 200 and the small diameter pipe 110 to which the upper coupler 200 is fixed and inserted into the fastening hole 411 of the upper coupling end 410 . [0055] The lower end periphery of the extension spring 400 is insertedly fitted to the pipe module 100 and fixed to the large diameter pipe 120 by means of the second fastening member p passed through the lower coupler 300 and the large diameter pipe 120 to which the lower coupler 300 is fixed and inserted into the fastening hole 421 of the lower coupling end 420 . [0056] Further, as shown in FIG. 4 , the plurality of main poles 500 is well known components, and they are hinge-coupled to the plurality of main pole coupling grooves 210 formed on the outer periphery of the upper coupler 200 . The plurality of support poles 600 is well known components, and they are hinge-coupled to the main poles 500 at their one end and hinge-coupled to the lower coupler 300 at their other end. The configurations of the main poles 500 and the support poles 600 and their hinge coupling structures are well known in the art, and therefore, a detailed explanation on them will be avoided for the brevity of the description. [0057] Now, an explanation on the operation of the automatic tent frame 1 according to the present invention will be in detail given. [0058] The small diameter pipe 110 is insertedly fitted to the upper coupler 200 , and next, the extension spring 400 is inserted into the small diameter pipe 110 . After that, the first fastening member p is passed sequentially through the coupling holes 231 of the upper coupler 200 , the coupling holes 111 of the small diameter pipe 110 , and the fastening hole 411 of the upper coupling end 410 of the extension spring 400 , thus fastening the extension spring 400 to the small diameter pipe 110 . Next, the large diameter pipe 120 is fitted to the outer peripheral surface of the small diameter pipe 110 , and next, the lower coupler 300 is insertedly fitted to the lower end periphery of the large diameter pipe 120 . After that, the second fastening member p is passed sequentially through the coupling holes 311 of the lower coupler 300 , the coupling holes 121 of the large diameter pipe 120 , the long slots h of the small diameter pipe 110 , and the fastening hole 421 of the lower coupling end 420 of the extension spring 400 , thus fastening the extension spring 400 to the large diameter pipe 120 . Next, the plurality of main poles 500 is hinge-coupled to the plurality of main pole coupling grooves 210 formed on the outer periphery of the upper coupler 200 , and the plurality of support poles 600 is hinge-coupled to the main poles 500 at their one end and hinge-coupled to the lower coupler 300 at their other end, thus finishing the formation of the automatic tent frame 1 . [0059] Next, the main poles 500 of the automatic tent frame 1 are fitted to outer surface loops 21 of the outer surface 2 of the automatic tent T, and the extension piece 423 of the extension spring 400 exposed to the outside through the through hole 330 of the lower coupler 300 is coupled to the upper loop 22 of the outer surface 2 of the automatic tent T. In this state, the whole automatic tent T is folded and packaged, thus finishing the assembling and packaging of the automatic tent T. At this time, the automatic tent T is folded in the state where the extension spring 400 is extended. [0060] On the other hand, if the upper loop 22 of the outer surface 2 of the automatic tent T, which is coupled to the extension piece 423 of the extension spring 400 exposed to the outside through the through hole 330 of the lower coupler 300 , is momentarily pulled upward by means of the instant contraction of the extension spring 400 of the automatic tent frame 1 , the main poles 500 are momentarily unfolded by means of the instant contraction of the extension spring 400 of the automatic tent frame 1 to instantly pull the outer loops 21 of the outer surface 2 fitted to the main poles 500 , thus folding the outer surface 2 of the automatic tent T and installing the automatic tent T within a short period of time. [0061] If it is desired to install the automatic tent T after an automatic tent installation area is found, that is, the main poles 500 are just pulled once toward both sides, so that the extended extension spring 400 of the automatic tent frame 1 is released from the balanced state and momentarily contracted. [0062] As shown in FIGS. 4 and 6 , the upper loop 22 of the outer surface of the automatic tent T, which is coupled to the extension piece 423 of the extension spring 400 exposed to the outside through the through hole 330 of the lower coupler 300 , is momentarily pulled upward, and at the same time, the lower coupler 300 coupled to the lower end periphery of the extension spring 400 is pulled upward, thus allowing one ends of the support poles 600 hinge-coupled to the support pole coupling grooves 320 formed the flange-shaped outer periphery of the upper portion of the lower coupler 300 to be momentarily pulled and thus allowing the main poles 500 to be momentarily pushed outward and unfolded by means of the other ends of the support poles 600 , so that the outer surface loops 21 fitted to the main poles 500 are pulled to unfold the outer surface 2 of the automatic tent T, thus installing the automatic tent T. [0063] At this time, if the extension spring 400 is contracted, as shown in FIG. 4 , the lower end periphery of the small diameter pipe 110 is brought into contact with the bottom surface of the lower coupler 300 , and the second fastening member p is inserted into the long slots h formed on the lower end periphery of the small diameter pipe 110 , so that a locking effect is generated from the small diameter pipe 110 through the second fastening member p to prevent the rotation or gap between the small diameter pipe 110 and the large diameter pipe 120 from being generated. Even if the automatic tent T falls down due to the application of an unexpected external pressure thereto, accordingly, no rotation or gap between the upper coupler 200 to which the small diameter pipe 110 is coupled and the lower coupler 300 to which the large diameter pipe 120 is coupled, thus preventing the support poles 600 supporting the main poles 500 from being damaged and further extending the life span of the automatic tent frame 1 . [0064] In the conventional practice, if the extension spring 400 is contracted, the lower end periphery of the small diameter pipe 110 is locked to the second fastening member p of the lower coupler 300 , so that the height of the head portion formed by coupling the pipe module into which the extension spring is inserted with the upper coupler and the lower coupler is relatively high in the whole height of the installed automatic tent, and contrarily, the height of the internal space of the automatic tent is not relatively high, which causes many inconveniences in standing or moving in the interior of the automatic tent. [0065] According to the present invention, as shown in FIGS. 4 and 6 , when the extension spring 400 is contracted, the second fastening member p is inserted into the long slots h formed on the lower end periphery of the small diameter pipe 110 , and in this case, the lower end periphery of the small diameter pipe 110 is brought into contact with the bottom surface of the lower coupler 300 , thus reducing the length of the pipe module 100 and further upwardly lifting the outer surface 2 of the automatic tent by the reduced length to ensure the interior of the automatic tent by a maximum height. Accordingly, the internal space of the automatic tent becomes enlarged to provide very pleasant camping. [0066] While the present invention has been described with reference to the particular illustrative embodiments, it is not to be restricted by the embodiments but only by the appended claims. It is to be appreciated that those skilled in the art can change or modify the embodiments without departing from the scope and spirit of the present invention.
The present invention relates to an automatic tent frame capable of preventing an upper coupler and a lower coupler from being rotated with respect to each other or preventing given gaps from being generated on the coupled portions of the upper coupler and the lower coupler even in a case where an automatic tent is not unfolded to its original shape by the reduction of the restoring force of an extension spring and thus falls down due to external impacts like wind, thus preventing support poles supporting main poles from being damaged to extend the life span of the automatic tent frame, and capable of reducing the length of a pipe module, while allowing the pipe module to have the same functions as in conventional one, thus upwardly lifting an outer surface of the automatic tent by the reduced length to increase the interior of the automatic tent by a maximum height.
4
BACKGROUND OF THE INVENTION The present invention relates generally to solid state gas sensing devices and specifically to a gas sensor using pyroelectric effects. In conjunction with studies related to high power sources of microwave and millimeter wave radiation, attention has focused on problems in the vacuum tube technology for generating this radiation. Specifically, the cathodes of such vacuum tube devices are sensitive to contamination by residual gases in the tube as well as out-gassing products from tube components as they heat up during operation. In view of the processing of these vacuum tubes (heating to temperatures in the vicinity of 450° C.) rather stringent environmental parameters are placed on any sensor utilized to measure internal contaminants. Pyroelectric substances are a class of substances which exhibit an induced surface charge when the temperature of the material changes. If a pyroelectric substrate is polarized at a temperature above its Curie temperature, and electrodes are placed on either side of the substrate (across the poling direction) a charge will be developed across the electrodes when the temperature of the substrate is changed. The amount of voltage and/or current will be proportional to the rate of change of temperature. An article appearing in Sensors and Actuators, Vol. 1, 1981, entitled "Non-FET Chemical Sensors", by Zemel, Keramati, Spivak and D'Amico examines the possibility of utilizing pyroelectric substrates as a gas sensor, and is herein incorporated by reference. The article discusses the anticipated signal from a pyroelectric substrate which is being heated over a period of time. A similar graph of signal output versus time is shown in FIG. 1. The solid line indicates that as heat is applied, the temperature of the substrate changes and this change in temperature provides an output signal from the electrodes on the substrate. However, if a material is placed on the substrate and begins to undergo a phase change at time T 1 the graph of signal versus time would be as shown in dotted lines. Although the heat input to the substrate is the same as the solid line graph, the heat required to change the state of the material on the substrate would prevent an increase in substrate temperature for some short period of time (until all the material has undergone phase change). Because the temperature of the substrate is not changing at this time T 1 , the signal will not increase normally and, in some instances, may actually decrease. This is analogous to the high school experiment in which a Bunsen burner is used to boil water in a thin plastic cup. The cup's temperature rises to that of boiling water and is maintained constant at that temperature until all of the water is boiled away at which time, of course, the cup is heated beyond the temperature of boiling water to its melting point and/or combustion point. However, while the water is boiling away, the temperature of the cup remains at a relatively steady temperature. In our pyroelectric substance, because the substrate is maintained at a relatively constant temperature while the material on its surface is changing phase, the signal output of the pyroelectric substrate is greatly diminished. Also disclosed in the article is the experimental response of a pyroelectric sensor to the melting of 8 mg of In-Sn solder located on the substrate suggesting that indeed such a pyroelectric sensor was possible. However, theoretical predictions do not necessarily take into account practical realities. It is desirable to be able to differentiate between two or more materials on the substrate surface and thus extremely small substrate temperature increments are desired in order to see the effect of each of two or more materials as they separately absorb heat from the substrate during their melting and/or vaporization. Further, the noise level of a single sensor clouds the sensitivity of the device such that it is difficult to know whether the output is an indication of a material on the substrate, or a random noise signal which has been acquired. Thus, selectivity and sensitivity are problems associated with the experimental pyroelectric gas sensor. Also known is the use of a pyroelectric substrate as a gas dosimeter as disclosed in U.S. Pat. No. 3,861,879 to Taylor, issued Jan. 21, 1975. Here the exothermic oxidation of carbon monoxide in the presence of a suitable catalyst causes a temperature change in the pyroelectric with a resulting charge redistribution which is sensed. SUMMARY OF THE INVENTION In accordance with the above disadvantages, it is an object of the present invention to provide a sensor capable of indicating the presence, concentration and identity of a fluid (gas or liquid) in a test medium (gas or liquid). It is a further object of the present invention to utilize a pyroelectric substrate as a sensor of a fluid in a test medium. The above and other objects are achieved in accordance with the present invention by providing a polarized pyroelectric substrate with sensor electrodes sandwiching the substrate in the polarized direction. The substrate is also provided with a heater element which applies a fluctuating heat input to the substrate. The constantly changing temperature of the substrate provides a periodic output from the sensor electrodes. In a preferred embodiment, two electrodes with substantially the same physical characteristics are operated together with only one electrode having a material capable of absorbing the fluid whose existence is to be determined. The outputs of the two electrodes are provided to a differential amplifier which provides an output indicative only of the difference between the signals produced by the two substrates. The fluctuating heat input gradually raises the temperature of the substrate cycle by cycle through the desorption temperature (that temperature at which the tested-for fluid melts, vaporizes, or sublimates). If an output is present at the differential amplifier then a fluid has desorbed from the material on the pyroelectric substrate. The extent of the output of the differential amplifier is an indication of the concentration of the desorbing fluid and the temperature at which desorption begins is an indication of the species or identity of the fluid. A further embodiment of the invention utilizes a lock-in amplifier driven at the same frequency as the pulsing heater input to the substrates which serves to amplify only the differential output which is directly resultant from the fluctuating heat input. A further embodiment utilizes a fluctuating fluid concentration supplied to the pyroelectric substrate with the substrate heated in a gradual manner. When the substrate temperature reaches the point at which desorption occurs during a pulse of low concentration and adsorption occurs during a pulse of high concentration, a large differential output will occur. This temperature is similarly indicative of the species of fluid while the magnitude of the differential signal is indicative of the concentration of the fluid. This pulsed-gas embodiment can also be advantageously combined with a lock-in-amplifier tied to the gas pulsation frequency. BRIEF DESCRIPTION OF THE DRAWINGS A more complete appreciation of the invention, and many of the attendant advantages thereof will be readily apparent by reference to the accompanying drawings, wherein: FIG. 1 is a graph of pyroelectric substrate signal versus time for a substrate with and without a fluid present thereon; FIGS. 2a, 2b and 2c are top, bottom and side views, respectively, of a pyroelectric gas sensor in accordance with the present invention; FIG. 3 is an electronic block diagram illustrating the connections and electronic processing of one embodiment of the present invention; FIGS. 4a, 4b, and 4c illustrate power applied to the substrate, substrate temperature, and current generated at the substrate electrodes, respectively, for the embodiment shown in FIG. 3; FIGS. 5a and 5b illustrate current versus time for the embodiment of FIG. 3 without and with the test fluid present, respectively; FIG. 6 is a further embodiment of the present invention where the fluid concentration is periodically varied; FIGS. 7a and 7b illustrate the difference signal output versus time and the substrate temperature versus time, respectively, for the pyroelectric gas sensor shown in FIG. 6; FIG. 8 is an electronic block diagram of a further embodiment of the present invention; and FIG. 9 is an electronic block diagram of a further embodiment of the present invention. DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS Referring now more particularly to the drawings, wherein like numerals represent like elements throughout the several views, FIGS. 2a, 2b and 2c illustrate one embodiment of the pyroelectric gas sensor 10. Although other materials could be used, lithium tantalate LiTaO 3 was chosen because of its high Curie temperature (618° C.). A z cut crystal of LiTaO 3 measuring 1.2×1.4×0.03 cm was prepared in the following manner. The LiTaO 3 wafer was first cleaned in trichloroethylene followed by acetone, alcohol and distilled water. The surface was then treated with cold HNO 3 /H 2 SO 4 solution to remove any metallic impurities followed by distilled water and ethyl alcohol. The wafer was then blown dry with pure N 2 . A 3000 Å thick Au film was deposited on the substrate. A positive A-J 1350 photoresist was spin coated on the wafer and subjected to the photoprocessing to provide the interdigitated electrode means A and B with a 50μ space separating adjacent fingers (the distance shown by the opposing arrows in FIG. 2a). After removal of the excess gold film by an aqua regia etch, the photoresist is then removed with acetone followed by an ethyl alcohol rinse and drying by means of nitrogen gas. The remaining interdigitated gold structure is shown in FIG. 2a as elements 12 and 14 associated with electrodes A and B, respectively. On the back side of the wafer (shown in FIG. 2b) an overall layer 100 Å of Cr 16 is deposited after which a layer of 3000 Å thickness of NiCr 18 is deposited to form the heater resistor 18. An additional 100 Å of Cr is deposited through a mask with a further 3000 Å Au 20 to form the heater contact pads. The resulting resistor has a resistance on the order of 2 to 4 ohms. As can be seen in FIG. 2c, the electrode contacts A and B are located on a plane normal to the polarization direction of the wafer (polarization direction indicated by the arrows in FIG. 2c). An activated charcoal film is provided on electrode A as shown in FIGS. 2a and 2c. Different materials could be substituted for the charcoal 22 in order to change the response of the pyroelectric gas sensor to different gases and/or liquids. The two interdigitated electrodes act as charge sensors for the pyroelectric structure and have the same total area. The interdigitating of the electrodes is to minimize the effect of any temperature inhomogeneities due to geometry or material properties of the thin film heater. As the substrate is heated, a current is generated at each electrode. Assuming that the heat loss at each electrode is the same, a differential signal at the two electrodes ought to be zero subject to the proviso that the area, emissivity, and gas desorption is the same for each electrode. FIG. 3 illustrates the electronic interconnections for utilizing information provided by the pyroelectric gas sensor. The pyroelectric substrate 1 has the electrical resistance heater 18 mounted on the bottom thereof which, together with ammeter 24 and power supply 26 comprise the means for varying the temperature of the pyroelectric substrate. A thermocouple 28 and temperature indicator 30 comprise a means for measuring and indicating the temperature of the absorbing/desorbing charcoal. A differential amplifier 32 provides an output indicative of the difference between signals produced by electrodes A and B. In a preferred embodiment, a lock-in amplifier 34 serves to amplify only input signals which are correlated with the heating means in this embodiment. In one embodiment, the power input to the resistance heater will be a series of pulses having a given frequency, and as can be seen from FIGS. 4a, 4b and 4c, the output of each individual electrode will be in a direct phase relationship with fluctuations in the substrate temperature caused by the pulsating heat input of the power supply. The lock-in amplifier serves as a notch filter for the frequency or subharmonic thereof of power supply 26. Turning to FIGS. 4a-4c, a better understanding of one embodiment of the present invention may be had. As previously noted, power is applied to the resistance heater 18 in a pulse-type fashion being on from time (a) until time (b) and then off from time (b) until time (c). In this embodiment, the on/off time durations are equal although they need not be. When heat is supplied to the pyroelectric substrate, its temperature will rise as indicated in FIG. 4b between times (a) and (b) and by virtue of conduction and radiation losses, the temperature of the substrate will drop when power is not applied to it as is shown between time periods (b) and (c). It will be recalled that a pyroelectric substrate only produces an output when the temperature of the substrate is changing, i.e., when dT/dt is not equal to zero. Additionally, because the heat lost (at least initially) between times (b) and (c) is less than the heat gained between times (a) and (b), the temperature of the substrate will gradually rise. However, because the conductive, convective and radiation losses of heat are greater at higher temperatures, the amount of temperature change for each additional heat pulse will be less as higher temperatures are reached. Because the temperature increase between pulses becomes less and less as the substrate warms up, the current or signal developed at the electrodes by the pyroelectric substrate will be of less magnitude as time goes on. This is illustrated as the difference in current magnitude in FIG. 4c at time (a) as compared with time (c). It can also be observed by referring to FIG. 4c that the temperature change of the substrate is less during the cooling cycle than in the heating cycle as the negative going polarity has a much lower amplitude than the positive going polarity. FIG. 5a illustrates current produced by one electrode over a substantial period of time in much the same manner as did FIG. 4c. It can be seen that after a period of time, a temperature will be reached at which the heat added during the power supply pulse is equal to the heat lost due to conduction, convection and radiation between pulses. Therefore, it would be possible to compute the current generated at a given electrode on the basis of the input heat, the convection, conduction and radiation losses expected from the substrate, and the thermal constant of the substrate, whether or not the substrate included an absorber/desorber material such as charcoal as previously noted. However, where there is a material absorbed into the absorber/desorber material, if its desorption temperature is within the operating range of the pyroelectric gas sensor, i.e., less than the maximum temperature reached by the substrate, then additional heat will be taken away from the substrate by this evaporation process. Because a greater than normal amount of heat will be taken away especially between pulses, the negative going current produced at the electrode will increase to a greater level than that shown in FIG. 5a. Furthermore, because the thermal energy is utilized to a certain extent in boiling off the fluid from the absorber/desorber, the temperature of the substrate will not increase as much per power pulse and thus the current generated at the electrode will be less in FIG. 5b than in FIG. 5a (compare current levels at time T 1 ). Thus, a single electrode can produce an indication of a fluid desorbing from the absorber/desorber material based on a comparison with the same electrodes current versus time profile without the fluid present. Additionally, the temperature at which the fluid desorbs (determined from the known temperature/time curve of FIG. 4b) will provide an indication of the species or type of material desorbing. For the purpose of this specification, fluid is defined as any unknown material for which the pyroelectric gas sensor is designed and could be a gas or liquid. Similarly, a test medium is defined as a gas or liquid medium in which the fluid is suspended and carried past the pyroelectric gas sensor. Such a single electrode pyroelectric gas sensor is illustrated in FIG. 8. The power supply 26 provides a pulsating current to resistance heater 18 on pyroelectric substrate 1. If the absorber/desorber material 22 located on electrode A has absorbed a fluid of interest, this fluid will have a characteristic temperature of desorption. As the substrate is heated and approaches the desorption temperature, the rate of change of substrate temperature (dT/dt) should be relatively constant although it might decrease to a greater extent at higher temperatures due to an increasing radiative loss component. The output of the lock-in amplifier 34 will reflect this relatively constant temperature change of the substrate with a relatively constant output. However, when the desorption temperature of the fluid on material 22 is reached, a portion of the heat generated by the resistance heater 18 will be utilized in vaporizing the fluid with the result that the rise in temperature of the substrate will be substantially less. Because the substrate temperature rise is less, the change in temperature per unit time (dT/dt) will drop as shown in the graph contained by output indicator 40. The actual temperature of the substrate when the drop in dT/dt occurs can be computed based on the time at which the change occurs times the average change per unit time. Thus, the presence of a fluid in the material 22 and its temperature of desorption is indicated on indicator 40. Such an indicator could be a cathode ray tube, an X-Y plotter, a digital printout, etc. The amount of fluid which desorbs from material 22 is indicated by the amount of time necessary to desorb the material once the desorption temperature is reached, i.e., the width of the gap in dT/dt on indicator 40. Again, utilization of phase lock amplifier 34 or other correlation equipment, while not critical, affords better signal acquisition and noise rejection. It is also possible to utilize the device shown in FIG. 8 without the output indicator 40 as in FIG. 9 by comparing dT/dt with the material 22 exposed to the unknown fluid with the dT/dt curve of the substrate without the unknown fluid present. This requires recording in recorder 60 at least one curve and then comparing the recorded curve with the opposite dT/dt output live (if the dT/dt for the unknown fluid is recorded, then the dT/dt for the substrate without the unknown fluid is live and vice versa) and looking for differences between the two signals. The time from timer 62 at which a significant difference occurs is indicative of the species of fluid desorbed from material 22 as the time of desorption can be related to the temperature of desorption which is characteristic of different fluids. A further embodiment of the pyroelectric gas sensor utilizes pulsations in gas concentration to vary the absorption/desorption on the material 22 and thus affect the rate of change of temperature of the pyroelectric substrate. Such an embodiment is illustrated in FIG. 6 in which a supply of the fluid to be tested 50 is pulsatingly added to the test medium by means of a rotating or pulsating valve 52. Thus, a periodically increasing/decreasing concentration of the fluid to be tested passes over the pyroelectric gas sensor 10 before the gas is exhausted. Although power supply 54 could provide a pulsating periodic output as in FIG. 4a or a sine wave output, in a preferred embodiment the power supply provides power to the resistance heater such that the temperature of the substrate increases linearly with respect to time, as shown in FIG. 7b. Although a single element sensor would work, a dual element sensor with a differential amplifier (such as that shown in FIG. 3) is believed to be a preferred embodiment. The differential amplifier and the individual elements are included in the pyroelectric gas sensor 10 shown in FIG. 6. The fluctuating fluid (gas or liquid) will absorb on the absorber/desorber material of the pyroelectric gas sensor and at low temperatures this surface will become saturated. As the gas pulsates in concentration, the saturated absorber/desorber material will be relatively unaffected and there will be no heat exchange due to absorption/desorption. Similarly, at very high temperatures, there is no substantial amount of gas absorbed on the absorber/desorber material surface because the mean residence time is so small due to molecular activity (regardless of the gas concentration). However, at some intermediate temperature, the absorber/desorber material will absorb fluid in the high concentration regime and desorb fluid during the low concentration regime. A consequence of this gas exchange is that heat is removed on desorption and added on absorption. Because there is a heat exchange, there will be a change in dT/dt and there will be a difference in the signal outputs of the electrode contacts of the pyroelectric gas sensor. The differential amplifier will provide the difference output and because this output will vary at a function of the gas pulsation frequency (although not necessarily at the same phase) the lock-in amplifier passes only that narrow frequency band corresponding to the rotating valve frequency. When the temperature is reached which achieves a maximum change in substrate temperature per gas pulse cycle, a peak will be reached as indicated in FIG. 7a at the dotted line. This dotted line temperature will be a characteristic of the species of fluid and the amplitude of the difference signal at the maximum will be a characteristic of the concentration of the fluid to be tested. This peak of "resonance" can be a very dramatic indication and with an appropriate lock-in amplifier or other correlation measurement is capable of indicating the presence and concentration of extremely minute quantities of fluid in the test medium. The pyroelectric gas sensor is described with regard to several examples. However, the concept of utilizing the absorption and/or desorption of a fluid onto a material to change the rate of change of temperature on a pyroelectric substrate can take many other forms, depending upon the specific requirements. The fluid to be tested could be a gas or liquid and the test medium could be a gas or liquid with the fluid dissolved therein. The test medium could easily be dispensed with or be considered a vacuum in either of the disclosed embodiments. The fluctuating power supply in the various embodiments could be a pulse, sine wave, or gradually increasing power. The pyroelectric gas sensor, particularly as discussed with reference to FIG. 3 could be exposed to the fluid to be tested and subsequently cycled through its temperature profile to determine the gas present. However, upon continuous exposure of the pyroelectric gas sensor to the fluid to be tested, a similar "resonance" would be encountered as the critical desorption temperature is reached for the particular fluid being tested. Because the temperature of the substrate fluctuates, it would tend to desorb a greater portion of the fluid at the higher temperatures and absorb more of the fluid at the lower temperatures. This periodic desorption and absorption would cause a much greater differential output from the gas sensor similar to that illustrated in FIG. 7a. Although the temperature of the absorber/desorber material can readily be calculated, it may be useful to include a temperature measuring means as previously discussed with reference to FIG. 3. The size of the pyroelectric gas sensor can be made extremely small by currently available photolithographic techniques. This reduction in size not only increases the frequency response of the pyroelectric gas sensor, but also increases its sensitivity to fluids being tested. It has also been found that some materials may be more suitable for the absorber/desorber material if a particular fluid presence and/or concentration is to be detected. One aspect of the pyroelectric gas sensor is the chemically sensitive layer. It is only necessary that it provide some temperature change as a consequence of the presence of the desired fluid in order for the sensor to provide an output indication thereof. Therefore, if a suitable enzyme or coenzyme is bonded to the surface of the pyroelectric (in the vicinity of one electrode in the dual or differential embodiment) it would be possible to detect the heat generated by the interaction of the bound enzyme or coenzyme with the corresponding coenzyme or enzyme, respectively. A catalytic material such as is disclosed in Taylor could also be used but with much greater accuracy as the sensor being driven with heat source provides a much more accurate indication of catalytic reactions on the pyroelectric substrate surface. In a catalytic embodiment, the reaction temperature like the previously discussed desorption temperature, would be an indication of the type of substance present in the fluid and the magnitude of the temperature shift (or difference in the differential measurement) would be an indication of the concentration of the substance present. It would also be possible to place the pyroelectric substrate directly on a field effect transistor as the gate such that charge redistributions caused by temperature changes in the pyroelectric substrate serve to control current flow through the transistor. Thus, an extremely small chemical sensor could be provided with a built in first stage amplifier. In view of the above discussion, many modifications and applications of the pyroelectric gas sensor will be obvious to those of ordinary skill in the art. Therefore, the invention described herein is limited only by the appended claims.
A pyroelectric substrate is provided with a heater and at least one set of electrodes for sensing charge redistributions due to changes in the substrate temperature. In a preferred embodiment, there are two interdigitated electrodes, one coated with an absorber/desorber material. The heater pulsatingly raises the temperature of the substrate past the desorption temperature of a fluid of interest. If the fluid was exposed to the absorber/desorber material prior to heating, a portion of the fluid will have been absorbed. When the substrate reaches the desorption temperature, additional heat pulses will not increase the substrate temperature significantly until the fluid has desorbed. Thus, heat used in changing state does not raise the substrate temperature and, lacking a temperature change, reduces the charge redistribution sensed by the electrode coated with the material. Its output is compared with the uncoated electrode (whose temperature continues to rise) and the difference is equal to the amount of fluid desorbed and the temperature is indicative of the species of fluid desorbed.
8
FIELD OF THE INVENTION The invention relates to a garment for ballistic protection and carrying equipment. PRIOR ART Combatants on foot generally have to put on several items of equipment for carrying and protection, including: a ballistic protection vest mainly designed to protect the thorax, abdomen and back from weapons fire, the protective vest including ballistic protection packs comprising superposition of layers of material adapted to absorb impacts, a tactical vest mainly designed to transport materiel which must be close at hand for the combatant, such as munitions and electronic equipment (radio communication set, computer unit, man-machine interface, a screen, and batteries), the tactical vest including a set of pockets for receiving the various equipment, a backpack designed to transport the rations of the combatant and the equipment as a function of his mission. Each item of equipment is currently designed independently and is generally not optimised to take into account the bulk and distribution of weight of other equipment. The consequence of this in use is that the superposition of various equipment can present difficulties. For example, dressing and undressing can prove complicated, which is disadvantage in the event of emergency. Also superposition of equipment can hamper the movements of the user. Also, the weights of individual equipment are added and constitute a considerable load on the combatant. Since ballistic protection and tactical vests essentially rest on the shoulders of the combatant, this can cause him back problems due to the considerable weight of this equipment. Finally, it is not possible to easily and rapidly adapt the equipment worn to the particular features of the mission of the combatant. SUMMARY OF THE INVENTION An aim of the invention is to propose a single garment which can ensure ballistic protection of the user and carry equipment as a function of needs. This problem is resolved within the scope of the present invention by a garment for ballistic protection and for carrying equipment, comprising: a carrying harness comprising a dorsal part suitable for covering the back of a user, the dorsal part comprising a cover to receive a ballistic pack for protection of the back, and straps adapted to encircle the shoulders of the user to suspend the harness on the shoulders, and two abdominal parts suitable for covering the torso of the user, each abdominal part being adapted to be fixed detachably on a respective strap of the carrying harness, the abdominal parts comprising a closing device for connecting the abdominal parts together to close the garment. The carrying harness constitutes autonomous equipment (that is, it is adapted to be held by itself on the user). However, the two abdominal parts are fixed on the carrying harness so as to form a vest. In this way, the abdominal parts can be easily detached and replaced as a function of the mission of the user. Accordingly, the carrying harness fulfils a protective function of the user, but can also be used for carrying equipment, especially because of the abdominal parts. The entire load is transferred to the carrying harness. The garment can also have the following characteristics: the carrying harness comprises a belt connected to the dorsal part and adapted to encircle the waist of the user to transfer some of the weight exerted on the carrying harness to the hips of the user, at least one of the abdominal parts comprises a cover to receive a torso protection pack, the abdominal parts being suitable for covering the torso by overlapping, in particular, one of the abdominal parts covers the other abdominal part over a covering area representing substantially half of the abdominal part, once the garment is closed, the torso protection pack and the back protection pack are positioned relative to each other such that they overlap in areas of the shoulders and in areas of the flanks of the user, the carrying harness comprises an electrical connection cable extending along the straps, passing over the shoulders of the user and the dorsal part and capable of connecting equipment positioned on one of the abdominal parts to equipment positioned on the other of the abdominal parts, the garment comprises a transport housing adapted to be connected detachably to the carrying harness by being positioned against the dorsal part, on an external wall of the cover, the abdominal parts comprise a set of pockets adapted to receive electronic equipment and/or munitions. PRESENTATION OF DRAWINGS Other characteristics and advantages will emerge from the following description which is purely illustrative and non-limiting and must be considered in conjunction with the attached figures, in which: FIG. 1 schematically illustrates a protective garment according to an embodiment of the invention, FIGS. 2 and 3 schematically illustrate a frontal and rear view of a user wearing the protective garment. DETAILED DESCRIPTION As is illustrated in FIG. 1 , the illustrated protective garment 1 comprises a carrying harness 2 and two removable abdominal parts 3 and 4 . The carrying harness 2 comprises a dorsal part 5 (or backrest), a right strap 6 , a left strap 7 , an abdominal belt 8 , as well as a transport handle 9 . The dorsal part 5 comprises a cover 51 and a ballistic pack 52 for protection of the back. The cover 51 has an internal wall 53 (that is, oriented to the back of the user) and an external wall 54 (that is, oriented to the outside) together forming a dorsal pocket 55 , and an opening 56 by which the pack 52 for protection of the back can be inserted inside the dorsal pocket 55 . The protection pack 52 generally comprises a multilayer complex constituted by a plurality of superposed layers designed to absorb the impacts of projectiles, such as fragments of explosive devices or bullets, or weapon fire, and optionally a tight protection pocket containing the complex to protect the complex from humidity and ultra-violet radiation. The internal wall 53 and the external wall 54 are formed of flexible fabric. The external wall 54 which is designed to be in contact with the back of the user comprises a so-called fabric of “three-dimensional structure” to promote circulation of air across the fabric and ventilation of the back. The dorsal part 5 can include an inner reinforcing plate. Also, the dorsal part 5 can include shock-absorbing blocks between the reinforcing plate and the external wall 54 , for example made of alveolar material. Each strap 6 , 7 is fixed permanently on the dorsal part 5 , and comprises a first end 61 , 71 connected to an upper are of the dorsal part 5 (or shoulder area) and a second end 62 , 72 connected to a lower area of the dorsal part 5 (or hips area). The straps 6 and 7 are adapted to encircle the shoulders of the user to suspend the harness 2 on the shoulders while the garment is placed on the user. Each strap 6 , 7 comprises a first connection element 63 , 73 , near its first end 61 , 71 and a second connection element 64 , 74 near its second end 62 , 72 . The connection elements 63 and 64 of the first strap 6 are intended to enable the first abdominal part 3 to attach to the harness 2 . The connection elements 73 and 74 of the second strap 7 are designed to enable the second abdominal part 4 to attach to the harness 2 . The abdominal belt 8 comprises a first portion 81 and a second portion 82 each having an end connected to a lower area of the dorsal part. At the level of its free end each portion 81 , 82 comprises complementary connection elements 83 , 84 for joining together the portions 81 and 82 of the belt. The belt 8 is designed to encircle the waist of the user to transfer some of the weight exerted on the carrying harness on the hips of the user and stabilise the garment on the user. Once the harness 2 is suspended on the shoulders of the user, the portions 81 and 82 are connected together to encircle the waist of the user. The portions 81 and 82 can comprise an adjustment device for adapting the belt to the morphology of the user. The connection elements 83 , 84 are for example complementary snap-locking buckles, wherein one of the buckles 84 is adapted to nest in the other buckle 83 , enabling rapid attachment and detachment of the belt 8 . The handle 9 helps transport the harness 2 and the entire garment 1 . The first abdominal part 3 comprises a cover 31 and a pack 32 for ballistic protection of the torso. The cover 31 presents an internal wall 33 and an external wall 34 together forming a pouch 35 , and an opening 36 via which the pack 32 for protection of the torso can be inserted inside the pouch 35 . The first abdominal part 3 can also comprise one or more extra pockets (not shown) adapted to house one or more rigid protection plates. The first abdominal part 3 also comprises two connection elements 37 and 38 capable of cooperating with the connection elements 63 and 64 of the first strap 6 to fix the first abdominal part 3 onto the harness 2 . More precisely, each element 37 , respectively 38 , 47 , 48 , is adapted to fit each element 63 complementary, respectively 64 , 73 , 74 , and be held in the complementary element 63 , respectively 64 , 73 , 74 by snap-locking. The second abdominal part 4 comprises a single wall 41 and does not take up a protection pack. The second abdominal part 4 also comprises two connection elements 47 and 48 capable of cooperating with the connection elements 73 and 74 of the second strap 7 to fix the second abdominal part 4 onto the harness 2 . The first abdominal part 3 and the second abdominal part 4 comprise a sliding closing device 10 for connecting together the abdominal parts 3 and 4 to close the garment 1 on the torso of the user. The closing device 10 comprises a first closure strip 101 fixed on the abdominal part 3 , a second closure strip 102 fixed on the abdominal part 4 , and a slider 103 capable of sliding on the strips for connecting the strips together. The first closure strip 101 extends substantially along a median line of the first abdominal part 3 , whereas the second closure strip extends along a border of the second abdominal part 4 . This arrangement of the closure strips 101 , 102 produces a garment 1 which closes across the front like a vest, and provides just one ballistic torso protection pack for better comfort during use. In fact, when the garment 1 is closed, the pack 32 substantially covers the entire torso of the user. Also, the second abdominal part 4 covers the first abdominal part 3 over a covering area representing substantially half of the abdominal part 4 . Also, once the garment closed on the user, the ballistic protection packs 32 and 52 are positioned relative to each other such that they overlap in the area of the shoulders and in the areas of the flanks to ensure continuity of protection between the back and the torso. As the abdominal parts 3 and 4 are removable, they can be replaced easily as a function of the mission the user is on. Also, abdominal parts 3 and 4 different can be provided for left-handed users and right-handed users. Also, the harness 2 comprises one or more cable(s) 11 for electrical connection, or a conduit adapted to receive such a cable, extending along each of the straps 6 and 7 and of the dorsal part 5 around the neck so as to be capable of attaching electrical equipment positioned on one of the abdominal parts 3 and 4 to electrical equipment positioned on the other of the abdominal parts 3 and 4 . More precisely, the cable 11 extends inside the dorsal part 5 and inside the straps 6 and 7 as it bypasses the neck of the user. As is illustrated in FIG. 2 , the abdominal parts 3 and 4 comprise also a set of pockets respectively 310 to 313 and 410 to 412 . The pockets 310 to 313 and 410 to 412 can be fixed detachably to the external walls 34 and 41 of the abdominal parts. These pockets 310 to 313 and 410 to 412 are adapted to contain materiel which has to be close at hand for the user when he is wearing such a garment, such as munitions and electronic equipment (radio communication set, computer unit, batteries, etc), normally stowed away in a separate tactical vest. As is illustrated in FIG. 3 , the garment 1 comprises a flexible or semi-rigid transport housing 12 adapted to be fixed detachably on the dorsal part 5 of the harness 2 against the external wall 54 . For this purpose, the dorsal part 5 comprises connection elements 57 to 59 and the housing 12 comprises complementary connection elements 121 to 123 capable of cooperating with the elements 57 to 59 to fix the housing 12 detachably on the harness 2 . The connection elements 57 to 59 and 121 to 123 are for example snap-locking buckles which enable rapid attachment and detachment of the housing 12 . The housing 12 can for example constitute a compartment for transporting small materiel normally stowed away in a separate backpack such as a first-aid kit for example. Because of the connection elements 57 to 59 and 121 to 123 , the housing 12 can be replaced easily by another housing, as a function of the mission of the user. The connection elements 57 to 59 and 121 to 123 also allow rapid dropping of the housing 12 in the event of emergency. As the use of an additional backpack is not necessary, the passage of the cable electrical along the straps 6 and 7 of the harness 2 does not impair comfort of the user. The belt 8 ensures transfer of some of the weight exerted on the carrying harness 2 on the hips of the user, and avoids overburdening the shoulders. This allows greater freedom of movement for the user and reduces back problems.
The invention relates to a garment for ballistic protection and carrying equipment, including: a carrying harness including a back portion suitable for covering the back of a user, the back portion including a cover for accommodating a back-protecting pack and straps suitable for being placed over the shoulders of the user in order to hang the harness from the shoulders; and two abdominal portions suitable for covering the torso of the user, each abdominal portion being designed to be removably attached onto a respective suspender of the carrying harness, the abdominal portions including a closing device for connecting the abdominal portions together in order to close the vest.
5
This application claims the benefit of U.S. Provisional Application No. 60/307,408, filed Jul. 24, 2001. BACKGROUND OF THE INVENTION Aqueous slurries of polyvinyl alcohol (PVA) polymer are useful in the adhesives industry as well as in the paper industry. To prepare aqueous slurries having a high-concentration of PVA polymer powder (high-concentration PVA slurries) it is necessary to disperse PVA polymer in water. However, dispersing PVA polymer in water can be problematical. Aqueous PVA mixtures can exhibit strong non-Newtonian behavior (exhibiting Bingham-plastic, shear thinning, and time dependent thixotropic properties), and can require extensive agitation when viscosity is high. PVA polymer in water can form gels, or gel-like mixtures. This is particularly true for high-concentration aqueous PVA mixtures wherein the concentration of PVA in water is more than about 14% PVA by weight, based on the total weight of the PVA/water mixture. PVA/water “gels” can be difficult to use in a manufacturing process because such PVA mixtures can be difficult, if not impossible, to agitate due to high viscosity. Using conventional mixing techniques can be ineffective in preventing the formation of PVA/water gels. For example, it has been observed that turbine-type impellers do not provide adequate mixing near the surface and along tank circumferences of PVA water mixtures. As a result of weak agitation near the surface a local build-up in viscosity in that region can occur, yielding gels near or at the surface of PVA/water slurries. Also, it can be conventional to use baffles to disrupt laminar flow in a mixing process and reduce or eliminate a vortex formed by the spinning action of an impeller. However, baffles are not suitable for use in the practice of the present invention. In fact, it is surprising that baffles can exacerbate gel formation. Without being held to theory, one explanation of this surprising result is that the baffles act to “hold up” PVA in the area of the baffles, thus causing a local viscosity increase in that region. Over time, the region high in viscosity can expand and cause the entire mixture to “set up” (that is, become gel-like). It is desirable to prepare an aqueous mixture of polyvinyl alcohol having at least 14% by weight of PVA by a process whereby the viscosity of the mixture does not approximate that of a gel at any time during the process. SUMMARY OF THE INVENTION In one aspect, the present invention is a process for preparing an aqueous polyvinyl alcohol (PVA) mixture having at least about 14%, by weight, of PVA comprising the steps: (a) metering water (1) and PVA (2) into a mixing vessel that contains water and is equipped with an impeller for mixing the contents of the vessel, wherein the metered PVA is at least about 14%, by weight, of the total weight of (1) and (2), and wherein the impeller is rotated at a speed of at least about 60 rpm before the PVA is metered into the vessel; (b) increasing the speed of the impeller during the process of metering (1) and (2) into the vessel; (c) optionally recirculating a portion of the mixed contents of the vessel back into the vessel such that the recirculated mixture is injected into the vessel at a speed and at a location that eliminates the vortex created by the impeller rotational action; and (d) continuing the addition of (1) and (2) as in step (a) until the mixture has a PVA content of at least about 14%, by weight of the mixture. In another aspect, the present invention is a process for preparing an aqueous polyvinyl alcohol (PVA) mixture having at least about 14%, by weight, of PVA comprising the steps: (a) metering water (1) and PVA (2) into a mixing vessel that contains water and is equipped with an impeller for mixing the contents of the vessel, wherein the metered PVA is at least about 14%, by weight, of the total weight of (1) and (2), and wherein the impeller is rotated at a speed of at least about 60 rpm before the PVA is metered into the vessel; (b) increasing the speed of the impeller during the process of metering (1) and (2) into the vessel; (c) optionally recirculating a portion of the mixed contents of the vessel back into the vessel such that the recirculated mixture is injected into the vessel at a speed and at a location that eliminates the vortex created by the impeller rotational action; and (d) continuing the addition of (1) and (2) as in step (a) until the mixture has a PVA content of at least about 14%, by weight of the mixture, wherein the impeller creates counter-flow mixing pattern in the mixture. In still another aspect, the present invention is a process for preparing an aqueous polyvinyl alcohol (PVA) mixture having at least about 14%, by weight, of PVA comprising the steps: (a) metering water (1) and PVA (2) into a mixing vessel that contains water and is equipped with an impeller for mixing the contents of the vessel, wherein the metered PVA is at least about 14%, by weight, of the total weight of (1) and (2), and wherein the impeller is rotated at a speed of at least about 60 rpm before the PVA is metered into the vessel; (b) increasing the speed of the impeller during the process of metering (1) and (2) into the vessel; (c) optionally recirculating a portion of the mixed contents of the vessel back into the vessel such that the recirculated mixture is injected into the vessel at a speed and at a location that eliminates the vortex created by the impeller rotational action; and (d) continuing the addition of (1) and (2) as in step (a) until the mixture has a PVA content of at least about 14%, by weight of the mixture, wherein the vessel does not include baffles. In another aspect, the present invention is an aqueous PVA mixture having at least about 14%, by weight, of PVA based on the total weight of the mixture made by the process comprising the steps: (a) metering water (1) and PVA (2) into a mixing vessel that contains water and is equipped with an impeller for mixing the contents of the vessel, wherein the metered PVA is at least about 14%, by weight, of the total weight of (1) and (2), and wherein the impeller is rotated at a speed of at least about 60 rpm before the PVA is metered into the vessel; (b) increasing the speed of the impeller during the process of metering (1) and (2) into the vessel; (c) optionally recirculating a portion of the mixed contents of the vessel back into the vessel such that the recirculated mixture is injected into the vessel at a speed and at a location that eliminates the vortex created by the impeller rotational action; and (d) continuing the addition of (1) and (2) as in step (a) until the mixture has a PVA content of at least about 14%, by weight of the mixture. DETAILED DESCRIPTION BRIEF DESCRIPTION OF THE DRAWING In the accompanying drawing: FIG. 1 is an image of a portion of a counter-flow agitator having 4 identical “switch pitch” blades. DETAILED DESCRIPTION OF THE INVENTION In one embodiment, the present invention is a process for preparing high concentration mixtures of PVA in water, wherein the concentration of PVA is greater than 14% by weight, based of the total weight of the mixture. Below a concentration of about 14%, a PVA/water mixture does not tend to exhibit the problem of gel formation to the extent that it interferes with agitation of the mixture. Above a concentration of about 14% gel formation can be a problem using conventional mixing methods. In a process of the present invention, PVA and water are added into a mixing vessel that is equipped with a means for stirring or agitating the contents. The mixing means is preferably an impeller connected to a shaft that is driven by a variable speed motor, that is a motor that is capable of driving the impeller at various rotational speeds. The impeller design must be such that the impeller imparts sufficient agitation to the fluid contents of the mixing vessel, providing shear to the fluid even in the outer regions of the vessel. The impeller can have a single blade, but preferably has at least two blades. The length of the blades is preferably from 80-90% of the diameter of the mixing vessel. If multiple blades are present, they can be at the same height or at different heights on the impeller shaft. Preferably they are at the same heights on the impeller shaft. The impeller blades are preferably designed such that they create a counter-flow mixing pattern in the fluid. By counter-flow, it is meant that in one region fluid moves in one direction, and in an adjacent region the fluid moves counter to the movement in the first region. For example, in one the impeller will cause the fluid to move in an upward direction, and in an adjacent region the impeller will cause the fluid to move in a downward direction, thus causing counter-flow in the area where the regions overlap. Particularly suitable for this purpose are blades that are initially pitched at an angle of from 15 to 75° relative to the impeller shaft. The blade pitch angle abruptly changes along the length of the blade to a pitch angle that is from 75 to 105° relative to the initial angle. Preferably the new pitch angle is 90° relative to the initial pitch angle. The preferred impeller creates a region of high shear in the area where the change in pitch angle occurs, and it is preferable that the change occurs closer to the sides of the mixing vessel. The pitch angle preferably changes at a distance that is from about 32% to about 68% of the radius of the mixing vessel, as measured from the impeller shaft radially to the sides of the vessel. A mixing vessel suitable for use in the practice of the present invention can be any that is conventional in the mixing art, except that the vessel cannot be equipped with baffles. A vessel of the present invention is optionally equipped to enable recirculation of the mixed fluid such that the fluid is added perpendicular to the surface of the mixture. In any event it is preferable that the recirculated mixture be added in the region of the impeller in such a way that the vortex formed by the rotation of the impeller in the fluid mixture is disrupted to the point of elimination. PVA and water can be added to an empty mixing vessel. However, the vessel preferably includes some water before addition of the PVA and water starts. If present before addition begins, water is preferably at less than 50% of the volume of the vessel. The PVA and water can be added together as a mixture, or as separate components. It is preferable to add the PVA and water as separate components such that they are added to the vessel in a ratio of at least about 14% by weight, based on the total of the components being added. The components can be added as quickly as practical, but it is preferable to add the components in such a manner that there is not a local increase in viscosity at the point where the PVA is mixed into the vessel. The temperature of the water in the tank initially, and added to the tank can be from 10° C. to 25° C., at standard atmospheric pressure. It is preferable that the temperature of the water be within 10° C. to 20° C. The contents of the vessel can be agitated at speeds of at least about 60 rpm. Preferably, the contents are mixed with progressively more energy as the addition proceeds (that is, increasing higher rpm) to provide suitable mixing of the PVA in the water, and control the viscosity of the mixture to a suitably low value. Preferably, the contents are mixed at from 80 to 275 rpm over the course of the addition. More preferably, the contents are mixed at from 80 to 175 rpm over the course of the addition. A portion of the contents of the vessel can be recirculated into the mixing vessel in any such a manner that the vortex formed by the action of the impeller is eliminated. It is preferred that the mixture is injected back into the vessel at an angle that is perpendicular to the surface of the liquid, and aimed in the region of the impeller. It is also preferable that the mixture is recirculated at a rate that is rapid enough that the recirculated mixture creates strong shearing action in the region surrounding the impeller. One skilled in the art would be able to determine the recirculation rate required for the desired result. In another embodiment, the present invention is a PVA/water mixture that is at least about 14% by weight PVA, based on the total weight of the mixture, wherein the mixture is obtained according to the process described above. It is preferred that the PVA mixture be at least 16% PVA, more preferably, at least 17%, and even more preferably, at least 19% by weight PVA. It is an object of the present invention to maximize the percentage of PVA dispersed in water. EXAMPLES The Examples and comparative examples herein are for illustrative purposes only, and are not intended to limit the scope of the present invention. It is the Applicant's intention that the Doctrine of Equivalents will apply to the present invention. Ex. 1. Comparative Example A mixing tank 14.5 inches in diameter and 12.9″ high was equipped with a 7″ reverse vane turbine impeller (a conventional 8 blade turbine impeller) and baffles with a thickness {fraction (1/10)} the diameter of the tank fitted along the entire length of the vessel. The tank contained 4.4 gallons water prior to the start of the addition of PVA and water. The contents were stirred initially at a rate of 150 rpm. At about the 14% solids (PVA) level gel abruptly formed at the periphery of the tank. The speed of the mixer was increased to 240 rpm without any effect on the gel. The addition was halted. Ex. 2 Comparative Example Experiment 1 was repeated except that the vessel was not equipped with baffles. Gel formed again at about 14% solids, but most of the gel was broken by increasing the mixing speed to 287 rpm. At 19% solids, gel formed again at the periphery and was broken by increasing the speed to 380 rpm. Addition was continued to 20% solids and the mixture again gelled, and the gel was broken again by increasing the speed to 420 rpm. Example 3 A mixing tank 14.5 inches in diameter and 12.9″ high, and no baffles, was equipped with two 10.25″ diameter dual blade counter-flow impellers, stacked one on top of the other and offset 90° from each other. The tank contained 4.4 gallons of water prior to the start of the addition of PVA and water. The contents were stirred initially at a rate of 250 rpm. Addition proceeded to 20% solids with no gel formation. Example 4 Example 3 was repeated, except that only one dual blade counter-flow impeller was used. Slight gel formation at above 17% solids around the rim of the tank at the surface. The speed was increased to 350 rpm to break the gel. Example 5 A tank with a diameter of 11.375″ and 12″ high, and no baffles, was equipped with a single 10.5″ diameter counter-flow impeller having 4 blades. The tank initially contained 2.1 gallons water prior to the addition of the PVA and water mixture. Stirring was initially at 150 rpm. PVA and water were added all within 60 seconds to 21% solids. Slight gel formation was observed near the end of the addition, but was easily broken up by increasing the speed of the impeller to 250 rpm. Example 6 A tank with a diameter of 14.5″ and height of 12.9″, and no baffles, was equipped with a single 12.6″ diameter counter-flow impeller having 4 blades. Each blade was an identical “switch-pitch” blade. The agitator was positioned 1⅛″ from the bottom of the tank. The tank initially contained 5½″ water prior to the addition of the PVA and water mixture. Stirring was initially at 110 rpm. PVA and water were added all within 60 seconds to 21% solids. Slight gel formation was observed near the end of the addition, but was easily broken up by increasing the speed of the impeller to 250 rpm. Example 7 Example 6 was repeated, with the exception that the water and PVA were added to the tank in stages. At 17-19% solids the rpm was increased to 240, at 21% solids the speed was increased to 250-270 rpm. Example 8 Example 6 was repeated using PVA powder with larger average particle size than in Example 6. The maximum speed required to eliminate gels was 160 rpm. Example 9 A tank with a diameter of 14.5″ and height of 12.9″, and no baffles, was equipped with a single 12.6″ diameter counter-flow impeller having two blade pairs. One pair of identical blades were attached directly to the shaft, and had a pitch angle of 450. The other pair of blades were mounted onto long arms which were attached radially to the shaft, so that the blades extended toward the sides of the tank. The blades mounted on the arms had a pitch angle of 90° relative to the other pair of blades. Blade pairs were offset by 900. The agitator was positioned 1-⅛″ from the bottom of the tank. The tank initially contained 5½″ water prior to the addition of the PVA and water mixture. Stirring was initially at 114 rpm. PVA and water were added all within 90 seconds to 19% solids. Slight gel formation was observed near the end of the addition, but was broken up by increasing the speed of the impeller to 200-280 rpm.
The present invention is a process for preparing high concentration polyvinyl alcohol (PVA) aqueous mixtures, wherein the PVA solid concentration is at least 14% in the mixture.
2
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a video tape recorder (VCR) of the helical scanning rotary head type for recording and reproducing video signals. 2. Description of Prior Art A known component type VCR for recording and reproduction of video signals employs a method in which a timebase reference for the video signal is produced by inserting several sinewaves of color burst (referred to as a burst wave) after a negative synchronizing (sync) pulse for one horizontal scanning period, prior to frequency modulation of the video signal for recording. In reproduction of the video signal with this method, a zero-cross point of the burst wave in a demodulated video signal is detected for producing a playback pulse following a timebase variation. The playback pulse then actuates a PLL circuit to produce a playback clock signal. The demodulated video signal containing a timebase variation is converted to a digital signal by an A/D converter controlled by the playback clock and stored in a memory. It is then read out from the memory by a reference clock which carries no timebase variation so that a resultant reproduced video signal is free from timebase variation. However, the burst wave which is used for timebase correction is inserted in each horizontal scanning period and the timebase frequency of the NTSC system becomes as low as about 15 KHz. If the video signal is timebase extended for each horizontal scanning period and is recorded on a plurality of channels, the timebase frequency will further be decreased to about 7.5 KHz. When the timebase correction is carried out at such a low frequency, its response speed will remain low. Accordingly, an abrupt timebase change caused by the switching of heads affects video data recorded in the beginning of each recording track. This develops a duration, equal to a multiple of H (H: horizontal scanning period), where no timebase variation can be corrected throughout several horizontal scanning periods. As the result, a visual failure known as skew distortion will appear in the upper portion of a reproduced image. For eliminating the above failure, a modified method has been proposed as disclosed in laid-open Japanese Patent Application No. S63-61577, in which a negative signal which is longer in duration than a negative sync pulse provided in each horizontal scanning period is inserted in the beginning of each track prior to recording, and this negative signal is detected for timebase correction during reproduction. However, even if the duration of the negative signal is adequately long, only one edge is used as a timebase reference. This provides a precision of timing almost equal to that given by the negative sync pulse in each horizontal scanning period and the effect of skew distortion will hardly be eliminated. SUMMARY OF THE INVENTION It is an object of the present invention to avoid the generation of visual error known as skew distortion which appears in the upper portion of a reproduced image due to an abrupt timebase change in the beginning of a track caused by the switching of the heads. According to an improved method of the present invention, in addition to a burst signal of sinewaves provided in each horizontal scanning period and acting as a first timebase reference signal, a series of sinewaves which is longer in duration than the burst signal is inserted into a video signal as a second timebase reference signal in 1H period prior to recording. During reproduction, a zero-cross point of the burst wave is detected for the correction of timebase variations and also, the second timebase reference signal is utilized for timebase correction of the beginning of each track at a high speed. More particularly, the response of the timebase corrector during a timebase correcting action can be optimized in speed at the beginning of each track. Consequently, skew distortion resulting from an abrupt timebase change in the beginning of a track and appearing in the portion of a reproduced image will be minimized. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a waveform diagram of a reference signal associated with a recording/reproducing apparatus according to the present invention; FIG. 2 is a waveform diagram of a first reference signal; FIG. 3 is a waveform diagram of a second reference signal; FIG. 4 is a view showing the recording pattern on a magnetic tape; FIG. 5 is a block diagram illustrating one embodiment of the present invention; FIG. 6 is a block diagram of a timebase corrector in the apparatus of the present invention; FIG. 7 is a block diagram of a first detector of the timebase corrector; FIG. 8 is a waveform diagram of the first detector; FIG. 9 is a block diagram of a second detector of the timebase corrector; FIG. 10 is a waveform diagram of the second detector; FIG. 11 is a block diagram of a modified timebase corrector; FIG. 12 is a block diagram of a second detector of the modified timebase corrector; FIG. 13 is a waveform diagram of the second detector of the modified timebase corrector; and FIG. 14 is a waveform diagram of the modified timebase corrector shown in FIG. 11. DESCRIPTION OF THE PREFERRED EMBODIMENT FIG. 1 is a waveform diagram showing three scanning line periods of a video signal recorded at the beginning of each recording track using a VCR of the present invention. FIG. 1 shows a horizontal sync signal 1, a first timebase reference signal 2, a second timebase reference signal 3 which is added to only at the beginning region of each track, and a picture signal 4. Waveforms after the second scanning period are identical to that of the second scanning period which comprises the first timebase reference signal 2 and the picture signal 4. FIG. 2 is a waveform diagram showing in more detail the first timebase reference signal 2, in which denoted by 5 is a burst wave consisting of four sine-wave cycles. Although the picture signal is a luminance signal 6 in this embodiment, it may be a chrominance signal or TDM signal formed by timebase multiplexing of two, chrominance and luminance, signals. FIG. 3 is a waveform diagram showing the second timebase reference signal 3, in which denoted by 7 is a burst wave consisted of a greater number of sine-wave cycles than that of the first timebase reference signal 2 for timebase reference. FIG. 4 illustrates the recording of those signals onto the recording tracks of a video tape 9. In particular, the second timebase reference signal 3 is allocated to a region 8 on a recording track 10 of the video tape 9. Each recording track contains at the beginning region thereof a video signal component X containing the second timebase reference signal 3. Also, a series of video signal components A containing the first timebase signals 2 are recorded onto succeeding regions 11 of the recording track 10 respectively. It is assumed that the scanning with a recording head is carried out in the direction denoted by the arrow 12. FIG. 5 shows a block diagram of a recording section of the VCR of the present invention. In operation, an input video signal containing the first timebase reference signals 2 is fed through an input terminal 13 to a sync separator circuit 14 where sync pulses are separated from the input video signal. The sync pulses are transmitted to a timing generator circuit 15 which in turn actuates a switch 16 for switching from the output of a memory 17 to the input video signal at the timing of the front end of each recording track. Each group of video signal components headed by the signal X is then fed through an FM modulator 18 to a rotary head 19 for recording onto a video recording tape 20. FIG. 6 is a block diagram of a timebase corrector (TBC) in the VCR of the present invention for a reproducing operation. In action, a video signal read out from a recording tape 21 with a rotary head 22 is fed to an FM demodulator 23 where it is frequency demodulated. The resultant frequency demodulated video signal carrying timebase reference components is delivered to a first timebase reference signal detector 24 (referred to as a first detector hereinafter) for detecting the first timebase reference signal and a second timebase reference signal detector 25 (referred to as a second detector) for detecting the second timebase reference signal. The first detector 24; upon detecting the first reference signal for one horizontal scanning period produces a pulse whose duration is equal to the horizontal scanning period. The frequency of the pulse is commonly about 15.73 KHz in the NTSC system. The pulse is transferred to a first phase comparator 26 where it is phase compared in each horizontal scanning period with the output of a voltage controlled oscillator (VCO) 28 which has been divided to about 15.73 KHz by a frequency divider circuit 27. The resultant output signal is then fed through an error amplifier 29 and a loop filter (low-pass filter) 30 (LPF 1) to the VCO 28. Similarly, the second detector 25; upon detecting the second timebase reference signal of each track; produces a pulse which is equal in period to the reference sine wave. The pulse is transferred to a second phase comparator 31 where it is phase compared in each horizontal scanning period with the output of the VCO 28 which has been divided by a divider circuit 32. The resultant output signal is then fed through an error amplifier 33 and a loop filter 34 (LPF 2) to the VCO 28. When the frequency in the reference sine wave is a few megahertz higher than the frequency in the horizontal scanning period, the second loop filter (LPF 2) 34 can allow a higher frequency signal to pass than that of the first loop filter (LPF 1) 30; thus providing a faster response speed. Accordingly, the response to skew distortion developed in the front end of each track signal will be speedier. A switch 35 is actuated to switch the loops because the second timebase reference signal is contained within the beginning region of each track signal. Its action is timed by a signal derived from the second detector 25 and passed through a pair of monostable multivibrators 36 and 37. Also, the video signal is converted by an A/D converter 38 into a digital form which is then stored in a memory 39. The action of the A/D converter 38 and the memory 39 is triggered by a sampling clock signal and a write clock signal respectively which are both output in the form of CK outputs of the VCO 28. A signal retrieved from the memory 39 using a clock signal CKR which is constant in the phase contains no timebase variation and will be transmitted further from an output terminal 40. When the frequency in the horizontal scanning period is 15.73 KHz, the frequency of an output of the VCO 28 becomes about 14.3 MHz after passing through the first divider circuit 27 having a dividing ratio of 910:1. If the second divider circuit 32 has a dividing ratio of 182:1, the frequency of the burst wave becomes 2.86 MHz. It would be understood that the foregoing values are given as examples. When the video signal is a PAL or HDTV signal of different scanning lines, or a recorded signal which is divided into a plurality of channels for reduction of a frequency band and extended with time thus having a scanning period frequency different from that of its original signal, it will be processed with equal success by the foregoing arrangement of the present invention. FIG. 7 is a block diagram of a detector employed for detection of the first timebase reference signal. An input video signal carrying the first timebase reference signal, whose waveform is shown in FIG. 8-A, is fed to an input terminal 41 and then, transferred to a first gate circuit 44 which is controlled by the combination of a sync separator circuit 42 and a timing circuit 43. The first gate circuit 44 converts a sinewave component of the video signal into a burst signal of a sinewave form shown in FIG. 8-B. The burst signal is waveform modulated to into a series of pulses by a comparator 45 provided for detection of a zero-cross point of the sinewave. One of the pulses is picked up by a second gate circuit 46 and delivered from an output terminal 47 as an output signal of the detector whose waveform is shown in FIG. 8-D. FIG. 9 is a block diagram of a detector employed for detection of the second timebase reference signal. An input video signal carrying the second timebase reference signal, of which waveform is shown in FIG. 10-A, is fed to an input terminal 48 and transferred to a gate circuit 49 where a sinewave component of the video signal is gated to produce a signal whose waveform is shown in FIG. 10-B. The resultant signal is then transferred to a comparator 50 where a zero-cross point of the signal is detected to produce a zero-cross signal shown in FIG. 10-C. The zero-cross signal is transmitted further from an output terminal 51. In action, the gate circuit 49 is controlled by a timing pulse produced by the combination of a sync separator circuit 52 and a timing circuit 53. A timebase corrector in accordance with another embodiment of the present invention will now be described referring to FIG. 11. In operation, an input video signal which has been frequency demodulated and contains timebase reference signal components is fed to an input terminal 54 and transferred to both a first timebase reference signal detector 55 for detection of the first timebase reference signal and a second timebase reference signal detector 56 for detection of the second timebase reference signal. Upon detecting the first timebase reference signal, the first timebase detector 55 having an arrangement similar to that shown in FIG. 6 produces a pulse whose duration is equal to the horizontal scanning period. The pulse is transferred to a first phase comparator 56 where it is phase compared in each horizontal scanning period with the output of a voltage controlled oscillator (VCO) 58 which is divided by a frequency divider 57. A resultant output is transferred through an error amplifier 59 and a loop filter (LPF) 60 to the VCO 58. Similarly, the second timebase detector 56 upon detecting the second timebase reference signal carried in the beginning end of each track signal produces a pulse in each track. The pulse is fed to a phase control terminal 61 of the VCO 58 and to a preset terminal 62 of the divider 57. Consequently, the VCO 58 is reset in phase for oscillation and the divider 57 is preset in phase for dividing action. Also, the VCO 58 produces an output CK which serves as a sampling clock for an A/D converter 63 and a write clock for a memory 64, similar to that shown in FIG. 6. An output signal from the memory 64 is delivered from an output terminal 65. As the result, the timebase corrector can provide a quicker response to the generation of skew distortion. Because the second timebase reference signal is longer in duration than the first timebase reference signal, the resultant pulses are less affected by unwanted signal components such as noise; thus exhibiting a higher accuracy. Hence, no phase error will be developed even if the response speed is high. FIG. 12 is a block diagram of a detector for detection of the second timebase reference signal. In action, an input video signal carrying a second timebase signal component which waveform is shown in FIG. 13-A is fed to an input terminal 66 and transferred to a gate circuit 67 where a sinewave component of the input video signal is gated to produce a signal shown in FIG. 13-B. The resultant signal is then filtered into a signal waveform shown in FIG. 13-C by a bandpass filter 68 which can pass frequencies of the second timebase reference signal. The signal waveform of FIG. 13-C exhibits an incremental shape of an envelope since the bandpass filter 48 allows a narrow range of frequencies to pass. Then, the filtered signal is converted to a zero-cross signal, shown in FIG. 13-D, by a comparator 69 which can detect a zero-cross point in the signal. The zero-cross signal is transferred to a gate circuit 70 where it is gated to produce a detection pulse shown in FIG. 13-E for delivery from an output terminal 71. In action, the two gate circuits 67 and 70 are controlled by timing pulses produced by a sync separator circuit 72 and a timing circuit 73. FIG. 14 is a timing chart showing the actions of primary parts of the timebase corrector shown in FIG. 11. More particularly, FIG. 14-A illustrates a waveform of a signal contained within the beginning region of each track signal of the input video signal which contains skew components. FIGS. 14-B and 14-C respectively represent two outputs of the first and second detector circuits 55 and 56. FIG. 14-D shows a preset amplitude of the divider 57 determined by the output of the second detector circuit 56. It should be noted that the preset amplitude P is equivalent to a clock difference (denoted by P in FIG. 14-C) between the pulse output of the first detector 55 and the pulse output of the second detector 56. This results from the fact that the pulse output of the second detector 56 is delayed by P from the pulse output of the first detector 55. Although the number of recording channels is not specifically defined in this embodiment, it may arbitrarily be determined for VCR multi-channel recording operation in which a video signal of each channel can successfully be processed according to the present invention.
An apparatus for recording a video signal onto tracks of a recording tape includes circuitry for producing a first time-base reference signal which is a color burst signal composed of a first predetermined number of sinewave cycles and a second time-base reference signal which is a burst signal composed of a second predetermined number of sinewave signals. The second predetermined number of cycles is larger than the first predetermined number of cycles. The apparatus further includes superimposing circuitry for superimposing the first time base reference signal on an input video signal at intervals of a horizontal scanning period of the video signal and for superimposing the second time base reference signal on the input video signal at intervals of a predetermined number of horizontal scanning periods of the video signal. The apparatus further includes a modulator for modulating an output signal of the superimposing circuitry to obtain a modulated signal and a recording arrangement for recording the modulated signal onto the tracks of the recording tape.
7
This is a continuation of application Ser. No. 322,995, filed Nov. 19, 1981, abandoned. BACKGROUND OF THE INVENTION This invention relates to certain novel 3-alkyl-5-(alkoxy- or alkylthio-phosphynyl or phosphinothioylthiomethyl)-1,2,4-oxadiazoles and their use as soil insecticides to combat corn root worm. In particular I have found that the compounds of this invention show surprisingly good activity in killing Diabrotica larvae. German Offenlegungschrift No. 2,919,621 discloses insecticidal compounds of the general formula: ##STR2## wherein X is oxygen or sulfur; R 1 is hydrogen, C 1 to C 4 alkyl optionally substituted with halogen, C 1 to C 3 alkoxy, or phenyl; R 2 is C 1 to C 4 alkyl; and R 3 is C 1 to C 4 alkyl, C 1 to C 6 alkylamino, allylamino or di-(C 1 to C 3 ) alkylamino where the two alkyl groups on the nitrogen may form a 5- or 6-membered ring which optionally may contain an oxygen atom. The compounds of the German Offenlegungschrift were disclosed as effective against "sucking" and "biting" insects as well as mites and ticks of the order Acarina. The examples showed testing certain of the compounds for insecticidal activity on red spider mites, bean aphids, houseflies, German cockroach, Mexican bean beetle larvae, corn beetle larvae, flour weevils and African boll weevil larvae. Commonly-assigned, U.S. Pat. No. 4,237,121 discloses the use of corn root worm insecticides of compounds of the formula: ##STR3## wherein X, Y, Z and V are sulfur or oxygen and R 1 , R 2 , R 3 are alkyl of 1 to 4 carbon atoms. Commonly-assigned U.S. Pat. No. 4,213,973 discloses the use of compounds of the formula ##STR4## wherein X, Y, Z and V are oxygen or sulfur; R 1 is hydrogen or alkyl of 1 to 6 carbon atoms and R 2 and R 3 are alkyl of 1 to 6 carbon atoms, as corn root worm insecticides. U.S. Pat. No. 3,432,519 discloses insecticidal and acaricidal compounds of the general formula ##STR5## wherein R represents a hydrogen atom, an alkyl group containing 1 to 6 carbon atoms optionally carrying an alkoxy substituent containing 1 to 4 carbon atoms or an aryl group (preferably phenyl) which may carry one or more substituents selected from hydrogen atoms, the nitro group and alkyl, alkoxy and alkylthio groups containing 1 to 4 carbon atoms, R 1 represents a hydrogen atom or an alkyl group containing 1 to 4 carbon atms, R 2 represents an alkyl group containing 1 to 4 carbon atoms and X represents an oxygen or sulfur atom. British Pat. No. 1,213,707 discloses insecticidal compounds of the general formula ##STR6## wherein X 1 and X 2 which may be the same or different, each represents an oxygen or sulfur atom; A represents an alkylene group; R 1 represents an alkyl group, R 2 represents an alkyl or alkoxy group; and R 3 represents a hydrogen atom or an optionally substituted carbamoyl or amino group. The examples of the British patent show testing of certain of the compounds for insecticidal activity on adult houseflies; mosquito larvae, diamond back moth larvae, aphids and adult mustard beetles; red spider mites; and white butterfly larvae. None of these tests involved application and use of the insecticide in the soil habitat of the insects. U.S. Pat. No. 4,028,377 discloses insecticidal compounds of the general formula: ##STR7## wherein R 1 represents hydrogen, unsubstituted alkyl, benzyl or phenyl, R 2 represents methyl or ethyl, and R 3 represents unsubstituted C 1 -C 7 alkyl optionally interrupted by oxygen or represents C 3 -C 4 alkenyl. The examples of the U.S. Pat. No. 4,028,377 show testing of certain of the compounds for insecticidal activity on ticks in cotton wool; larvae of ticks; mites; and on root-gall-nematodes in soil. In the latter test, the soil infested with the root-gall-nematodes was treated with the compounds to be tested and then tomato seedlings were planted either immediately after the soil preparation or after 8 days waiting. British Pat. No. 1,261,158 discloses compounds of the general formula: ##STR8## wherein R 1 represents an alkyl group, R 2 represents an alkyl or alkoxy group, X represents an oxygen or sulfur atom; A represents a saturated divalent aliphatic hydrocarbyl group; Y represents a halogen atom or an alkyl or alkoxy carbonyl group; and n is 0, 1 or 2. The compounds of the examples of British Pat. No. 1,261,158 were tested for insecticidal effectiveness on flies, mosquito larvae, moth larvae, mustard beetles, aphids, spider mites and butterfly larvae. As described in the Ortho Seed Treater Manual, copyright 1976, Chevron Chemical Company, page 27, corn root worms have been controlled with chlorinated hydrocarbon insecticides, but in areas where resistance to such treatment has developed, good control has been obtained with organic phosphorus or carbamate soil insecticides such as Diazinon and Carbofuran insecticides. The chemical names and formulas for these latter insecticides are given below: ##STR9## SUMMARY OF THE INVENTION The 3-alkyl-5-(alkoxy- or alkylthio-phosphynyl or phosphinothioyl-thiomethyl)-1,2,4-oxadiazole compounds of this invention are represented by the formula: ##STR10## wherein X is sulfur or oxygen, Y is sulfur or oxygen, R 1 is methyl, ethyl, isopropyl, or cyclopropyl and R 2 is ethyl or isopropyl, provided that when R 1 is methyl or ethyl, R 2 is not ethyl. Among other factors, the present invention is based on my finding that the substituted oxadiazole compounds of my invention are surprisingly effective as insecticides for killing corn root worms. The compounds are very effective in killing corn root worms when applied to their soil habitat. This is especially surprising, since certain closely related compounds have shown poor activity as insecticides against corn root worm. Preferred compounds include those where X is sulfur, R 1 is methyl or ethyl and R 2 is isopropyl. As used herein, the following terms have the following meanings, unless expressly stated to the contrary. The term "root worm" is used herein to include the Northern, Southern and Western species of the corn root worm. All of these are of the Diabrotica genus. The scientific name of the Northern species is Diabrotica longicornis, the scientific name of the Southern species is Diabrotica undecimpunctata howardi, and the scientific name of the Western species is Diabrotica virgifera. DETAILED DESCRIPTION OF THE INVENTION The compounds used in the present invention may be prepared by subjecting the appropriate 3-alkyl-5-chlo-1,2,4-oxadiazoles (II) to a phosphorylation reaction. ##STR11## The phosphinate salts have the general formula (III) wherein X, Y and R 2 are as previously defined and M is a group IA metal cation or NH 4 + . The phosphorylation reaction may be carried out in an inert organic solvent such as methyl ethyl ketone, acetone, acetonitrile, ether, methanol or benzene. Preferably, equimolar amounts of reactants are employed, although a small excess of either may be used. Either reactant may be added to the other reactant in the solvent; however, it is preferred to add the solid phosphinate salt to a solution of the 3-alkyl-5-chloromethyl)-1,2,4-oxadiazole (II). The addition is carried out at temperatures in the range of 15° to 30° C. Upon completion of addition of the salt, the temperature of the salt is raised, preferably to about 50° C.; the reaction mixture is then stirred until the reaction is complete, about 1 to about 24 hours. At completion of the reaction, the solvent is stripped under reduced pressure. The product, a liquid, is then isolated by conventional procedures such as extraction, chromatography, filtration. The salts used in the phosphorylation reaction may be prepared according to the reaction scheme: ##STR12## wherein X, Y and R 2 are as defined in conjunction with Formula I and M is a group IA (alkali) metal cation or NH 4 + . Reaction (2) is carried out by adding an approximately equimolar amount of V to a stirred solution of IV in benzene. An approximately equimolar amount of VI was slowly added in a dropwise amount over a period of from about 0.5 to 1 hour. After the addition was complete, the reaction mixture was stirred for an extended period of time, about 16 hours, filtered and the solvent stripped. Other inert organic solvents such as toluene may be used in place of benzene. The MSH used in reaction (3) is prepared in situ by dissolving MOH in isopropyl alcohol by stirring, followed by a period of additional stirring from about 2 to 4 hours. Hydrogen sulfide (gas) was added by bubbling it through the MOH-alcohol mixture. The resulting mixture was then stirred for about 2 to 4 hours to give the (VIII). Reaction (3) was carried out by adding product VII (of Reaction (2)) to mixture VIII in a ratio of about two equivalents of VIII per equivalent of VII in several portions. The reaction mixture was stirred for an extended period of time, about 5 to about 12 hours, and then refluxed for about 1 to about 3 hours. The solvent was stripped, and toluene was used to chase the solvent. The product, (III), was washed with hexane and ethyl ether. The 3-alkyl-5-chloromethyl-1,2,4-oxadiazoles, II, used in the preparation of the compounds of this invention may be prepared by the condensation of the appropriate alkylamidoximes with alpha-chloroacetyl chloride according to the following reaction scheme: ##STR13## wherein R 1 is as previously defined in connection with Formula I. Further details of this preparation are disclosed in commonly-assigned U.S. Pat. No. 4,237,121 to King and Wheeler, which is incorporated by reference. An alternate method of preparing the oxadiazole intermediates of formula II which is suitable for the large scale production of such compounds and which produces those intermediates in increased yields is disclosed in the commonly-assigned, copending U.S. patent application of R. N. Reynolds titled "Process for Preparing 5-Halomethyl-1,2,4-Oxadiazoles and Intermediates Therefor." In the use of the compounds of my invention as corn root worm insecticides, optimum formulation concentrations and the manner and frequency of application may vary somewhat with the particular species of corn root worm, the degree of infestation, the environment, including type of soil, soil conditions and weather conditions (e.g. rain fall), and can be obtained by routine experimentation. A further understanding of my invention can be had from the following non-limiting examples. EXAMPLE 1 Preparation of Ethyl-O-isopropyldithiophosphinate Potassium Salt ##STR14## To a stirred mixture of 74.2 g (0.455 moles) ##STR15## Ethylthiophosphoric acid dichloride in 400 ml benzene, 30.1 g (0.5 moles) isopropyl alcohol was added. To that mixture 50.6 g (0.5 moles) triethylamine was added at a dropwise rate overnight. The mixture was then warmed for about 1 hour. The mixture was filtered by gravity. Most of the solvent (benzene) was stripped off under reduced pressure and heat to give ##STR16## The KSH was prepared in situ by the following procedure: 56.5 g (1 mole) KOH was dissolved in about 350 ml isopropyl alcohol with stirring; the mixture was allowed to stir for about 2 hours. H 2 S was added to the mixture by bubbling the gas through it (about 35 g). The resulting KSH mixture was then allowed to stir for 1 hour. To the KSH mixture, the product of the first step, ##STR17## was added in several portions, cooling the reaction mixture with water if needed. The reaction mixture was stirred overnight and then refluxed for two hours. The solvent was removed under reduced pressure and toluene was used to chase the solvent. The product was then washed with hexane:ethyl ether (3:2). The salts used to make the compounds in Table I may be prepared according to the above procedure. Optionally, an NaSH mixture is substituted for the KSH mixture. EXAMPLE 2 Preparation of ##STR18## To about 75 ml methyl ethyl ketone, 3.3 g (0.025 moles) 3-methyl-5-chloromethyl-1,2,4-oxadiazole and 6.7 g (0.03 moles) of the product of Example 1 were added with stirring. The reaction mixture was heated to about 55° C. with stirring for 6 hours. The methyl ethyl ketone was stripped under reduced pressure to give the crude product. Water (about 50 ml) and methylene chloride (about 75 ml) were added to the product and the resulting mixture stirred. The product was extracted into the methylene chloride and washed twice with 50 ml water. The product was separated with the methylene chloride (organic) phase. Magnesium sulfate was added to the methylene chloride phase to dry it. Filtering of the methylene chloride phase followed by chromatography on silica gel eluting with hexane and methylene chloride, yielded 6.4 g of the product, a light yellow liquid. Elemental analysis for C 9 H 17 N 2 O 2 PS 2 showed: calculated %C 38.6, %H, 6.11, and %N 9.99; found %C 40.8, %H 6.43, and %n 10.08. EXAMPLE 3 Preparation of ##STR19## To 75 ml methyl ethyl ketone, 3.3 g (0.025 moles) 3-methyl-5-chloromethyl-1,2,4-oxadiazole and 7.2 g (0.03 moles) ethyl-S-isopropyldithiophosphinate potassium salt were added with stirring. The reaction mixture was heated to 55° C. with stirring for 6 hours. The methyl ethyl ketone was stripped under reduced pressure to give the crude product. Water (about 50 ml) and methylene chloride (about 75 ml) were added to the product and the mixture was stirred for about 10 min. The aqueous and methylene chloride phases were separated, the product separating with the methylene chloride phase. The methylene chloride phase was dried with magnesium sulfate and filtered to give 5.2 g of the product, a yellow liquid which was chromatographed on silica gel and eluted with hexane:methylene chloride (1:1). Elemental analysis for C 9 H 17 N 2 OPS 3 showed: Calculated %C 36.5, %H 5.78, and %N 9.45; found %C 38.6, %H 6.05, and %N 10.85. EXAMPLE 4 Preparation of ##STR20## To 75 ml acetone, 2.8 g 3-isopropyl-5-chloromethyl-1,2,4-oxadiazole was added and the resulting mixture stirred for a few minutes. To that mixture 2.9 g ##STR21## Ethyl-O-ethylthiophosphinate sodium salt was added and the resulting mixture stirred for about 10 minutes and then refluxed for about 4 hours. The reaction mixture was then stirred overnight. The acetone was stripped under reduced pressure to give the crude product. Methylene chloride (about 75 ml) and water (about 50 ml) were added. The water served to wash the product, removing NaCl resulting from the reaction. The aqueous and methylene chloride phases were separated, the product separating with the methylene chloride phase. The methylene chloride phase was dried with magnesium sulfate. The product was obtained by column chromatography of the methylene chloride phase, eluting first with hexane and then hexane:methylene chloride (1:1). Elemental analysis for C 10 H 19 N 2 O 3 PS showed: calculated %C 43.16, %H 6.88, and %N 10.07; found %C 42.82, %H 6.91, and %N 10.62. Compounds made in a manner consistent with Examples 1 to 4 are found in Table I. EXAMPLE 5 Control of Diabrotica Larvae A number of the compounds of the present invention were evaluated for control of Diabrotica larvae by the following procedure: For each test compound, a dilution series to give 6.4, and 2.5 ppm (weight:weight) active ingredient in soil was prepared by diluting an acetone-test compound mixture with the appropriate amount of water containing a small amount of Ortho X-77 nonionic spreader. A 300 g batch of soil was treated with a test compound mixture to give the appropriate concentration in soil (i.e. 6.4, 2.5 or 1 ppm). About 20 two- to four-day old Diabrotica eggs were placed in the bottom on three 8 oz. plastic cups. Half of the treated soil was evenly split between the three cups. Ten corn seeds which have been pre-soaked in water were evenly distributed on top of the soil in each cup. Ten ml of water was gently added to each cup and the remaining soil divided equally between the three cups, thus covering the corn seeds. The soil surface of the cups was lightly sprayed with water to provide a water seal on each cup. The cups were incubated at 70° F. for 10 days, with daily watering. After 10 days, each test cup was examined under a dissecting scope by observing the corn roots and soil through the clear plastic walls of the cup. Control of newly-hatched larvae was evaluated by visually evaluating the degree of corn root damage by feeding larvae in conjunction with the visible presence of live and/or dead larvae. The compounds tested, the concentration of test compound in soil (ppm) and percent control of Diabrotica larvae are given in Table II. I have found from the results of biological testing that certain relatively closely related compounds showed no or poor effectiveness in controlling corn root worm as measured by the test of Example 5. Some of those compounds are shown in Table III, and such compounds are accordingly excluded from the scope of the present invention. TABLE I__________________________________________________________________________Compounds of the Formula ##STR22##Com- ELEMENTAL ANALYSISpound Physical % Carbon % Hydrogen % NitrogenNo. X Y R.sub.1 R.sub.2 State Calc. Fd. Calc. Fd. Calc. Fd.__________________________________________________________________________1 S O CH.sub.3 CH(CH.sub.3).sub.2 Yellow 38.6 40.8 6.11 6.43 9.99 10.1 liquid2 S O CH.sub.2 CH.sub.3 CH(CH.sub.3).sub.2 Yellow 40.79 39.88 6.51 6.23 9.52 9.74 liquid3 S S CH.sub.3 CH(CH.sub.3).sub.2 Yellow 36.5 38.6 5.78 6.05 9.45 10.9 liquid4 S S CH.sub.2 CH.sub.3 CH(CH.sub.3).sub.2 Amber 38.7 41.3 6.17 6.47 9.03 10.7 liquid5 O O CH(CH.sub.3).sub.2 CH.sub.2 CH.sub.3 Colorless 43.16 42.82 6.88 6.91 10.07 10.62 liquid6 S O CH(CH.sub.3).sub.2 CH.sub.2 CH.sub.3 Yellow 40.8 41.3 6.51 7.05 9.52 10.4 liquid__________________________________________________________________________ TABLE II______________________________________Compound Soil Treatment % ControlNo. ppm Day 0 Day 17 Day 31______________________________________1 6.4 100 95.5 -- 2.5 97.5 93.5 -- 6.4 100 96 2.5 96 942 6.4 62 99.2 6.4 100 2.5 100 2.5 2.5 1003 6.4 100 6.4 100 99.2 2.5 100 2.5 9 1004 6.4 99.4 -- 52* 2.5 99.4 -- 23*5 6.4 81 -- -- 2.5 0 -- --6 6.4 99.2 -- -- 2.5 18 -- --______________________________________ *Day 27 TABLE III______________________________________Compounds of the Formula ##STR23## Con- SoilCom- cen- Treatmentpound tration % CNo. X Y R.sub.1 R.sub.2 (ppm) Day 0______________________________________11 S O CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.3 6.4 0 2.5 012 0 0 CH.sub.3 CH.sub.2 CH.sub.3 6.4 0 2.5 0______________________________________
Oxadiazole compounds of the formula ##STR1## wherein X is sulfur or oxygen; Y is sulfur or oxygen; R 1 is methyl, ethyl isopropyl or cyclopropyl; and R 2 is ethyl or isopropyl, provided that when R 1 is methyl or ethyl, R 2 is not ethyl, are effective as corn root worm insecticides.
2
TECHNICAL FIELD [0001] The technical field generally relates to vehicle electrical systems, and more particularly relates to methods to control power to one or more auxiliary power outlets in a vehicle. BACKGROUND [0002] The amount of the electrical load on a vehicle is growing and is ever more complex. When all systems are in operation concurrently, a vehicle may consume upwards of 300 amps. Not only is the amount of the electrical load growing, but the sophistication of the load is also growing with more and more processors and other electronic features and equipment being added. [0003] As more features are added to a vehicle, power management with a goal to conserve the power in the vehicle battery is growing more important. Typically alternators generate up to 185 amps. However, transient current of about 350 amps may be experienced due the use of features such as power steering, heated seats and the use of hybrid systems. Steady state current in a vehicle is approximately 77 amps. Off power mode vehicle current may drop to as low as 20 mA. [0004] One ubiquitous exemplary electronic device that commonly uses the vehicle battery via an auxiliary power outlet is the cell phone. Cell phones may draw approximately one Amp (e.g., 750 mA) during full charging mode. Left on for a long enough period of time, a cell phone can drain a vehicle battery. Other portable electronic devices can do likewise. [0005] Accordingly, it is desirable to preserve a vehicle battery by reducing power consumption by rechargeable devices. Furthermore, other desirable features and characteristics of the present invention will become apparent from the subsequent detailed description and the appended claims, taken in conjunction with the accompanying drawings and the foregoing technical field and background. SUMMARY [0006] A method for controlling an accessory power outlet (APO) in a vehicle while charging a battery powered device is provided. The method comprises connecting the battery powered device to the accessory power outlet, synchronizing communications between the battery powered device to a computing device of the vehicle, and determining when the battery powered device is connected to an electric bus and is charging. When the battery powered device is either not connected to the electric bus or the battery powered device is not charging, then disconnecting power from the accessory power outlet. [0007] A system for controlling an accessory power outlet (APO) in a vehicle while charging a battery powered device. The system comprises a battery, an electrical bus electrically connected to the battery, at least one auxiliary power outlet in electrical communication with the battery and configured to mate with a battery charging port of a battery operated device; and an electronic control unit (ECU). The ECU is configured to synchronize communications between the battery powered device and the ECU; and, to determine when the battery powered device is connected to the electric bus and is charging. When the battery powered device is either not connected to the electric bus or the battery powered device is not charging then power is disconnected from the accessory power outlet. [0008] A vehicle is provided for. The vehicle is comprised of a battery, an electrical bus electrically connected to the battery, at least one auxiliary power outlet in electrical communication with the battery via the electrical bus and configured to mate with a battery charging port of a battery powered device. The vehicle is further comprises an electronic control unit (ECU). The ECU is configured to synchronize communications between the battery powered device and the ECU and to determine when the battery powered device is connected to the electric bus and is charging. When the battery powered device is either not connected to the electric bus, or the battery powered device is not charging, then the accessory power outlet is deenergized. DESCRIPTION OF THE DRAWINGS [0009] The exemplary embodiments will hereinafter be described in conjunction with the following drawing figures, wherein like numerals denote like elements, and wherein: [0010] FIG. 1 is a simplified vehicle in accordance with an embodiment; [0011] FIG. 2 is a simplified logic flow diagram of a method for controlling an auxiliary power outlet (APO) in a vehicle. DETAILED DESCRIPTION [0012] The following detailed description is merely exemplary in nature and is not intended to limit the application and uses. Furthermore, there is no intention to be bound by any expressed or implied theory presented in the preceding technical field, background, brief summary or the following detailed description. [0013] Those of skill in the art will appreciate that the various illustrative logical blocks, modules, circuits, and algorithm steps described in connection with the embodiments disclosed herein may be implemented as electronic hardware, computer software executing on a processor, or combinations of both. Some of the embodiments and implementations are described above in terms of functional and/or logical block components (or modules) and various processing steps. However, it should be appreciated that such block components (or modules) may be realized by any number of hardware, software executing on a processor, and/or firmware components configured to perform the specified functions. [0014] To clearly illustrate this interchangeability, various illustrative components, blocks, modules, circuits, and steps may be described above generally in terms of their functionality. Whether such functionality is implemented as hardware or software depends upon the particular application and design constraints imposed on the overall system. Skilled artisans may implement the described functionality in varying ways for each particular application, but such implementation decisions should not be interpreted as causing a departure from the scope of the present invention. For example, an embodiment of a system or a component may employ various integrated circuit components, e.g., memory elements, digital signal processing elements, logic elements, look-up tables, or the like, which may carry out a variety of functions under the control of one or more microprocessors or other control devices. In addition, those skilled in the art will appreciate that embodiments described herein are merely exemplary implementations. [0015] The various illustrative logical blocks, modules, and circuits described in connection with an electronic control unit (ECU) in the embodiments disclosed herein may be implemented or performed with a general purpose processor, a digital signal processor (DSP), an application specific integrated circuit (ASIC), a field programmable gate array (FPGA) or other programmable logic device, discrete gate or transistor logic, discrete hardware components, or any combination thereof designed to perform the functions described herein. A general-purpose processor may be a microprocessor, but in the alternative, the processor may be any conventional processor, controller, microcontroller, or state machine. A processor may also be implemented as a combination of computing devices, e.g., a combination of a DSP and a microprocessor, a plurality of microprocessors, one or more microprocessors in conjunction with a DSP core, or any other such configuration. [0016] The word “exemplary” is used exclusively herein to mean “serving as an example, instance, or illustration.” Any embodiment described herein as “exemplary” is not necessarily to be construed as preferred or advantageous over other embodiments. [0017] The steps of a method or algorithm described in connection with the embodiments disclosed herein may be embodied directly in hardware, in a software module executed by a processor, or in a combination of the two. A software module may reside in RAM memory, flash memory, ROM memory, EPROM memory, EEPROM memory, registers, hard disk, a removable disk, a CD-ROM, or any other form of storage medium known in the art. An exemplary storage medium is coupled to the processor such the processor can read information from, and write information to, the storage medium. In the alternative, the storage medium may be integral to the processor. The processor and the storage medium may reside in an ASIC. The ASIC may reside in a user terminal. In the alternative, the processor and the storage medium may reside as discrete components in a user terminal. [0018] In this document, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Numerical ordinals such as “first,” “second,” “third,” etc. simply denote different singles of a plurality and do not imply any order or sequence unless specifically defined by the claim language. The sequence of the text in any of the claims does not imply that process steps must be performed in a temporal or logical order according to such sequence unless it is specifically defined by the language of the claim. The process steps may be interchanged in any order without departing from the scope of the invention as long as such an interchange does not contradict the claim language and is not logically nonsensical. [0019] Furthermore, depending on the context, words such as “connect” or “coupled to” used in describing a relationship between different elements do not imply that a direct physical connection must be made between these elements. For example, two elements may be connected to each other physically, electronically, logically, or in any other manner, through one or more additional elements. [0020] FIG. 1 is a simplified diagram of a vehicle 1 illustrating an exemplary embodiment of the subject matter disclosed herein. Among other components, the vehicle comprises wheels 3 , drive train 4 and a body 2 . The vehicle 1 further comprises a battery 30 . Battery 30 may be a battery of any size and voltage required for the proper operation of the vehicle 1 . As non-limiting examples, the battery 30 may provide a potential of 12 volts, 110 volts or 220 volts. [0021] The power from the battery 30 may is distributed via a direct current (DC) bus 40 . The illustrated DC bus 40 is simplified for the sake of clarity and brevity. The DC bus 40 may be a single conducting element such as a wire or may comprise a more complex circuit with distribution lines such as exemplary distribution lines 40 A and 40 B. The various distribution lines of the DC bus 40 may supply any number of DC loads in the vehicle such as the electronic control unit (ECU) 20 , a wireless transceiver 10 and the auxiliary power outlets (APO) 50 A and 50 B. [0022] The DC bus 40 may also include ancillary circuitry to step up or step down voltages in any part of the DC bus 40 . For example, distribution line 40 A may include one or more DC-DC converters as are well known in that art to step down a 110 volt potential to a 6 volt potential. The DC bus 40 may also have ancillary circuitry as ay be well known in the art to transmit digital data through the DC bus to the ECU 20 or other equivalent computing device in the vehicle. [0023] The APOs ( 50 A/ 50 B) may include one or more physical sockets configured to accept one or more fittings (e.g., a plug) comprised on an electronic device 60 or on a charging cable for an electronic device that is configured to charge the battery (not shown) of the electronic device. Non-limiting examples of an electronic device include a cell phone, a computing device, a music storage device and a gaming device. Further, non-limiting examples of plugs/ports include a USB port, a conventional cigarette lighter port, cylindrical plugs, one pin plugs, multi-pin plugs, molex connectors, Tamiya connectors, Empower plugs, Deans connectors, SAE connectors, ISO 4165 connectors and cell phone connectors of all types. [0024] In embodiments herein, the electronic device(s) 60 include a means for wired and/or wireless communication with the wireless transceiver 10 . Means for wired and wireless communications within a vehicle are manifold and well known in the art. Thus, the myriad forms of wired and wireless communications will not be discussed further herein in the interest of clarity and brevity other to say that communications protocols for such communications may be Ethernet, Zigbee™, Bluetooth™, Wifi and any other protocol that may be developed in the future under IEEE standards 802.15, 802.11, or under any follow-on wired or wireless IEEE standards that may be developed in the future. [0025] FIG. 2 is a logic flow diagram of a method 100 for controlling power to APOs in a vehicle. For simplicity, and by way of example only, the following discussion will focus on the charging of cell phones. However, Applicants do not intend the subject matter herein to be so limited. The following may apply to any electric/electronic devices that require a battery charge. Non-limiting examples include Ipods™, Ipads™, laptop computers, electronic tablets, pagers, Blackberrys™, portable radios, electronic book readers (i.e., a Nook™), etc. [0026] At process 110 , a cell phone is, or has been, wirelessly synchronized to a computing device within the vehicle 1 and is physically connected to an auxiliary power outlet 50 A/B for recharging. Synchronization occurs when a mobile device communicates with applications on a computing device or a server. This is often referred to simply as a “sync” or a “docking ” Mobile devices must have some way of loading applications, updates, and changes to their operating systems or settings. Even devices capable of wireless networking must have some way of loading software, if only to load what is needed to create the wireless connection in the first place. You can do this by synchronizing the device's operating system and applications with either a central management program or individual applications on a vehicle's computing device. [0027] Most mobile devices use a cable, docking unit, or cradle to communicate with a computer, usually through a USB port. Applications on the device can transfer and receive data from applications on the computer so that both the computer and the device have the same information. For example, Date Book software on a Palm device can communicate and exchange appointments with a Microsoft Outlook Calendar on a Windows computer. Wireless devices can synchronize over the Internet or wireless networks. Wireless sync eliminates the need for the device to be physically connected to the computer. [0028] In this example it will be assumed that the central computing device is the ECU 20 . Synchronizing cell phones to a vehicle's computing device for communication purposes is well known in the art and will not be discussed further herein in the interest of simplicity and clarity. An elapsed time clock is also started at process 110 . [0029] At decision point 120 , the ECU 20 determines whether there is a cell phone 60 present (i.e., plugged in) and charging at an APO 50 A/B. This may be accomplished in a variety of ways too numerous to chronicle herein. However, one exemplary method would include the wireless communication of a “charging” flag being set in the cell phone's software. This software may be included in an “app” (i.e. an application) that is installed on the cell phone by a user or may be part of the cell phone's operating system. In any event, the indication of “charging” is communicated to the ECU 20 wirelessly. [0030] Determining whether there is a cell phone 60 present (i.e., plugged in) and charging at an APO 50 A/B may be done continuously or discontinuously. Discontinuous monitoring is contemplated herein as being periodic or non-periodic and includes randomly, variably and/or a following fixed timing pattern that is not periodic. [0031] In alternative embodiments, the indication of “charging” may be sent digitally to the ECU 20 via the DC Bus 40 as a wired communication. Communication of digital data over a power line such as a connected indication is well known in the art (e.g., I phone™) and will not be discussed herein in the interest of clarity and brevity. [0032] In other embodiments, the indication of “charging” may include a communication of a state of charge (SOC) or a change in the SOC (ΔSOC). State of charge (SOC) is the equivalent of a fuel gauge for a conventional battery or a battery pack in an electric vehicle (BEV), hybrid vehicle (HEV), or plug-in hybrid electric vehicle (PHEV). The units of SOC are percentage points (0%=empty; 100%=full). An alternate form of the same measure is the depth of discharge (DoD), the inverse of SOC (100%=empty; 0%=full). SOC is normally used when discussing the current state of a battery in use, while DoD is most often seen when discussing the lifetime of the battery after repeated use. [0033] Another indication of charging may be a detection of a trickle current through a particular distribution line 40 A/B. Means for detecting a current through a wire are well known in the art. For example, a sensing resistor 41 A/ 41 B may be placed in the distribution line 40 A/B. [0034] When it is determined that the cellphone 60 is either not present or is not charging (i.e., battery is full) the ECU 20 shuts down power to the APO at process 150 . This may be done by selectively opening a relay in the distribution line to the APO with the cell phone 60 or the ECU may shut down power to all APOs. [0035] At decision point 130 , the ECU 20 determines whether or not the SOC of the cell phone battery is below a predetermined threshold. Such a determination may be made by receiving an indication of the SOC from the cell phone via the wireless transceiver or via wired communication. The indication may be any suitable indication known in the art. Non-limiting examples of indications include a minimum voltage, an amp-hour calculation result, and a number of “bars” as is commonly shown on a cell phone. The predetermined threshold may be set at manufacture or maybe configured by a user. [0036] When the SOC is less than the predetermined threshold, then the respective APO(s) are energized until the threshold is determined to have been met at process 140 , wherein the APO(s) are subsequently deenergized at process 150 . [0037] At process 160 , an elapsed time is checked since the last determination was made at process 110 . If the elapsed time has passed then the method 100 returns to process 110 and the method 100 is repeated. The elapsed time may be set at manufacture or may be configured by a user. [0038] When the SOC is at or greater than the predetermined threshold, then an elapsed time is checked on the timer since the last determination at process 110 , at process 160 . If the elapsed time has passed then the method 100 returns to process 110 and the method 100 is repeated. [0039] While at least one exemplary embodiment has been presented in the foregoing detailed description, 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 disclosure in any way. Rather, the foregoing detailed description will provide those skilled in the art with a convenient road map for implementing the exemplary embodiment or exemplary embodiments. It should be understood that various changes can be made in the function and arrangement of elements without departing from the scope of the disclosure as set forth in the appended claims and the legal equivalents thereof.
Methods, systems are provided for controlling an auxiliary power outlet in a vehicle. The method includes connecting the battery powered device to the accessory power outlet, synchronizing communications between the battery powered device to a computing device of the vehicle, and determining when the battery powered device is connected to an electric bus and is charging. When the battery powered device is either not connected to the electric bus or the battery powered device is not charging, then disconnecting power from the accessory power outlet. The system includes a battery, an electrical bus electrically connected to the battery, at least one auxiliary power outlet in electrical communication with the battery and configured to mate with a battery charging port of a battery operated device; and an electronic control unit (ECU). The ECU is configured to disconnect power from the accessory power outlet when the battery is charged.
8
BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a device for preventing a gland nut used in a valve such as a ball valve from loosening as a consequence of rotation of the valve. 2. Description of Prior Art Heretofore, a device illustrated in FIGS. 6 and 7 has been known as a means to effect the kind of prevention of interest herein. This preventive device has found utility in a ball valve such as is provided with a fitting flange for fixing an actuator. This ball valve is adapted to open and close a ball by rotating a stem, accommodate packing in a packing chamber specifically provided in the fitting flange as a shaft sealing structure for the stem, and press this packing by tightening through a gland the packing with a hexagonal nut 1 helically coupled with the stem. This hexagonal nut 1 has the helical union between itself and the stem loosen as a consequence of the opening and closing motion of the valve. Therefore, this loosening of the nut 1 is prevented by a lock plate 3. As illustrated in FIG. 6, the lock plate 3 has a pair of opposite engaging faces 2 engage with the opposed lateral faces of the hexagonal nut 1 and forms therein a fitting hole 5 provided with a pair of opposite engagement faces 4 fit for the stem, thereby enabling the nut 1 to be fixed to the stem. According to this conventional device, however, since the lock plate 3 has the engaging faces 2 thereof engage with the two opposed faces of the hexagonal nut 1, the lock plate 3, detached from the nut 1, has to be re-attached to the nut 1 each time the nut 1 is rotated by an angle of 60 degrees in order to lock the nut 1 and the stem. When the hexagonal nut 1 fitted with the lock plate 3 is used to tighten the packing, therefore, the nut 1 must be rotated by an angle of 60 degrees from the position of the lock plate 3. The device, as an inevitable consequence, entails such problems as enabling the tightening of the packing by the nut 1 to be only adjusted every 60-degree rotation of the nut 1 and requiring a considerable tightening force in order to ensure the 60-degree rotation. SUMMARY OF THE INVENTION The present invention has been developed for the purpose of solving the problems attendant with the prior art, and has the object of providing a device for preventing a gland nut in a valve from loosening that allows the gland nut to be fixed at a position to be reached after each rotation in one half of the angle required heretofore, and further enables the rotation of the gland nut to press a packing, thereby finely adjusting the sealing property of the packing. To attain the object mentioned above, this invention provides a device for preventing a gland nut from loosening. The gland nut has a plurality of lateral faces and intervening corners and is used in a valve comprising a valve body having an open chamber, a valve member inside the valve body, a gland packing accommodated in the open chamber, and a stem projecting from the open chamber for operating to open and close the valve member. The stem is helically coupled with the gland nut, which serves to press the gland packing. The device comprises a locking piece inserted non-rotatably on the stem. A pair of engaging claws formed on the locking piece enable engagement with one of the lateral faces of the gland nut and also with two lateral faces of the gland nut adjoining each other astraddle an intervening corner of the gland nut. The locking piece can have a plate face formed therein with a fitting hole incorporating therein an engaging part adapted to engage with a flat face of the stem, and formed thereon with the the pair of engaging claws. The prevention of loosening of the gland nut can be fortified by providing a plurality of such pairs of engaging claws at opposed positions, for example. The gland nut can be locked by setting the engaging claws of the locking piece fast in position on the lateral faces of the gland nut and can be locked further infallibly by causing the engaging claws to be set astraddle the corner of the gland nut. In the case of a hexagonal gland nut, for example, the sealing property of the packing can be finely adjusted because this nut can be locked after each of the rotations of 30 degrees at a time. Thus, the interval of rotations of adjustment of this gland nut is halved as compared with the conventional gland nut. The object, other objects, advantages and feature of the present invention will become more apparent to those skilled in the art from the accompanying drawings and following description of the present invention with reference to the drawings. BRIEF DESCRIPTION OF THE DRAWINGS FlG. 1 is a partially longitudinal section illustrating one embodiment of the present invention. FIG. 2 is a magnified exploded view illustrating a stem, a gland nut, and a locking piece shown in FIG. 1 in a separated state. FIG. 3 is a plan view illustrating the gland nut of FIG. 2 having the locking piece of FIG. 2 fitted thereon. FIG. 4 is a front view of FIG. 3. FIG. 5 is a plan view illustrating the locking piece of FIG. 3 set in position by a rotation of 30 degrees. FIG. 6 is a plan view illustrating a nut and a locking piece in a typical conventional device for preventing the nut from loosening. FIG. 7 is a front view of FIG. 6. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT A preferred embodiment, in which a device of the present invention for preventing a gland nut from loosening is applied to a ball valve will be described below with reference to FIG. 1 to FIG. 5. As illustrated in FIG. 1, an open chamber 13 is formed in a flange part 11 adapted to fix an actuator (not shown) and formed on a body 10 of a ball valve, and a gland packing 12 is fitted in the chamber 13. The body 10 is provided therein with a ball 15 containing a through hole 14, and this ball 15 is rotated by a stem 16 for rotary operation. This stem 16 is projected from the open chamber 13. A screw part 17 is formed in the projected part of the stem 16, and a flat face 23 is formed in an oval shape above the screw part 17. The actuator has a drive shaft (not shown) and a handle (not shown) disposed above the stem 16. In FIG. 1, reference numeral 28 designates a ball seat, numeral 18 a gland, numeral 19 a washer, numeral 20 a gland nut that will be specifically described hereinbelow, and numeral 21 a locking piece which will be specifically described hereinbelow. The gland nut 20 is helically joined to the screw part 17 of the stem 16 so as to press the gland packing 12 through the gland 18 and washer 19 and help the packing 12 to retain its sealing property. The present embodiment uses a hexagonal nut as the gland nut 20. The locking piece 21 is obtained by press-molding a metal plate. As illustrated in FIGS. 1 and 2, it has a plate face 22 with a fitting hole 25 formed therein having an engaging part 24 for engagement with the flat face 23 of the stem 16. At opposed positions of this plate face 22, two sets of engaging claws 26 and 27 for engagement with lateral faces 20a of the gland nut 20 are respectively formed. One set of the engaging claws 26 and 27 are disposed such that they can be engaged with one lateral face 20a of the gland nut 20 (FIG. 4) and can also be engaged with two lateral faces 20a and 20a of the gland nut 20 which adjoin each other astraddle an intervening corner 20b of the gland nut 20 (FIG. 5). Next, the operation of the embodiment described above will be explained. Since the gland nut 20 is loosened by being sympathetically rotated as a consequence of the repeated rotational motion of the stem 16, it is provided with the locking piece 21 which is adapted to fix the gland nut 20 and the stem 16 relative to each other. This locking piece 21 is mounted on the gland nut 20, as shown in FIG. 1, with the fitting hole 25 thereof fit on the stem 16 when one of the lateral faces 20a of the gland nut 20 and the flat face 23 of the stem 16 are parallelly positioned. The two sets of engaging claws 26 and 27 of the locking piece 21 are engaged with the opposed lateral faces 20a of the gland nut 20 to lock the nut 20 and the stem 16 to each other. In that state, the gland nut 20 retains the sealing property of the gland packing 12. In order to make the sealing property more reliable, the gland nut 20 is tightened to press the gland packing 12. In this case, the locking piece 21 is separated from the stem 16 and the gland nut 20 is rotated by angles of 30 degrees at a time so that each set of engaging claws 26 and 27 are engaged with two lateral faces 20a of the gland nut 20 adjoining to each other astraddle an intervening corner 20b of the gland nut 20 as illustrated in FIG. 5. Since the tightening of the gland packing 20 can be finely adjusted at intervals of 30 degrees as described above, the rotation of the gland nut 20 for the adjustment is halved as compared with the conventional equivalent, thus improving the process. Though this embodiment has depicted a case of specifically using a ball valve, the present invention does not need to be limited to a ball valve, but may be effectively applied to other valves. The gland nut does not need to be a hexagonal nut but may be any other polygonal nut. The embodiment described above contemplates providing two opposed pairs of engaging claws. One pair of engaging claws suffices to effect the expected prevention of loosening. The discrimination between one pair and a plurality of pairs of engaging claws may be decided depending on the thoroughness with which the loosening is to be prevented. It is clear from the description given above that since this invention uses the locking piece which is capable of locking the gland nut both on a pair of opposed lateral faces and on two pairs of opposed lateral faces, each pair being lateral faces adjoining to each other astraddle an intervening corner, it produces prominent effects such as fixing the nut at positions which are each reached by the rotation of one half of the angle required for the prior art lock plate, permitting fine adjustment of the sealing property of the packing, and helping the valve to manifest the sealing function for a long time. Since the device is simple in structure, it permits inexpensive quantity production.
A device for preventing a polygonal gland nut helically coupled with the stem of a valve from loosening includes a locking piece inserted non-rotatable on the stem. A pair of engaging claws are formed on the locking piece to engage with one of the lateral faces of the gland nut and also with two lateral faces of the gland nut adjoining each other straddled an intervening corner of the gland nut.
5
BACKGROUND AND SUMMARY OF THE INVENTION FIELD OF THE INVENTION The present invention relates generally to rear view mirror assemblies for motor vehicles and more particularly to exterior motor vehicle mirror assemblies which incorporate auxiliary warning lights. DISCUSSION Auxiliary warning lights have long been incorporated on the sides of motor vehicles to provide a means of communicating the intentions of the operator thereof to adjacent vehicles such as for example the intention to change traffic lanes or to make a turn. Such lights are advantageous in providing notice to an adjacent vehicle that may be located in a blind spot and positioned such that the signaling vehicle's tail lights are not visible to the adjacent vehicle's operator. While incorporation of such auxiliary warning lights is relatively easy and straightforward on work-type vehicles it becomes a somewhat more complex problem when passenger-type vehicles are involved due in part to the importance of aesthetic appearance. Other considerations which may apply to any type of vehicle include the need to position the lights so as to minimize any impact on the vision of the vehicle operator and to maximize the area to the side and rear of the vehicle from which the auxiliary lighting is visible. Additionally, because in many cases the vehicle manufacturer may want to offer the auxiliary lighting arrangement as an option on certain vehicles, it is highly desirable that the lighting system be designed to easily and conveniently integrate with the existing vehicle design so as to minimize added labor and/or costs associated with its installation. The present invention provides a highly effective and aesthetically pleasing auxiliary lighting system which is integrated into the vehicle's exterior rear view mirror assembly. Preferably, the auxiliary warning light of the present invention will be positioned on the laterally outer surface of the vehicle's exterior rear view mirror in such a manner as to be visible throughout an arc extending about 90 degrees rearwardly from a line extending generally perpendicular to the longitudinal axis of the vehicle. In this manner maximum visibility of the auxiliary warning light is provided to vehicles coming alongside the equipped vehicle while still preventing the emitted light from being visible to the vehicle operator or oncoming traffic. It should be noted, however, that the auxiliary warning light may be positioned so as to be visible to oncoming traffic in addition to the above referenced arc should this be desired and may in fact replace fender side marker lights required in certain countries. In one form the light is integrated into a removable decorative covering which is secured to the mirror housing and a pigtail is provided for connecting the light to a wiring harness in the interior of the mirror housing. In a modification of this embodiment, the decorative cover member incorporating the light assembly is provided with a plug and the mirror housing includes a receptacle whereby electrical contacts on the cover member may be “plugged into” the receptacle as the decorative cover member is fitted to the housing. This last arrangement further reduces the costs associated with final assembly as no separate effort is required to make the electrical connections for the auxiliary warning light. Further, the integration of the light assembly into the decorative cover member greatly facilitates the offering of the auxiliary lighting feature as an option because only the decorative cover member need be changed to add or delete this auxiliary lighting feature. Additional advantages and features of the present invention will become apparent from the subsequent description and the appended claims taken in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a fragmentary perspective view of a side of a motor vehicle having an exterior rear view mirror assembly incorporating an auxiliary warning light provided thereon all in accordance with the present invention; FIG. 2 is a side view of the mirror assembly of FIG. 1; FIG. 3 is a section view of the mirror light assembly of FIG. 1, the section being taken along line 3 — 3 of FIG. 1; FIG. 4 is a perspective view of a mirror housing with alternative decorative cover members shown in position for installation thereon, all in accordance with the present invention; FIG. 5 is a view of the back side of a decorative cover member having a light assembly incorporated therein which includes an integrally formed electrical connector in accordance with the present invention; FIG. 6 is a view of a portion of a mirror housing incorporating an electrical outlet adapted to mate with the plug shown in FIG. 5, all in accordance with the present invention; and FIG. 7 is a plan view of a motor vehicle having mirrors in accordance with the present invention secured to opposite sides thereof. DESCRIPTION OF THE PREFERRED EMBODIMENT Referring now to the drawings and in particular to FIGS. 1 and 7, there is shown an exterior rear view mirror assembly indicated generally at 10 installed on the door 12 of a motor vehicle 14 . Mirror assembly 10 is of the typical breakaway design and includes a housing 16 pivotably supported on an arm 18 extending outwardly from a generally triangularly shaped mounting plate 20 . As shown in FIG. 7, preferably two mirrors 10 will be mounted on a vehicle 14 , one on each side thereof. Housing 16 may be of any desired shape and includes an upper wall portion 22 , a lower wall portion 24 , a forwardly facing wall portion 26 and inner and outer wall portions 28 and 30 all of which merge smoother together so as to present a pleasing appearance. The rearwardly facing portion of housing 16 is open and is adapted to receive a reflective mirror 32 . Mirror 32 may be either of any suitable type such as flat, concave or convex or of the type which automatically adjusts to reduce glare. A suitably shaped support member (not shown) is secured within the housing and serves to movably support mirror within the opening. The support member may include suitable drive motors and the like for remote control adjustment of mirror as well as means for heating the mirror if desired. Housing 16 also contains a recessed portion 34 extending over at least a part of upper, inner, outer and forwardly facing portions 22 , 28 , 30 and 26 which is adapted to receive a decorative cover member 36 which cover member may be chromed, colored to match the vehicle or of some other finish to present an aesthetically pleasing appearance. As thus far described, mirror assembly 10 is typical of existing rear view mirror assemblies currently employed on various motor vehicles. However, mirror assembly 10 of the present invention also incorporates an auxiliary warning light assembly 38 integrated with the decorative cover member 36 . As best seen with reference to FIG. 3, auxiliary warning light assembly 38 includes a light housing comprising a base member 40 having an opening 42 therein which is adapted to receive a suitable electrical socket 44 having a light source 46 provided thereon. Preferably opening 42 will be designed with two or three radially outwardly and circumferentially extending open portions whereby segmented inner flange 48 of light socket 44 may be inserted and then turned a few degrees to lock it in place. It should be noted that any suitable available light source 46 may be utilized. A suitable pigtail and associated electrical connector 50 is also provided extending outwardly from socket 44 which is adapted to be connected to connector 52 of wiring harness 54 provided in housing 16 . A lens member 56 is secured to base member 40 and is designed so as to direct light emitted from light source outwardly from mirror housing through an arc 58 extending approximately 90 degrees rearwardly from a line 60 passing through the mirror 10 and extending substantially perpendicular to the longitudinal axis 62 of the motor vehicle 14 . In order to enhance the visible light transmitted by the lens 56 the inner surface 64 of base member 40 will preferably be coated with a reflective material and shaped so as to direct a maximum amount of light from the light source 46 to the lens 56 . Light assembly 38 will preferably be mechanically secured to decorative cover member 36 by means of integrally formed snap fasteners so as to form a one-piece assembly therewith. Although any other suitable manner of securing light assembly 38 to decorative cover member 36 may be used such as for example adhesive bonding, sonic welding, molding or even suitable separate fasteners. It is desirable that lens 38 have an outer surface which is shaped so as to form a substantially smooth continuation of the outer contour of decorative cover member as is shown in FIGS. 1 and 2. In order to accommodate light assembly 38 , housing 16 is provided with an opening 66 on the recessed part of outer surface portion 30 which underlies decorative member 36 . While housing 16 is shown as providing an opening 66 to accommodate light assembly 38 , in some applications it may be desirable to provide an enclosed recess in place thereof. Additionally, as mentioned above, a wiring harness 54 having a suitable electrical connector 52 will be provided within housing 16 so as to be accessible through opening 66 or within the recess if such is provided in place of the opening 66 . In order to assemble decorative member 36 and associate light assembly 38 , one need merely interconnect the two electrical connectors 50 , 52 and thereafter assemble decorative member 36 to housing 16 . As shown in FIG. 4, decorative member 36 is provided with a plurality of spaced outwardly extending tangs 68 on the back surface 70 thereof. These tangs 68 are designed to be received within suitable openings provided in housing 16 and to cooperate with latch members provided therein to retain the decorative member 36 thereon in the same manner as in currently available mirror assemblies of this type. Warning light assembly 38 is intended to be interconnected with the vehicle turn signal system so that when one or the other of the turn signals are actuated, the light assembly 38 provided on the exterior mirror on the corresponding side of the vehicle will also be actuated. In this manner any other vehicle that may be approaching the vehicle equipped with the subject invention or that may be traveling in its blind spot will immediately be appraised of the equipped vehicle's intention to turn or change lanes even though they may not be in a position to see the vehicle tail lights. However, because the light is positioned on the outer wall portion 30 of the mirror assembly, the housing 16 and mirror 32 will prevent the driver of the vehicle from being distracted by this light when actuated. As previously mentioned, the subject invention is particularly well suited for offering of the auxiliary warning light as an optional accessory by vehicle manufacturers. As shown in FIG. 4, the overall size and shape of the decorative member 36 incorporating the light assembly 38 is such that it may be easily and conveniently interchanged with a decorative member 72 which does not include the light assembly. Thus, during final assembly of the mirror, the assembler need merely select one or the other of the two decorative cover members 36 , 72 for attachment to the mirror housing 16 depending upon the desires of the intended customer. Further, should a purchaser of a vehicle decide at a later date to either add or delete the auxiliary lighting feature, it is only necessary to replace the decorative cover member 36 or 72 with the other cover member. Referring now to FIGS. 5 and 6, another embodiment of the subject invention is disclosed which further facilitates rapid and low cost assembly of the subject invention. In this embodiment, base member 40 , light socket 44 and connector 50 are replaced by a base member 73 and a light socket 74 having a pair of electrically conductive pins 76 extending outwardly therefrom. Mirror housing 16 ′ is also modified by replacing opening 66 with a molded-in cavity 78 in which a pair of spaced openings 80 are provided positioned so as to receive pins 76 when decorative member 82 is assembled thereto. Thus, with this embodiment the assembler need not first interconnect the two electrical connectors 50 , 52 but rather needs merely install the decorative cover member 82 during which pins 76 will be received within openings 80 thereby electrically connecting light assembly to the existing vehicle turn signal system. As with the previous embodiment, should a purchaser not desire to include the light assembly, a cover member without the light assembly included is easily assembled to mirror housing 16 and will cover and conceal cavity 78 provided therein. While it will be apparent that the preferred embodiments of the invention disclosed are well calculated to provide the advantages and features above stated, it will be appreciated that the invention is susceptible to modification, variation and change without departing from the proper scope or fair meaning of the subjoined claims.
An exterior rear view mirror assembly is disclosed which incorporates a warning light actuatable in conjunction with the vehicle turn signals to alert adjacent motor vehicles of an anticipated turn. The warning light is integrated into a first decorative cover member and may be connected to the vehicle turn signal circuit by way of connectable electrical leads or by an integrally formed plug and outlet arrangement. A second decorative cover member may be substituted for the first decorative cover member when it is not desired to incorporate the warning light.
1
CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This application is related to U.S. Provisional Application Ser. No. 60/651,653 filed Feb. 11, 2005 and the benefit under 35 USC1 19(e) of such U.S. Provisional Application is claimed. BACKGROUND OF THE INVENTION [0002] 1. Field of the Invention [0003] This invention relates to a method of refining wood pulp; more especially the invention relates to such a method in which pulp consistency in the refiner is adjusted by controlled addition of dilution water to the refiner. [0004] In a preferred embodiment, the present invention relates to a method for controlling TMP (thermomechanical pulp) refiners by adjustment of the refining intensity. Pulp consistencies in the refiner are controlled and adjusted to achieve stable refining intensity and to compensate for disturbances such as the ones associated with changes in production rate. [0005] 2. Description of the Prior Art [0006] The quality of the pulp in thermomechanical pulp (TMP) refining is very much a function of the applied specific energy defined as the energy per tonne of production. The conventional approach to control pulp quality is therefore to adjust the specific energy either through changes in refiner motor load or through changes in refiner throughput, Owen J. et al “A practical approach to operator acceptance of advanced control with dual functionality. Proceedings Control Systems 98, Porvoo, Finland”. [0007] Pulp quality also depends on the rate at which this energy is applied as expressed by the refining intensity or the specific energy per bar impact, Miles K. “A Simplified Method for calculating the residence time and refining Intensity in a chip refiner” Paperi ja Puu, 73(9):852-857 (1991)”. In practice, at a given specific energy, this refining intensity varies with pulp consistency. Pulp consistency affects the pulp residence time which itself is inversely proportional to the refining intensity. In an increasing number of installations the consistency of the pulp, as measured or estimated in the blow line, is controlled by adjusting the flow rate of dilution water into the refiner. Such consistency control helps to maintain discharge consistency in the appropriate range for the good operation of the refiner. [0008] In large modern TMP refiners such as the Sunds CD 82 or some of the CD 76 refiners operating at very high refining consistency, there are up to three possible dilution flows that can be adjusted to change pulp consistency (as shown in FIG. 1 ): the infeed dilution or water added to the pulp or the chips before the refining zones, dilution water added to the flat zone of the refiner, and in some modern installations, the dilution water added to the conical zone. The purpose of adding dilution water in the conical zone is to reduce the occurrence of very high consistencies at the periphery of the plates and the associated plugging of the plates. [0009] Although pulp consistency varies and normally increases from the refiner inlet to the refiner discharge or blow line, the term refiner pulp consistency conventionally denotes the consistency of the pulp at the refiner discharge. This pulp consistency is either measured on manual samples, estimated using predictive models, or measured on-line using commercially available sensors. In an increasing number of installations the consistency of the pulp is controlled through a single control loop where the three mentioned flow dilutions (in-feed, flat zone and conical zone dilution) are manipulated according to an established ratio (as illustrated in FIG. 2 ). The single loop consistency control scheme of the prior art has many limitations; one of them is its effect on specific energy. Indeed small changes in in-feed dilution or in flat zone dilution required for consistency control have significant impact on refiner motor load and much more so than changes in conical zone dilution. Another limitation of the single loop consistency control scheme is that the same discharge consistency can be obtained with different distributions of dilution water flows among in-feed, flat zone and conical zone dilutions. On the other hand, refining intensity and pulp quality will be different at these different distributions, a source of problems if not properly recognized. This explains why a refining condition that is evaluated only in terms of specific energy and blow line consistency can produce very different pulp properties. [0010] This problem is partly addressed in U.S. Pat. No. 6,778,936 B2 where consistency profile is estimated using temperature sensors and a refining zone consistency is controlled either by manipulation of a dilution flow or by changing the refiner feed rate. However, in this previous U.S. patent no distinction has been made in the use of dilution water added before or during refining for consistency control. Only one consistency is being controlled. The objective there was to stabilize refining consistency not to adjust the target consistency for quality control. For example, there is no mention of the need to adjust refining consistency as a function of production rate to overcome loss of certain pulp properties. The same issue of quality loss due to production rate change is another limitation of the single loop control scheme. [0011] A very common problem in TMP installations is the loss of pulp quality at high production rate, Murton K. D. et al., “Production rate effect on TMP pulp quality and energy consumption. J. Pulp Paper Sci., 23(8): J411-J416, 1990”. It has been suggested that this loss of pulp strength at high production rate could be attributed to an increase in refining intensity associated with a decrease in pulp residence time. Indeed at high production rate the motor load has to increase to apply a sufficient amount of energy per tonne. At higher motor load, more steam is generated. The higher rate of steam generation results in a higher steam velocity at the same specific energy, and therefore a lower pulp residence time and a higher refining intensity. This problem can be partly offset by proper adjustment of refining consistency but there is no indication in the literature on how to achieve this compensation and how to adjust refining consistencies as a function of production rate. [0012] Although control of discharge consistency is common practice, current methods of control do not recognize the possibility to control independently refiner inlet consistency, which is solely dependant of the in-feed and flat zone dilution, production and consistency of the incoming stock; and the discharge consistency, and this creates severe limitations in the ability to change refining intensity. SUMMARY OF THE INVENTION [0013] References herein to conical disk refiners are to be understood as references to high consistency conical disk refiners as used in TMP (thermo-mechanical pulp) or CTMP (chemothermo-mechanical pulp) plants as primary, secondary, tertiary or reject refiners and operating at blow line consistencies greater than 30% . [0014] It is an object of this invention to provide an improved method of refining wood chips or pulp in a high consistency conical disc refiner. [0015] It is a particular object of this invention to control the consistency of wood pulp at the discharge outlet of a conical disc refiner to a target consistency. [0016] It is a further object of this invention to establish a pulp consistency for acceptable refining intensity in the refiner. [0017] It is a more specific object of the invention to maintain a target pulp consistency at discharge by a controlled addition of dilution water to the conical refining zone of a conical disc refiner. [0018] It is a further more specific object of the invention to establish a desired refining intensity in a conical disc refiner by controlled addition of dilution water to the refiner, upstream of the conical refining zone. [0019] In accordance with one aspect of the invention, there is provided a method of refining wood pulp comprising: i) providing a conical pulp refiner comprising a refiner housing having a pulp inlet and a pulp outlet with a refining zone therebetween, said refining zone comprising a flat upstream refining zone and a conical downstream refining zone, ii) feeding pulp through said pulp refiner from said pulp inlet to said pulp outlet and refining the pulp in said refining zone, and iii) adding a controlled amount of dilution water to said pulp upstream of said conical refining zone to establish a pulp consistency in said refining zone effective to maintain an acceptable refining intensity for refined pulp quality. [0020] In accordance with another aspect of the invention, there is provided a method of refining wood pulp comprising: i) providing a conical pulp refiner comprising a refiner housing having a pulp inlet and a pulp outlet with a refining zone therebetween, said refining zone comprising a flat upstream refining zone and a conical downstream refining zone, ii) feeding pulp through said pulp refiner from said pulp inlet to said pulp outlet at a selected production rate, and refining the pulp in said refining zone with discharge of refined pulp of a target consistency at said pulp outlet, and iii) adding a controlled amount of dilution water to said conical refining zone to maintain said target pulp consistency at said pulp outlet. [0021] In accordance with still another aspect of the invention, there is provided a method of refining wood pulp comprising: a) providing a conical pulp refiner comprising a refiner housing having a pulp inlet and a pulp outlet with a refining zone therebetween, said refining zone comprising a flat, upstream refining zone and a conical, downstream refining zone, b) feeding pulp through said pulp refiner from said pulp inlet to said pulp outlet at a selected production rate, and refining the pulp in said refining zone with discharge of refined pulp of a target consistency at said pulp outlet, c) adding a first controlled amount of dilution water to said pulp upstream of said conical refining zone, in response to loss of water in said pulp, to establish a pulp consistency effective to maintain an acceptable refining intensity for refined pulp quality, relative to said production rate in said refining zone, and d) adding a second controlled amount of dilution water to said conical refining zone, to maintain said target pulp consistency at said pulp outlet. [0022] In another aspect of the invention, there is provided a method of operating a conical disk refiner comprising: monitoring a pulp discharge consistency of the refiner, and controlling the discharge consistency to a desired value by adjustment of the flow rate of dilution water fed to a conical zone of the refiner. [0023] In still another aspect of the invention, there is provided a method of operating a conical disk refiner comprising: monitoring pulp consistency at an inlet of a refining zone of the refiner, and controlling the pulp consistency to a desired value by adjustment of at least one of: (i) flow rate of infeed dilution water to the refining zone, and (ii) flow rate of dilution water to a flat zone of the refining zone. [0024] A key element of this invention is adjusting refining intensity through changes in refining consistency profile and thus compensating for the detrimental effect of high production rate on pulp quality. [0025] Pulp consistency is controlled by two control loops in two locations rather than by one single control loop at one location as commonly practiced in the prior art. The two locations are: at the inlet of the refining zone (feed consistency) and at the refiner discharge (blow line consistency). The refiner discharge or blow line consistency is controlled independently of the inlet consistency by manipulation of dilution water flow rate within the refining zone (CD zone in conical disc refiners). [0026] Inlet consistency (or consistency at the beginning of the refining zone) is controlled by adjustment of the feed or flat zone dilution or both. [0027] Target inlet consistency is adjusted to achieve the desired refining intensity. In the prior practice with modern conical disc refiners, the dilution water is added in the conical refining zone thus presenting an additional variable to manipulate for the control of the refiner. [0028] In accordance with the invention, consistency at the inlet of the refiner can be increased while maintaining the discharge consistency (blow line consistency) constant. As a result the average refining consistency becomes higher while the consistency of the pulp at the periphery of the plates remains constant, thus avoiding plugging of the plates. The refiner motor load will also increase but can easily be brought back to its original value through an increase in the plate gaps. The result is an operation at the same motor load and specific energy but higher average refining consistency which means higher pulp residence time, and therefore lower refining intensity. It becomes then possible to adjust refining intensity at constant specific energy and in particular compensate for some of the deterioration of pulp quality associated with an operation at high production rate. Very important also is the fact that the consistency at the periphery of the plate can be maintained in an acceptable range while the average refining consistency is adjusted over a much wider range than was possible previously, and without addition of water in the refining zone. BRIEF DESCRIPTION OF THE DRAWINGS [0029] FIG. 1 is a simplified schematic diagram showing input variables and the two refining zones of a conical disc refiner. [0030] FIG. 2 is a schematic single control loop for adjusting discharge consistency according to the prior art. [0031] FIG. 3 is a schematic of two control loops to control the discharge consistency and the inlet consistency in accordance with the invention. [0032] FIG. 4 shows an example of two consistency profiles; profile ( 1 ), where all the dilution water is added at the in-feed. This resulted in a low inlet consistency. Profile ( 2 ) corresponds to a certain repartition of the total dilution flow between in-feed and conical zone. As can be seen, in profile ( 2 ), both the inlet consistency and the average refining consistency are higher while maintaining the same discharge consistency. This provides an increase of the residence time while maintaining constant specific energy and blow line consistency. DESCRIPTION OF PREFERRED EMBODIMENTS WITH REFERENCE TO THE DRAWINGS [0033] With further reference to FIG. 1 , a conical refiner 10 is illustrated schematically. Conical refiner 10 has a gap flat zone 12 , and a gap conical zone 14 . [0034] Conical zone 14 may be considered to comprise a multiplicity of zones of different radii, for example at radii r 1 , r and r 2 in FIG. 1 . Conical zone 14 has an angle of slope θ. [0035] Refiner 10 has an inlet 16 for chips or pulp to be refined, and dilution infeed line 18 , dilution flat zone line 20 and dilution conical zone line 22 for feed of dilution water to inlet 16 , flat zone 12 and conical zone 14 , respectively. Line 22 may have branch line 24 , 26 and 28 for feeding dilution water in line 22 to different parts of conical zone 14 . Thus, for example, branch line 24 feeds dilution water to an upstream or inlet end of conical zone 14 . [0036] With further reference to FIG. 2 , there is shown schematically a prior art refining system in which a refiner 30 has a dilution unit 32 and a controller 34 . [0037] The dilution unit 32 has a dilution infeed component 36 , a dilution flat zone component 38 and a dilution conical zone component 40 , all of which are activated together by controller 34 in response to information dispatched in line 42 from the refiner 30 , which information is typically an actual measurement of blow line consistency or an actual predicted blow line consistency. The controller 34 comprises the information on blow line consistency in line 42 with an established blow line consistency set point 44 and responds with a change in the dilution water flow rate as required, which change in dilution water is dispatched to all three components 36 , 38 and 40 , respectively in proportions α, β and Φ of the amount i.e. α+β+Φ=1. The proportions α, β, and Φ are typically determined from experience. [0038] In this prior art system, there is no provision for feeding dilution water independently to the different refining and feed zones of the refiner 30 . [0039] FIG. 3 illustrates a refining system of the invention in which a refiner 60 has independent controllers 62 and 64 . [0040] Controller 62 has a dilution conical zone line 66 for feed of dilution water to the conical refining zone of the refiner 60 in response to information dispatched into a line 68 from refiner 60 to controller 62 . [0041] This information is, for example, a measurement of actual blow line consistency, or an actual predicted blow line consistency of the operating refiner 60 . [0042] The controller 60 compares this information with a blow line consistency set point 70 , developed from the production rate 72 in accordance with a relationship equation 74 and responds with dispatch of dilution water, as required, to maintain the target blow line consistency (i.e. the blow line consistency set point 70 ). [0043] Controller 64 has a dilution line 76 having a dilution infeed branch line 78 and a dilution flat zone branch line 80 , for feed of dilution water to the infeed and flat zone of refiner 60 , in response to information dispatched in line 82 from refiner 60 . This information is, for example, the predicted inlet consistency of the operating refiner 60 . The controller 64 compares this information with an established inlet consistency set point 84 developed from the production rate 86 with a relationship equation 88 and responds with dispatch of dilution water, as required, to maintain the target inlet consistency (i.e. the inlet consistency set point 84 ). [0044] The relationship equation 74 is equation (11b) described hereinafter; and the relationship equation 88 is equation (11a) described hereinafter. The total dilution water dispatched by controller 64 is the sum of the in-feed dilution water and flat zone dilution water which are respective proportions α and β of the total dilution i.e. α+β=1. These proportions can be selected arbitrarily as long as individual dilution flow rates are sufficiently large to avoid plugging of the dilution orifices. DETAILED DESCRIPTION OF THE INVENTION [0045] This invention provides a method by which the discharge consistency of a conical disk refiner may be monitored using commercially available blow line consistency sensor or any model based method and is controlled to any desired value purely by adjustments of the dilution water flow to the conical zone of the refiner. [0046] The invention also provides a method by which the pulp consistency at the inlet of the refining zone may be predicted and monitored using conventional material balance equations and may be controlled to any desired value by adjustment of the infeed dilution flow rate, the flat zone dilution flow rate, or any combination of both of these flows. [0047] In these methods, the refiner inlet and discharge consistencies may be maintained to desired values by two independent consistency control loops such as is shown in FIG. 3 . [0048] The refiner inlet consistency target may be adjusted for the purpose of changing refining intensity, and in particular, the pulp residence time and therefore refining intensity may be adjusted without changing the consistency of the pulp at the refiner discharge. [0049] The inlet consistency target may be adjusted as a function of production rate in accordance with equations 11a) and b) hereinafter. [0050] The refining intensity may be adjusted as a function of production rate; and in particular, the refining intensity may be decreased with increasing production rate in order to compensate for losses in pulp quality associated with an operation at high production. [0051] Conical disc refiners (CD refiners) are becoming widely utilized in North American mechanical pulping processes. These refiners are made of two discs, one rotating and the other stationary. They also have two refining zones: the flat zone (FZ) and the conical zone (CZ). The chips or pulp are fed through the centre of the stator towards the centre plate of the rotor to be partially refined in the flat zone and then are driven by centrifugal forces into the conical zone where most of the refining takes place. The variables that can be adjusted in the refining flat zone are the throughput rate, the flat zone plate gap, the in-feed dilution, and the flat zone dilution. The manipulated variables in the refining conical zone at a given throughput rate, are conical zone gap and conical zone dilution. The flow of dilution water to the conical zone may be added at the beginning of the zone, somewhere in the middle of the zone, toward the end of the conical zone, or fed as a certain combination of all the above, FIG. ( 1 ). The variables that can be controlled are the refiner motor load, the specific energy, the refining intensity, the outlet consistency (blow line consistency), and the inlet consistency. With so many manipulated variables and so many interacting control variables, the CD refiner is a very complex system, difficult to operate, and to understand. [0052] The settings of the manipulated variables affects the residence time of the pulp, and therefore affects the quality of the pulp. Among the control variables that have a large impact on the pulp quality are the applied specific energy and the refining intensity. These two variables depend largely on the mentioned input variables but more specifically they depend on the throughput and on the refining consistency. [0053] The effect of the throughput on pulp quality was addressed in many articles, Murton K. D. et al., “Production rate effect on TMP pulp quality and energy consumption. J. Pulp Paper Sci., 23(8): J411-J416, 1990”. The throughput-pulp quality relationship is greatly dependant on whether the refiner is a flat disc or CD disc configuration. It can also depend on plate design and most importantly it depends on the throughput operating range. When the throughput operating range is very large and the objective of the pulp quality control is to meet a given freeness, a high increase of the throughput often results in a decrease in specific energy. This may be attributed to an increase in the generated steam which will increase the velocity of the pulp and therefore will result in a decrease of the pulp residence time. Some pulp properties will then be affected by the associated increase in refining intensity. To overcome this situation, an increase in the throughput should be accompanied by a decrease in the refining intensity in order to overcome the degradation of certain pulp properties that were lost. The easiest way to manipulate the refining intensity is by changing the refining consistency. However a much larger impact is obtained when modifying the refiner's rotational speed as described in the U.S. patent U.S. Pat. No. 6,336,602 (by K. Miles) and also in the article “Refining intensity and pulp quality in high consistency refining”, by K. Miles, Paperi ja Puu 72(5):508-514, 1990. The approach considered here is restricted to changing the refining intensity through changing the refining consistency as will be explained in the following. [0000] Consistency Profile [0054] Refining consistency was recognized in the article “The flow of pulp in chip Refiners” by K. Miles et al., J. Pulp Paper Sci., 16(2): J63-J72, 1990, as one of the very important variables that have a direct effect on pulp strength. Operating within the correct consistency range which is somewhat narrow is very critical, Strand, B. C. et al., “Effect of production rate on specific energy consumption in high consistency chip refining. Proc. Intl. Mechanical Pulp Conf., Oslo, (1993)”. Increasing consistency within acceptable limits yields an operation at wider plate gaps and helps to develop long fibers, maintain high bulk and avoid clashing plates. Operating outside that range tends to lead to less stable refiner operation. Low consistency yields narrow plate gaps and can result in fiber cutting and loss in strength properties. At very high consistency shivy pulp is produced and the so called dry fibre cutting can take place. [0055] Pulp consistency can be adjusted by changing dilution water flow rates. Some recent CD refiners are equipped with in-feed dilution, flat zone dilution and one or more conical zone dilutions. For such refiners, at the same throughput rate and at the same motor load, a discharge consistency target may be obtained with many different combinations of the dilution flows. That can result in a different consistency profile in the refining zones and different pulp strength properties. [0056] The consistency profile, for a flat disc refiner, can be predicted by the following formula developed in the article “Predicting the performance of a chip refiner. A constitutive approach”, by K. Miles et al., J. Pulp Paper Sci., 19(6): J268-J274, 1993. C o = 1 1 C i - ( r 0 2 - r in 2 ) ( r out 2 - r in 2 ) ⁢ E 0 L , ( 1 ) where L is the latent heat at the refiner inlet approximated to L≈2258kJ·kg −1 , r in is the inlet radius of the flat zone, r out is outlet radius of the flat zone and r o is the radius at any point in the flat zone at which consistency is being evaluated. E 0 is the specific energy and C i is the inlet consistency to the refiner defined as: C i = prod prod C p + dilution , ( 2 ) where C p is the consistency of the stock before entering the screw feeder to the refiner, prod is the throughput rate, dilution is the water added at the refiner inlet, and equal distribution of energy in the refining zone is assumed. This is the case for flat disc refiners. However, for CD refiners, it is observed that the two refining zones (flat zone and conical zone) do not distribute energy equally to the pulp. Moreover, most of the energy is being applied to the pulp in the conical zone. This is supported by the fact that, in many installations conical zone plates tend to wear more rapidly than the flat zone plates. Therefore, if the energy applied to the fibres in the flat zone is neglected, then the formula of equation (1) can be modified and used to estimate the consistency profile, C cz , for the CD refiner. The expression of that profile will depend on the location r c in the conical zone where the water is being added. Therefore, at the entrance to the conical zone, the consistency, C i1 , is given by: C i ⁢   ⁢ 1 = prod prod C p + dilution infeed + dilution FZ , ( 3 ) where dilution infeed is the in-feed dilution, and dilution FZ is the flat zone dilution. Then, at any given location, r, prior to r c , the consistency C cz is given by: C cz = 1 1 C i ⁢   ⁢ 1 - ( r 2 - r 1 2 r 2 2 - r 1 2 ) ⁢ ( E 0 L ) . ( 4 ) where C i1 is as defined in equation (3), r 1 is the outlet radius of the flat zone, r 2 is the outlet radius of the disc at the end of the conical zone, FIG. ( 1 ). [0057] For r=r c , the consistency C cz is given by: C cz = 1 1 C i ⁢   ⁢ 2 - ( r c 2 - r 1 2 r 2 2 - r 1 2 ) ⁢ ( E 0 L ) , ( 5 ) where C i2 is given by: C i ⁢   ⁢ 2 = prod prod C p + dilution infeed + dilution Fz + dilution CZ , ( 6 ) where dilution CZ is the conical zone dilution and C i2 is the consistency at the point where dilution occurs in the conical refining zone. [0058] And then, for any given r after r c , the consistency C cz is given by: C cz = 1 1 C i ⁢   ⁢ 2 - ( r 2 - r 1 2 r 2 2 - r 1 2 ) ⁢ ( E 0 L ) . ( 7 ) [0059] The discharge consistency or the blow line consistency, C BL , is obtained when r=r 2 , given by: C BL = 1 1 C i ⁢   ⁢ 2 - 0.0016 ⁢ E 0 . ( 8 ) [0060] This last equation shows that the same blow line consistency, C BL , is obtained by more than one possible way of combining in-feed dilution, flat zone dilution, and conical zone dilution. Each one of these combinations would result in a different consistency profile along the refining zones and therefore, different average refining consistency. To illustrate that, FIG. ( 4 ) shows an example of two consistency profiles; profile ( 1 ), where all the dilution water is added at the in-feed. This resulted in a low inlet consistency. Profile ( 2 ) corresponds to a certain repartition of the total dilution flow between in-feed, flat zone and conical zone. As can be seen, in profile ( 2 ), both the inlet consistency and the average refining consistency are higher while maintaining the same discharge consistency. This provides an increase of the residence time while maintaining constant specific energy and blow line consistency. [0061] For a given consistency profile the changes and the fluctuations of the C i2 , inlet consistency, affect the variations of the blow line consistency, C BL . In fact, taking the derivative of C BL , equation (8), with respect to C 12 leads to: ∂ C BL ∂ C i ⁢   ⁢ 2 = ( C BL C i ⁢   ⁢ 2 ) 2 . ( 9 ) [0062] This implies that ∂ C BL = ( C BL C i2 ) 2 ⁢ ∂ C i2 . ( 10 ) [0063] Knowing that C BL >C i2 , this equation shows that variations of C 12 are largely amplified and that they contribute tremendously to the variations of the discharge consistency. The higher the discharge consistency, the more important are these variations. This illustrates the need to control and stabilize inlet consistency variations. An independent control of discharge consistency using the dilution flow in the refining zone will also alleviate this problem. With such discharge consistency control, changes in inlet consistency are feasible. This feature can be exploited at high production rate as described in the following section. [0000] High Throughput Rate [0064] As mentioned before, when refining at high production rate, more steam is generated which reduces the pulp residence time, consequently affecting certain pulp strength properties. One way to overcome this problem is by reducing the refining intensity at high production rate. As explained in the article “Refining intensity and pulp quality in high consistency refining”, by K. Miles, Paperi ja Puu 72(5):508-514, 1990, this can be done using one of the two following ways. The most effective but also the most difficult one is by adjustments of the refiner rotational speed. The second method which is more practical for an existing operation, is by increasing refining consistency. For CD refiners, that can be accomplished by increasing C i1 while keeping the discharge consistency to an acceptable level that will be dependent on the production rate. C i1 is indicative of the inlet consistency to the refiner. Therefore the in-feed dilution and the flat zone dilution serve to adjust the consistency of the flow to the refiner while the conical zone dilution adjusts C cz (r=r c ), equation (5), which will result in adjustment of the discharge consistency, C BL and prevents the pulp from drying when C i1 is too high. [0065] To overcome the degradation of certain pulp properties at high production rate, the inlet consistencies, C i1 and the discharge consistency C BL should be adjusted to target values, which are adjusted as a function of production rate, such as: C i1 =α infeed prod+β infeed   (11a) C BL =α BL prod +β BL   (11b) [0066] Note, that C BL is function of C i1 and C cz (r=r c ). Furthermore, C BL can be adjusted by adjusting C cz (r=r c ) without affecting C i1 . Coefficients α infeed , β infeed , α BL , and, β BL are selected to ensure consistency targets within the stable operating range, to provide sufficient response of the motor load to changes in plate gap and a positive response of the motor load to increases in the in-feed and/or flat zone dilution flow rate. A situation where an increase in this dilution water flow rate leads to an increase in the motor load is considered abnormal and undesirable. An on-line estimation of process gains is implemented to detect abnormal or undesirable operating conditions. The production rate influences the specific energy to a given freeness and the pulp properties for conical disc refiners, Strand B. C. et al., “Effect of production rate on specific energy consumption in high consistency chip refining. Proc. Intl. Mechanical Pulp Conf., Oslo, 1993”. The consistency should be adjusted in order to allow increase of the specific energy that will compensate for this effect and maintain a stable pulp quality at various levels of production rate. The relationships, equation (11a) and (11b), between production rate and target inlet and discharge consistencies are determined experimentally. The coefficients in equation (11a) are determined first. Assuming that the operating production rate can change between a low production rate, denoted by Prod low , and a high production rate, denoted by Prod high and, assuming also that the refiner operates around its normal discharge consistency denoted, C BLoperation then, the determination of the coefficients, α infeed and β infeed , is carried out in two steps. First step consists in adjusting the production rate to Prod low , then in gradually increasing and decreasing the in-feed and/or flat zone dilution flow rate, i.e. in decreasing and an increasing the refiner inlet consistency C i1 , in order to cover the range of stable operating conditions. For each change in the dilution flow rate, C BL is adjusted to C BLoperation by adjusting dilution water in the conical zone. For each of these operating conditions, a pulp sample is taken from the blow line, is strength is measured and associated to C i1 . From this set of experiments, an optimal C i1 , denoted C i1optimal — low , that corresponds to the strongest pulp measured is chosen. Similar experiments are then carried out at high production, Prod high , to determine C i1optimal — high . During these two set experiments, at low and high production rate, the flat zone gap and the conical zone gap are maintained constant. The discharge consistency, C BL , is also maintained constant at C BL =C BLoperation , by adjusting C cz . Only inlet consistency through the in-feed and/or flat zone dilution flow rate are varied. The coefficients α infeed and β infeed are determined by: α infeed = C i ⁢   ⁢ 1 ⁢ optimal_high - C i ⁢   ⁢ 1 ⁢ optimal_low Prod high - Prod low ( 12 ⁢ a ) β infeed = C i ⁢   ⁢ 1 ⁢ optimal_low ⁢ Prod high - C i ⁢   ⁢ 1 ⁢ optimal_high ⁢ Prod low Prod high - Prod low ( 12 ⁢ b ) [0067] Note that the coefficient β infeed is always positive, implying that the inlet consistency has to increase when the production rate increases. [0068] Up to this point, it can be decided to keep the discharge consistency constant, C BL =C BLoperation for the entire production rate which would correspond to α BL =0 and β BL =C BLoperation in equation (11b). This is a sub-optimal solution that guarantees that for the same discharge consistency, C BL =C BLoperation , the inlet consistency would increase when the production rate increases. This would result in a decrease of the refining intensity and therefore an increase of the pulp residence time which is the very desired effect. [0069] In order to determine the optimal values for parameters α BL and β BL , the production rate and the inlet consistency are first adjusted respectively to Prod low and C i1optimal — low . Then the conical zone dilution flow rate is gradually increased and decreased, i.e. the discharge consistency C BL is decreased and increased, in order to cover a wide range of stable operating conditions. For each conical zone dilution change a pulp sample is taken from the blow line and its strength is measured and related to C BL . From these set of experiments, C BL optimal, denoted C BLoptimal — low , that would result in strongest pulp is chosen. Similar experiments are considered at Prod high and C i1 =C i1optimal — high to determine the optimal discharge consistency, C BLoptimal — high . Once the optimal discharge consistencies at high and low production rate are known then the coefficient α BL and β BL are given by: α BL = C BL ⁢   ⁢ optimal_high - C BL ⁢   ⁢ optimal_low Prod high - Prod low ( 13 ⁢ a ) β BL = C BL ⁢   ⁢ optimal_low ⁢ Prod high - C BL ⁢   ⁢ optimal_high ⁢ Prod low Prod high - Prod low ( 13 ⁢ b ) [0070] This approach avoids the current situation where the blow line consistency is the main parameter used in consistency control. Since it can be changed with either the in-feed, the flat zone or the conical zone dilution flows, the same blow line consistency can be achieved with very different refining zone consistency. Since the consistency affects the refining intensity and thus the pulp properties, unknown variations in the refining consistency could be avoided. This approach also allows an increase of the inlet consistency, C i1 , while maintaining the discharge consistency to an acceptable level or constant such that the average refining consistency becomes higher which would imply higher pulp residence time, and therefore lower refining intensity at the same specific energy. [0000] Motor Load Control [0071] When the refining intensity in the main part of the refining zone is maintained at an optimum level by adjusting the inlet consistencies, a stable specific energy can be achieved by controlling the motor load through adjustments of the plate gap. The target motor load is adjusted to obtain the desired specific energy at various production rates, as should normally be done. This is only possible if the consistencies are high enough to ensure a significant response in motor load to a change in plate gap. [0072] The current situation is that both plate gap and consistency are generally used to control motor load. This way, both the refining intensity and the refining energy may be changed at the same time and it is difficult to predict what the consequences will be for the pulp properties in any given situation. The new approach described here gives a better control of the pulp properties based on the current understanding of how the refining intensity and the specific energy affect the pulp properties, Miles K. B. et al. “Wood characteristics and energy consumption in refiner pulps. J. Pulp Paper Sci. 21: J383-J389, 1995”. When each factor is controlled separately, it becomes easier to correct pulp quality problems in a systematic way during the daily operation.
A method is proposed for improving pulp quality at high production rates on conical disc refiners. It permits a reduction in refining intensity by enabling fibre residence time to increase by increasing consistency, while avoiding the problem of plate plugging normally associated with high discharge consistency. In practice, inlet consistency is increased by the in-feed dilution, flat zone dilution or both, but without allowing the discharge consistency to rise. Instead, the discharge consistency is controlled at a fixed optimum value by the addition of dilution water within the conical zone. The result is that residence time is increased, and refining intensity decreased, by raising the consistency in the inner region of the refining zone, while avoiding the plate plugging caused by excessive consistency in the outer region of the refining zone.
3
BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a drilling device and process, and is more particularly concerned with an hydraulically controlled drilling rig which is designed to be mounted onto various types of vehicles, and the process of using the same. 2. Description of the Prior Art Hydraulically controlled drilling rigs are generally well known in the art, and have traditionally utilized similar structures within the various types of drills. The Acker Company of Scranton, Pa., has manufactured several various types of drill rigs, which rigs exemplify features that have not been significantly modified since the early part of this century. For example, the Acker ADII typifies one of the most commonly used drill rigs, employing features that are quite well known. This type of drill rig incorporates a derrick which supports two, parallel hydraulic cylinder feed assemblies. These feed assemblies raise and lower an exposed drill head by simultaneously applying force in the same direction to both the left side and right side of a support frame, which is integrally attached to the drill head. Because two feed assemblies are used in this manner, the drill head could be subjected to a turning force, perpendicular to the direction the drill head is moving, if the support frame was not incorporated to react the force provided by the two cylinders. Using two feed assemblies instead of one adds to the overall weight of the drill rig. This undesirable effect is augmented by the fact that the support frame for the rotary assembly is also required. Further, this twin feed assembly design, which incorporates redundant structure, necessitates a substantial support structure that requires a heavy, sliding base for movement onto on and off-hole positions. This structure requires that the drill rig be mounted on a large vehicle, which limits the rig's versatility. This drill rig additionally is designed to be used in vertical applications, only. Another critical limitation of this type of drill rig is that this design requires a heavy, square shaft, or Kelly bar, which acts as a drive shaft. This shaft is exposed and, therefore, is a safety hazard, and further adds to the weight of the device. Further, because the drill head slides on the outside of the feed cylinders, the drill rods are contained between the base supports for the feed cylinders. When the head is in a raised position, the distance between the base supports limits the size of the auger which can be driven by the device. Additionally, because of the arrangement of the hydraulic support jacks, the control panel for the rig cannot be placed along the rear of the rig at a safe distance from the rotating elements. The Acker Core-Max drill rig utilizes a large, folding derrick which is raised and lowered by two double-acting hydraulic cylinders. The drive head is releasably mounted to a movable carriage that is slidably engaged with a mast mounted within the derrick. The feed cylinder is also mounted within the derrick in parallel, eccentric relationship to the drill rods, rather in direct, concentric alignment. Since the feed cylinder is not concentric with the drill rods, a bending moment results with respect to the force applied to the moving carriage. This results in less efficient application of force, and wear on the carriage and mast assemblies. This arrangement also requires a large amount of structural steel and, therefore, is a comparatively heavy rig with numerous parts. The rotation elements of the rotary assembly are also mostly exposed, providing a safety hazard. The Acker Mountaineer drill rig incorporates many of the same features utilized by both devices previously discussed, including the dual, parallel feed assemblies, the large derrick, exposed rotating elements, control panel position close to the moving parts, and the heavy sliding base. Consequently, this design also has many of the same limitations referenced above. The Acker Soil Sentry drill rig is an example of a relatively lightweight drill rig, however, it includes limitations such as feed assembly eccentric to the drill rods, support frame required to react the force applied by the feed assembly, exposed rotating parts, and limited performance characteristics which limit its applications. SUMMARY OF THE INVENTION Briefly described, the present invention includes a link assembly adapted to be mounted onto a vehicle. The link assembly is hydraulically actuated and carries a mast assembly in slidable engagement. The link assembly moves the mast assembly in selected positions, from a horizontal position in parallel relationship to the bed of the vehicle, to a vertical position, normal thereto. The link assembly is further adapted to move the mast assembly in on-hole and off-hole positions. The hydraulic control system is designed to be capable of automatically maintaining the mast assembly in a predetermined angled position while it is being moved on and off hole. The mast assembly fully encloses the feed assembly, which effectively feeds the drill rods during the drilling operation, and also encloses substantially all of the rotary assembly which turns the drill rods. The enclosure of these elements improves the safety of the present invention over that of the prior drill rigs. The feed assembly is positioned so as to be concentrically aligned with the drill rods. All principal moving elements of the drill rig are powered hydraulically by pumps, mechanically linked to a power take off on the vehicle. The hydraulic circuit is especially designed with selection, speed and directional limitation means to provide for safe operation of the device. In operation, actuation of the link assembly properly positions the mast assembly for drilling. During the drilling operation, the entire mast assembly moves relative to its slidable engagement with the link assembly. When the mast assembly reaches its lowermost position during drilling, it is then raised, and another section of drill rod is added. With a few exceptions, the entire operation is controlled from a single control panel. The invention is thus designed with a minimum of structural elements, so as to be relatively lightweight to permit it to be mounted onto a relatively small vehicle, for increased mobility and economy. The present invention, however, retains the performance characteristics of the larger drill rigs of the prior art. Accordingly, it is an object of the present invention to provide a drilling apparatus and method for using the same which overcomes the above-referenced limitations of the prior art. Another object of the present invention is to provide a drilling apparatus which is simple in structure, inexpensive to manufacture, durable in structure, and efficient in operation. Another object of the present invention is to provide a drilling apparatus which is lightweight and capable of being supported by a relatively small vehicle. Another object of the present invention is to provide a drilling apparatus which is designed for safe operation. Another object of the present invention is to provide a drilling apparatus in which the feed cylinder assembly is concentric with the drill rods. Another object of the present invention is to provide a drilling apparatus which utilizes a sliding mast assembly. Another object of the present invention is to provide a drilling apparatus in which the rotary assembly is substantially enclosed within the mast assembly. Another object of the present invention is to provide a drilling apparatus in which the rotary assembly hydraulic circuit and cathead hydraulic circuit have incorporated therein speed and directional limitations. Another object of the present invention is to provide a drilling apparatus in which the rotation of the rotary assembly and cathead is immediately stopped when a shutdown circuit is energized. Another object of the present invention is to provide a drilling apparatus in which the mast assembly can be automatically maintained in a vertical or other preselected angled position, regardless of its horizontal position relative to the bed of the support vehicle. Another object of the present invention is to provide a drilling apparatus capable of drilling at selected, incremantal angles or drilling vertically when the support vehicle is positioned on a grade. Another object of the present invention is to provide a drilling apparatus which can be used for both auger drilling and core drilling. Another object of the present invention is to provide a drilling apparatus which incorporates a control panel which groups valve controls for limiting functions. Another object of the present invention is to provide a drilling apparatus which can be operated safely and efficiently by two individuals. Another object of the present invention is to provide a drilling apparatus which is capable of selectively delivering both high speed and/or high torque to the drilling rods. Another object of the present invention is to provide a drilling apparatus which incorporates a hydraulic control circuit designed to lock all cylinders in place in the event of loss of power. Another object of the present invention is to provide a drilling apparatus which utilizes a hydraulic system which is sealed and pressurized to eliminate the induction of contaminates. Another object of the present invention is to provide a drilling apparatus which utilizes outriggers to stabilize the support vehicle during drilling operations. Another object of the present invention is to provide a drilling apparatus, the hydraulically driven components of which are powered by hydraulic pumps mechanically linked to a power take-off assembly mounted on the support vehicle. Another object of the present invention is to provide a drilling apparatus which is capable of immediately stopping the rotation of either the rotary assembly or the cathead when an electrical circuit is activated. Another object of the present invention is to provide a drilling apparatus which includes a regenerative hydraulic circuit to operate the feed assembly. Another object of the present invention is to provide a drilling apparatus which includes means to override the regenerative hydraulic circuit operating the feed assembly. Other objects, features and advantages of the present invention will become apparent from the following description when taken in conjunction with the following drawings, wherein like reference characters designate corresponding parts throughout the several views. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a perspective view of the drilling apparatus in a transport position; FIG. 2 is a perspective view of the link assembly with the mast assembly in a horizontal position. FIG. 3 is an enlarged view of the attachment of the feed assembly to the mast link. FIGS. 4A and 4B are a longitudinal cross-sectional views of the mast assembly. FIGS. 5a, 5b, and 5c are schematic representations of the hydraulic control circuit. FIG. 6 is a side elevational view of the drilling apparatus in an on-hole position, with the apparatus in an off-hole position shown in phantom lines. DESCRIPTION OF THE PREFERRED EMBODIMENTS Referring now in detail of the embodiments chosen for the purpose of illustrating the present invention, numeral 10 denotes generally a conventional truck 10 having cab 11 and flat bed 12. Drilling apparatus 9 is shown mounted onto flat bed 12 of truck 10. Securely mounted onto the rear portion of bed 12 are spaced, upstanding brackets 13. Each of spaced brackets 13 are preferably mounted onto bed 12 equidistantly from the side of bed 12 to which the respective bracket is closest. Pivotally mounted in brackets 13 by pins 14 is support member or off-hole link 15. As best shown in FIGS. 1 and 2, off-hole link 15 includes upstanding, tapered rear panel 16 and identical side panels 17. Securely attached to side panels 17 and extending toward cab 11 are triangular support brackets 18. Support brackets 18 are angled inwardly, as shown in FIG. 2, and securely support journal member 19, having lower holes 27 and upper holes 36. The top portion of side walls 17 terminate in identical upstanding brackets 20. Off-hole link 16 is actuated about pins 14 by off-hole cylinder assembly 21. Cylinder assembly 21 is a short stroke hydraulic piston and cylinder assembly including cylinder 22 having trunnions 23, and rod 24 having trunnions 25. As shown in FIG. 2, trunnions 23 are pivotally mounted in upstanding parallel spaced brackets 26, which brackets 26 are secured to bed 12. At the other end of cylinder assembly 21, trunnions 25 are received in the lower portion of journal member 19 through lower holes 27. Cylinder assembly 21 is preferably a short stroke hydraulic cylinder having a stroke limited to approximately 8 inches. Pivotally attached to upper bracket 20 of off-hole link 16 is support member or mast link 28. Mast link 28 is symmetrical and includes identical side walls 29 and triangular supports 30 which terminate at brackets 31, as shown in FIG. 2. Pins 32 join mast link 28 to upstanding brackets 20, so that mast link 28 pivots about pins 32. Mast link cylinder assembly 33 is pivotally connected by trunnions 34 of cylinder 35 to bracket 31. Pivotally connected to journal member 19 by trunnions 37 being received in holes 36 is rod 38 of cylinder assembly 33. Mast assembly 39 slidably engages mast link 28 through dovetail runners 40 and dovetail clamps 41. Two identical dovetail runners 40 are secured to mast frame 42, as depicted in FIG. 2. These dovetail runners 40, communicate with dove tail clamps 41, so that mast assembly 39 is fixed to mast link 28. The engagement of runners 40 and clamps 41 permit mast assembly 39 to slide along mast link 28 but do not permit mast assembly 39 to tilt or fall away from mast link 28. Mast frame 42 is preferably formed of box steel and is square shaped in cross-section and defines channel 43 within its back side 44, as depicted in FIG. 2. One dovetail runner 40 is mounted onto mast frame 42 on each side of and parallel to channel 43. Mast link 28 includes cradle 45 which extends into channel 43 of mast frame 42. Mast assembly 39 is depicted in FIG. 4 in longitudinal cross-section. Mounted entirely within mast frame 42 is feed cylinder assembly 46. Cylinder assembly 46 is securely mounted to plate 48 which is attached within mast frame 42 at its upper end 49. Cylinder 47 and rod 50 extend within frame 42, as shown in FIGS. 4A and 4B. The free end 51 of rod 50 includes boss 52 with flattened surface or wrench flat 53. Shaft 54 extends from and is concentric with boss 52 and is of a smaller diameter than boss 52, thus forming shoulder 55. Shaft 54 is externally threaded and is received within hole 55A of cradle 45, until shoulder 55 abuts cradle 45. Shaft 54 is long enough to extend through cradle 45 and is secured to cradle 45 with lock washer 56 and nut 57. Mounted within the lower end 58 of mast frame 42 is rotary assembly 59. Rotary assembly 59 includes spacer plate 60 which is secured to variable-displacement motor 61. Linked to motor 61 is two-speed gear box 62. Linked to gear boss 62 is planetary gear 63 which is a fixed ratio planetary gear. A tapered key shaft with a threaded nut (not shown) extends from planetary gear 63. Attached to the tapered key shaft is spindle adapter 64 with spindle 65 extending from the bottom portion 58 of frame 42. The variable speed motor 61, gear box 62, planetary shift 63 and spindle adapter 64 are all mechanically linked, the structure of which linkage is well known in the art and is not further described herein. Cover plate 66 encloses the bottom end 58 of frame 42. Cover plate 66 is provided with a centrally disposed hole so that only spindle 65 protrudes therefrom. Therefore, with the exception of spindle 65, rotary assembly 59 is completely enclosed within mast frame 42. This is an important safety feature as in the present invention there are much fewer moving parts associated with the rotary assembly for operators to come in contact with. Since motor 61 is centrally mounted onto spacer plate 60, spacer plate 60 assists in maintaining rotary assembly 59 in a central longitudinal alignment within mast frame 42. Rotary assembly 59 is securely fixed to mast frame 42 by bolts 67 extending through mounting plate 68 which is securely fixed to rotary assembly 59. Hydraulic winch 69 is secured to the upper end 49 of mast frame 42, as depicted in FIG. 4, so that when mast frame 42 is in its vertical position, winch 59 faces away from truck 10, as shown in FIG. 6. Mounted on the side of plate 48, away from cylinder 47, is hydraulic fluid counter-balance valve 70. Counter-balance valve 70 permits hydraulic fluid to exit from cylinder 47 above piston 50, normally only when that hydraulic circuit is powered, when a sufficient external force is applied to mast assembly 39 or in case of extreme thermal conditions, as will be discussed hereinafter. Also mounted within mast frame 42 at its upper end 49 is electronic level 71, which functions in conjunction with the hydraulic control circuit 100 to automatically maintain the mast assembly 39 at a preselected angle, as will be discussed hereinafter. Cover plate 72 is mounted on the top end 49 of frame 42 to fully enclose frame 42. Capstan or cathead drum 73 is journaled on a shaft extending from hydraulically powered motor 74, which is securely mounted to off-hole link 18, as shown in FIG. 2. The entire drill rig assembly is powered principally by hydraulic pumps, cylinders and motors, and incorporates a hydraulic circuit as depicted in schematic form on FIGS. 5a, 5b, and 5c, which figures align according to their respective match lines. The hydraulic circuit incorporates a combination of known elements which are connected by conventional hydraulic lines are well known to those skilled in the art, and so are not further described herein. The valves and other control elements contained in the hydraulic circuit are also conventional elements well known in the art, however, their particular arrangement within the present invention is designed to increase the safety and efficiency of the present invention. Referring to FIGS. 5a, 5b, and 5c, the hydraulic circuit, denoted generally on the three figures and numeral 100, includes main pumps 101 and 102 and charge pump 103 which collectively provide hydraulic pressure within the entire circuit 100. Pumps 101, 102 and 103 are driven mechanically by a power take-off gear box (not shown) incorporated with the transmission (not shown) of truck 10. Such power take-offs and the engine controls and the engine protection devices associated therewith are generally well known by those skilled in the art, and are not further discussed herein. Main pump 101 and charge pump 103 are responsible for providing hydraulic pressure and flow to the circuit which includes the rotary assembly 59 and the hydraulic cathead motor 74. Charge pump 103 is a constant displacement pump which maintains a positive pressure at the suction port of main pump 101. Charge pump 103 provides a constant flow of fluid through the fluid conditioning circuit 105, and also provide the pressure for the remote control of displacement of rotary motor 61, gear box 62, and valve 106 and also controls flow rate and direction of fluid from pump 101. Pump 101 is connected to relief valve 104 which feeds fluid in the circuit to a fluid reservoir or tank T which is included generally in the hydraulic fluid conditioning circuit denoted generally as numeral 105. Hydraulic conditioning circuit 105 contains conventional elements of hydraulic conditioning including radiators, hydraulic fluid filters, the hydraulic fluid reservoir or tank T, and the necessary relief valves and check valves associated therewith. These elements are widely known in the art and understood by those skilled in the art and, therefore, will not be further discussed herein. When pumps 101 and 103 are operating, the hydraulic circuit 100a is pressurized, preferably to 230 p.s.i. to 5,000 p.s.i. Manual control valve 106 is a directional control valve which directs fluid at 230 p.s.i. pressure to shuttle valve 107. Shuttle valve 107 is a pilot operated three-way valve which allows pressurized fluid to operate either the rotary assembly 59, the cathead motor 74, or neither of these elements. Therefore, neither of the rotary assembly 59 or the cathead motor 74 can operate simultaneously. This is a safety feature which is built into the device to prevent the operator from operating the rotary assembly 59 and watching the drilling operation while the cathead 73 is in a hoisting operation. In the past, operators have been injured while both of these operations were being conducted simultaneously. With the present invention, this would be impossible. When the rotary assembly 59 is selected for rotation by valve 106, pressurized hydraulic fluid is directed through shuttle valve 107 to variable displacement motor 61. As discussed earlier, variable displacement motor 61 is mechanically connected to gear box 62. Manual control valve 108 directs the pilot pressure to variable displacement motor 61 in order to control the displacement of motor 61. Motor 61 is preset to 100% displacement or approximately 40% displacement. Manual control valve 109, sends pilot pressure to gear box 62 in order to shift gears from a high range of 1 to 1, to a low range of 3.46 to 1. Manual valve 108 shifts the displacement in variable displacement motor 61 from either 100% displacement to 40% displacement. Since the variable displacement motor 61 and two-speed gear box 62 are in series, the rotary assembly 59 is capable of turning at four different speed ranges. Each range is controlled by varying the speed with pump displacement. Manual control valve 106 is a dual pressure regulating valve with the following functions: incrementally increase fluid flow to the rotary assembly 59 in a full clockwise direction, reverse the rotary assembly 59 in a counterclockwise direction, incrementally increase fluid flow to the cathead motor in a forward direction, or stop all fluid flow to the rotary assembly 59 or the cathead motor 74. Manual valve 106 also can be operated to actuate shuttle valve 107 to direct fluid to cathead motor 74 which drives cathead drum in a counterclockwise direction, only. Ball valve 110 prevents hydraulic fluid from entering motor 74 and driving cathead drum in the opposite direction. This is a safety feature which eliminates the obvious danger of turning the cathead drum in the opposite direction. The control panel (not shown) limits the travel of manual valve 106 in one direction which allows the rotary assembly to be energized in the reverse direction at only approximately 15% of the full speed of the forward direction. This is an additional safety feature. In case of an emergency situation associated with the rotary assembly 59 or the cathead 73, solenoid shuttle valve 111 is provided as an emergency stop switch to immediately stop the rotation of either rotary assembly 59 or cathead 73. Hydraulic pressure from pump 103 is reduced in pressure regulator 112, for pilot pressure to solenoid directional control valve 111. When solenoid shuttle valve 111 is deenergized, hydraulic pressure is delivered to servo valve 113 which delivers pressure to swash plates in pump 101 to drive the swash plate to 0 degrees. Fluid flow from pump 101 is immediately stopped in the rotary assembly 59 and/or cathead 73, depending which is being utilized at the time, is immediately stopped from turning. Also associated with pump 101 are the necessary relief valves 114 and ball valves 115 to assist in the maintenance of the proper pressure and directional flow, respectfully in the hydraulic circuit. Their function is well known to those skilled in the art. Mechanically driven pump 102 provides hydraulic pressure for the remaining hydraulic components of the drilling assembly. The hydraulic circuit for feed assembly 46 and water pump 119 is denoted generally by numeral 100b. Pressure compensated valve 116 monitors the pressure in the circuit and controls pressure to the swash plate control which is integral to conventional hydraulic pump 102, to ensure that the circuit is maintained at a proper pressure, preferably approximately 2,500 p s.i. Relief valve 117 acts as a backup to pressure compensated valve 116 to ensure that the circuit is not over pressurized. Relief valve is preferably set at approximately 2,600. Should the circuit for some reason pressurize over this limit, relief valve will open and direct fluid to tank T in fluid conditioning circuit 105. Fluid flow control 118 is preset to limit the fluid flow entering the feed cylinder assembly 46 and hydraulically powered water pump 119. Preferably fluid flow control valve 118 is set to permit approximately 11 gallons per minute of hydraulic fluid flow through valve 118. Manually operated detent control valve 120 allows fluid to enter the hydraulic lines servicing feed assembly 46. Adjustable relief valve 121 selectively, incrementally controls the pressure applied by feed assembly 46, commonly referred to as bit pressure. Adjustable flow control valve 122 controls the speed or rate of downward feed assembly travel. As shown in FIG. 5b, fluid passes through adjustable flow control valve 122 through ball valve 123 and into cylinder 47 below piston 47a. As fluid enters cylinder 47 from flow control 122, piston rod 50 is retracted into cylinder 47 and mast frame 42 is then forced downwardly. Counterbalance valve 70 is also actuated when fluid flows through adjustable flow control valve 122. Counterbalance valve 70 is a conventional spring biased counterbalance valve of a type which is well known in the art, and is designed to prevent hydraulic fluid from exiting cylinder 47 above piston 47A, unless the counterbalance valve is powered. Practically, this ensures that feed cylinder assembly 46, and therefore mast assembly 39, is retained in a fixed position until control valve 122 is actuated. This is a safety feature which prevents the mast frame 42 from dropping upon loss of power. When counterbalance valve 70 is powered by fluid passing through ball valve 123, fluid is allowed to bleed from cylinder 47 above piston 47A and back to tank T in circuit 105. Temporary override valve 124 is provided to allow adjustable flow control valve 122 to be manually bypassed, thereby allowing relatively increased flow through ball valve 123 and into cylinder 47 in order to permit the mast frame 42 to be dropped quickly. This feature is desirable when, for example, new sections of drill rods are being added, in order to save time. Manually operated detent valve 120 can also be actuated to bypass adjustable relief valve 121, in order to direct fluid through counterbalance valve 70 and into cylinder 47 above piston 47A. When fluid is directed into cylinder 47 above piston 47a, rod 50 is extended from cylinder 47, and mast frame 42 is raised. As fluid so enters cylinder 47, piston 47A is pushed downwardly and fluid below piston 47A is pushed out of cylinder 47 through ball valve 125 and join the fluid flowing from fluid flow control valve 118. This is, thus, a regenerative type circuit which is well known in the art, and thus increases the flow rate entering cylinder 47 above piston 47A relative to the situation when fluid is directed into cylinder 47 below piston 47A. Because fluid flow control valve 118 is preferably set to allow 11 gallons per minute (g.p.m.) of fluid flow into the circuit, this regenerative circuit allows 22 g.p.m. to enter cylinder 47 above piston 47a. Since the area of the bore of cylinder 47A is twice the area of piston rod 47, directing twice the amount of fluid into cylinder 47 above piston 47A results in the feed cylinder assembly 46 raising and lowering the mast frame 42 at approximately the same rate. Manually operated detent valve 126 is provided to circumvent the above-described regenerative circuit. When valve 126 is actuated, and valve 120 is directing fluid into cylinder 47 above piston 47A, the fluid exiting cylinder 47 below piston 47A is directed through valve 126 at approximately zero resistance, back to tank T in circuit 105. Therefore, only approximately 11 g.p.m. of fluid will flow into cylinder 47 above piston 47A. Because the area of the bore of cylinder 47 is approximately twice the area of piston rod 50, rod 50 will be forced out of cylinder 47 at only half of its normal, full rate and at twice the normal force. This is useful when, for instance, the operator needs to raise the mast assembly 39 at a greater force and slower speed in order to pull drill rods which are stuck. Pump 116 also delivers pressurized fluid through flow control valve 127 to manually operated control valve 128. Valve 128 is a detent valve in two positions, stop and run, and a spring biased valve for a reverse flush function. When valve 128 is actuated, pressurized fluid is directed through water pump motor 119 and is circulated back through ball valve 129 to fluid conditioning circuit 105. Pump 116 also directs pressurized fluid through fixed flow control valve 130 to a conventional multisectional, directional control valve block 131. This control valve block is a conventional, off the shelf product, such as that manufactured by the Gresen Manufacturing Company, and will not be further discussed herein, except that the block includes five manually controlled spring biased control valves. These valves control the fluid flow to the hydraulic circuit denoted generally with reference numeral 100C. Control valve 131A controls the mast cylinder assembly 46, control valve 131B controls the off-hole cylinder assembly 21, control valve 131C controls the winch 69, control valve 131D controls left outrigger jack assembly 139 and control valve 131E controls right outrigger jack assembly 142. Fluid from manual control valve 131A is selectively directed through counterbalance valve 134 into mast cylinder 35. Counterbalance valve 134 is a conventional counterbalance valve, similar to counterbalance valve 70, and functions to prevent fluid from exiting mast cylinder 35 both above and below piston 35A, unless counterbalance valve 134 is powered. This is a safety feature which normally prevents mast assembly 39 from changing positions unless manually operated control valve 131A is actuated, or unless automatically powered by double solenoid valve 135. Double solenoid valve 135 is electronically linked to electronic level or plumb bob sensor 71 contained in mast frame 42. Electronic level 71 is a conventional electronic plumb bob level which sends an electric signal when the level is placed in a preselected position. When electrical switch 136 is biased, energizing electronic level 71, electronic level 71 will automatically send a signal to the appropriate side of double servo valve 135, which in turn hydraulically actuates the counterbalance valve 134 which allows fluid to flow through counterbalance valve 134 into mast cylinder 35 above or below piston 35A as needed to orient mast assembly 39 in the proper position. Thus, mast assembly 39 is actuated in one direction or the other, until mast assembly 39 reaches a preselected angle programmed into electronic level 71. This provides an automatic override circuit in order to automatically position and maintain mast assembly 39 in an appropriate angle. Those skilled in the art understand that electronic switch 136 can be eliminated and the entire automatic positioning system can be made fully automatic. Conventional multisectional direction control valve 131 is designed so that valves 131A, 131B, 131C, 131D, and 131E are arranged in parallel so that the function controlled by these valves can be conducted simultaneously. Manual control valve 131B controls off-hole cylinder assembly 21 by directing fluid to cylinder 22 through double check valve 137. Manually operated control valve 131C operates the winch motor 69A to turn winch 69 in either direction. The winch motor and brake for winch 69 are not shown, however, the winch motor is integral with the winch brake and is a conventional, hydraulically powered winch. Manually operated control valve 131D operates left outrigger cylinder assembly 140, and manually operated control valve 131E operates right outrigger cylinder assembly 142. Those skilled in the art will understand that the hydraulic control system described herein can be modified in numerous ways using conventional hydraulic and/or electronic components. The control circuit described herein is described for the purpose of illustration, only, and other circuits can perform satisfactorily if those circuits incorporate appropriate components for the safety features disclosed herein. Control box 138 houses the various gauges and mechanically operated controls discussed above. This control box is positioned as far away from the mast assembly as possible, while still providing the operator with an unobstructed view of the drilling operations. All functions of the assembly 9 are controlled by the manually operated valves contained in control box 138 except for the second emergency shut-down switch, the power take-off engaging lever, and certain motor circuit valves. The vehicle 10 is stabilized by outrigger assembly 139 which consists of left outrigger cylinder assembly 140 left outrigger jack 141, right outrigger cylinder assembly 142, and right outrigger jack 143, as shown in FIG. 1. These outrigger jacks 141 and 142 are conventional stabilizing jacks, but provide the advantage of more stability over vertically disposed stabilizing jacks normally utilized in drilling apparatus of the prior art. The various components relating to the drill rods and the water hose connections from the drill rods to the water pump 119A are not part of the present invention and are, therefore, not depicted. Those skilled in the art understand how these components are utilized with drilling apparatus 9. In operation, the vehicle 10 is positioned so that mast assembly 39 can be raised over a selected location for drilling. Outrigger assembly 139 is then actuated to stabilize vehicle 10. The operator then actuates mechanically operated control valve 131A to raise mast cylinder into a vertical position, as is depicted in FIG. 6. When the mast assembly 39 is in a nearly vertical position, the operator will bias electronic switch 136 which sends electronic signals to electronic level 71, which in turn controls double servo valve 135. Double servo valve 135 then maintains mast assembly 39, in a predetermined angled position, as described above. The mast assembly 39 depicted in phantom lines in an off-hole position in FIG. 6, can then be actuated by manually operated control valve 131B to move mast assembly 39 horizontally, onto an on-hole position as depicted in FIG. 6. During this procedure, the mast assembly 39 is maintained in the predetermined, angled position by electronic level 71, as described above. The mast can then be lowered for the attachment of drill rods (not shown) and the drilling operation can commence. It will be obvious to those skilled in the art that many variations may be made in the embodiments here chosen for the purpose of illustrating the present invention, and full result may be had to the doctrine of equivalents without departing from the scope of the present invention, as defined by the appended claims.
A drill rig assembly adapted to be mounted on a vehicle and having a pivotal link assembly mounted to the vehicle. Attached in slidable relationship to the link assembly is a mast assembly containing feed means and rotary means fully enclosed within the mast assembly. An electronic level within the mast assembly automatically maintains the mast assembly in a predetermined, angular position. The drill rig assembly is capable of drilling either vertically or at selected, incremental angles. The drill rig assembly is designed to be safe in operation and lightweight, while providing performance characteristics of larger drill rigs.
4
This is a division of application Ser. No. 07/560,384, filed Jul. 31, 1990, now U.S. Pat. No. 5,065,225. TECHNICAL FIELD The present invention relates generally to semiconductor devices, in particular, to complex semiconductor devices called integrated circuits, and more particularly to tunneling diffusion barriers for local interconnect and polysilicon high impedance devices for use in integrated circuits. BACKGROUND OF THE INVENTION There are a large number and variety of basic fabrication steps used in the production of modern semiconductor devices. In order to fabricate a circuit consisting of thousands of components on a single silicon substrate, the movement of electrons is critical to the proper functioning of each device according to specified design rules. The production of electrons and associated holes enhancing the electrical characteristics of any given semiconductor device fabricated on the surface of a silicon wafer can be further enhanced by introducing controlled quantities of impurities or doping material. Doping elements such as phosphorus, arsenic, and antimony create n-type substrates while doping elements such as boron, indium, gallium, or aluminum create p-type substrates. Free electrons will move from a n-type substrate to a p-type substrate created by the doping process. A limitation in the electrical characteristics of a device arises when doped polysilicon is deposited by chemical vapor deposition over a layer of silicon substrate. This process is used in forming a silicon gate. While the electrical devices created from the deposition of the doped polysilicon such as high impedance devices or local interconnects allow for conduction of electrons the dopant material from the polysilicon layer will migrate into an adjoining layer. Any migration of dopant material will ultimately change the electrical characteristics of the devices such as the resistance value of the high impedance device, determined by the dimension of the high impedance device, and the dopant level within the region creating the high impedance device. The fabrication of one type of semiconductor device, an electrical conductive contact and associated interconnect layers is described in U.S. Pat. application Ser. No. 502,526 filed Mar. 30, 1990 to Nicholls et. al abandoned and entitled "Semiconductor Devices and Fabrication Thereof." A method of fabricating an insulating layer of silicon dioxide as part of an overall process of fabricating conductive or semiconductive layers to form a contact is described in U.S. Pat. No. 4,877,483 issued Oct. 31, 1989 to Bergemont et. al. Another limitation arises where a layer of aluminum is deposited by chemical vapor deposition over a silicon substrate. Junction spiking results when aluminum atoms pass through the underlying silicon substrate into the layer beneath the silicon substrate. This junction spiking causes a hole and disrupts the junction between the silicon substrate and the layer beneath the silicon substrate resulting in a short circuit condition. A further limitation arises where a dielectric or insulator exists between a doped polysilicon or aluminum layer and the underlying silicon substrate. A dielectric may provide enough resistance to prevent tunneling of electrons through the dielectric to or from the doped polysilicon or aluminum layer and into or out of the underlying silicon substrate. Tunneling of electrons does occur, however, where the dielectric is thin enough to allow current to flow across the dielectric. Tunneling currents are discussed in the IEEE Transaction On Electron Devices, Vol. 37, No. 8, August 1990 in an article entitled "Thickness Limitation of SiO 2 Gate Dielectrics for MOS ULSI"; in S. Pantelides, Physics Of SiO 2 And Its Interfaces, (1978) in an article by M. Av-Ron, et. al at pp. 47-51 entitled "The Nature Of Electron Tunneling In SiO 2 "; and, in R. Muller, T. Kamis, Device Electronics For Integrated Circuits, Section 3.4 "Junction Breakdown" (1977). The electrical properties of silicon nitride as taught in the present invention are discussed in general in the 1987 ECS Symposium Proceeding entitled "Silicon Nitride And Silicon Dioxide Thin Insulating Films" in an article entitled "Electrical Properties Of Thin LPCVD Si 3 N 4 Films On Mono- And Polycrystalline Silicon." SUMMARY OF THE INVENTION In accordance with the present invention, a semiconductor device is disclosed in which the device is an electrical element covered over a thin dielectric layer which is further disposed over a substrate layer allowing for tunneling of electrons through the dielectric layer into and out of the electrical element while simultaneously preventing the diffusion of dopant material through the dielectric layer into and out of the electrical element. A feature of the invention is a thin dielectric layer deposited between the conductive electrical element layer of the tunneling of electrons while simultaneously preventing the diffusion of the dopant material between the conductive layer and the substrate. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic sectional view illustrating a portion of an integrated circuit device of the present invention at one stage in a process for making the devices. FIG. 2 is a schematic sectional view illustrating a succeeding step in the process. FIG. 3 is a schematic sectional view illustrating a succeeding step in the process. FIG. 4 is a schematic sectional view illustrating a succeeding step in the process. FIG. 5 is a schematic sectional view illustrating an alternative succeeding step in the process. FIG. 6 is a schematic sectional view illustrating a succeeding step in the process. FIG. 7 is a schematic sectional view illustrating a succeeding step in the process. FIG. 8 is a schematic sectional view illustrating a succeeding step in the process. FIG. 9 is a schematic sectional view illustrating a succeeding step in the process. FIG. 10 is a schematic sectional view illustrating a portion of an integrated circuit device of the present invention at one stage in a process for making the devices. FIG. 11 is a schematic sectional view illustrating a succeeding step in the process. FIG. 12 is a schematic sectional view illustrating a succeeding step in the process. FIG. 13 is a schematic sectional view illustrating a succeeding step in the process. DETAILED DESCRIPTION OF THE INVENTION Referring to FIG. 1, there is shown a cross-section of a portion of an integrated circuit device of the present invention, indicated generally by the reference numeral 10. The device 10 includes a substrate layer 9 as known in the art. The device comprises an isolation field oxide layer 12 positioned below and adjacent to gate 14. Gate 14 comprises two layers, a silicide layer 16 superimposed on a conductive layer 18. A sidewall oxide spacer 15 is formed as known in the art adjacent to the silicide layer 16 and conductive layer 18. A silicon dioxide layer 20 is deposited on top surface 17 of gate 14. Photoresist pattern 22 is deposited on the silicon dioxide layer 20 using standard photoresist techniques, after which the unmasked portions of layer 22 are etched away using an etchant which selectively attacks the oxide. Referring to FIG. 2, the etching process thereby removes the exposed silicon dioxide portion between the remaining layer 20 as shown. Following the etching step, an ion implant step is performed in a known manner, if necessary, to protect the integrity of the etched opening. Referring to FIG. 3, the photoresist layer 22 is removed using known techniques thereby leaving a contact opening 24 and remaining silicon dioxide layer 20. Referring to FIG. 4, a silicon nitride layer 26 is deposited on silicon dioxide layer 20 and silicide layer 16 at contact opening 24 by chemical vapor deposition by heating dichlorosilane and ammonia at approximately 700° C. to produce silicon nitride, hydrogen, and hydrogen chloride gas having a thickness range of between 5 Angstroms and 50 Angstroms. At the thickness range of about 5 Angstroms to about 50 Angstroms, the silicon nitride layer 26 will allow tunneling of electrons through layer 26. The current flow through layer 26 is a function of the area of the silicon nitride layer 26, the thickness of the silicon nitride layer 26, the activation energy required for the electrons to cross the silicon nitride layer 26 at surface interface 17 of gate 14, and the probability that each electron from silicide layer 16 of gate 14 actually crosses surface 17 and tunnels through the silicon nitride layer 26. While the silicon nitride layer 26 permits tunneling of electrons through the silicon nitride layer 26, the silicon nitride layer 26 continues to perform as a barrier prohibiting diffusion of dopant material through the layer from silicide layer 16 of gate 14. The silicon nitride layer 26 is, however, thin enough to allow electrical currents to flow through the layer to or from adjacent layers. Referring to FIG. 5, to form a local interconnect, polysilicon layer 28 is deposited on silicon nitride layer 26. Polysilicon is deposited by known chemical vapor deposition methods by heating silane at around 600° C., releasing hydrogen gas from silane and depositing silicon. Polysilicon layer 28 is then doped with an appropriate p-type dopant by known diffusion or implantation methods. The next step is to deposit a silicide layer 30 on polysilicon layer 28 by known deposition methods. The silicon nitride layer 26 prohibits the dopant material in local interconnect film 28 from diffusing through the silicon nitride layer 26 into silicide layer 16 of gate 14. Referring to FIG. 6, a second silicon dioxide layer 32 is thermally grown on top of silicide layer 30. A second photoresist pattern 34 is deposited on the second silicon dioxide layer 32, using standard photoresist techniques, after which the unmasked portions of layer 34 are etched away using an etchant which selectively attacks oxide. Referring to FIG. 7, the etching process performed in a known manner thereby removes the second photoresist layer 34 and second silicon dioxide layer portions between the remaining layer 32 as shown thereby leaving an opening 36. Following the etching step, an ion implant step is performed in a known manner, if necessary, to protect the integrity of the etched opening. Referring to FIG. 8, the photoresist layer 34 is next removed using known techniques. Referring to FIG. 9, a second silicon nitride layer 38 is deposited on the second silicon dioxide layer 32 and the silicide layer 30 at opening 36 by chemical vapor deposition in a known manner having a thickness range of about 5 Angstroms to about 50 Angstroms. At the specified thickness range, the silicon nitride layer 38 will allow tunneling of electrons through layer 38. A second polysilicon layer 40 is deposited on second silicon nitride layer 38. The second polysilicon layer 40 is doped with an appropriate p-type dopant or lightly doped n-type dopant by known diffusion methods to form a high impedance device with a known resistance value. The second silicon nitride layer 38, acting as a barrier, prohibits the dopant material in second polysilicon layer 40 from diffusing through the second silicon nitride layer 38 into the silicide layer 30. This barrier prevents alteration of the high impedance device value through dopant diffusion into or out of the high impedance device. Referring to FIG. 10, there is shown a cross-section of a portion of an integrated circuit device of the present invention, indicated generally by the reference numeral 42. The device 42 comprises an isolation field oxide layer 44 and substrate layer 60 as known in the art. The device 42 further comprises an active region 46 in substrate layer 60 adjacent to isolation field oxide layer 44. The silicon dioxide layer 48 is deposited on isolation field oxide layer 44 and active region 46. Photoresist pattern 50 is deposited on the silicon dioxide layer 48 using standard photoresist techniques, after which the unmasked portions of layer 50 are etched away using an etchant which selectively attackes oxide. Referring to FIG. 11, the etching process thereby removes the exposed silicon dioxide portions between the remaining layer 48 as shown. Referring to FIG. 12, the photoresist layer 50 is removed using known techniques thereby leaving a contact opening 52 and remaining silicon dioxide layer 48. Referring to FIG. 13, a silicon nitride layer 54 is deposited on an active region 46 at contact opening 52 and the remaining silicon dioxide layer 48 by chemical vapor deposition having a thickness range of between 5 Angstroms and 50 Angstroms. An interconnect film 56 comprise aluminum is deposited on silicon nitride layer 54. Aluminum is deposited by various known methods. Silicon nitride layer 54 prevents junction spiking from aluminum interconnect film 56 through the silicon nitride layer 54, across active region 46 and into a substrate layer 60 underlying active region 46; thereby preventing a short circuit across the junction of active region 46 and substrate layer 60. The various fabrication methods such as etching, chemical vapor deposition, ion implantation, and photoresist techniques are well known in the art. The following references may be referred to for detailed descriptions of fabrication methods: W. Maly, Atlas of IC Technologies, An Introduction To VLSI Process, (1987); J.A. Cunningham, CMOS Technology, (1987); P. Van Sant, Microchip Fabrication, A Practical Guide To Semiconductor Processing, (2nd ed. 1990).
A semiconductor device is described in which a conductive layer overlaps a dielectric layer forming a composite electrical device deposited over selected portions of a semiconductor substrate chemically isolating the conductive layer portion of the composite electrical device from the substrate, thereby preventing diffusion of dopant material through the dielectric layer into and out of the conductive layer while simultaneously allowing for tunneling of electrons through the dielectric layer to and from the conductive layer and the semiconductor substrate.
7
This is a continuation of application Ser. No. 664,811, filed on Oct. 25, 1984. FIELD OF THE INVENTION The invention relates to a gearlike tool and, more particularly, to a gearlike tool having tooth flanks which are coated with hard-material grains, for example diamond grains, preferably for the purpose of dressing abrasive gearlike precision tools for machining the tooth flanks of gears, for which purpose the inventive tool is moved into meshing tooth engagement with the precision machining too. The term "gearlike" is intended to include "worm-shaped" or the like. BACKGROUND OF THE INVENTION Gearlike tools are known for precision machining of gears and have hard-material grains embedded in a binding agent or have a toothed metallic base member with tooth flanks which have hard-material grains embedded in a binding agent. The hard-material grains can, for example, be grains of cubic boronnitride (CBN). These known tools are exposed to a certain amount of wear during use and must be dressed from time to time in order to again obtain their original profile. The dressing tools which are used for this dressing include, as a rule, a toothed metallic base member with a coating of diamond grains which are embedded in a binding agent. The dressing tools often have dimensions substantially identical to those of the gears which are machined by the precision machining tools which are to be dressed, because with this a retooling of the machine for the dressing operation is not needed; the dressing tools are fed to the machine in place of the gears and are removed after the dressing. Particularly in the case of tooth systems with a small modulus, producing an even coating with the diamond grains at times creates considerable difficulties, since a galvanic or other treatment in the relatively narrow gaps between teeth often yields unsatisfactory results. The cause for this is to be seen in the closely side-by-side tooth flanks on each side of each tooth gap, through which the diamond grains are deflected during the coating operation. Due to this, a basic purpose of the invention is to provide a gearlike dressing tool of the above-mentioned type, in which the described difficulties during coating do not occur. In addition to the attainment of this purpose, a further purpose, insofar as it is possible at the same time, is to make possible the solution to yet another problem which occurs in such dressing tools, namely, to reduce the enormous amount of time required for grinding the tooth flanks of the dressing tool. In the interest of the work result during precision machining, the precision machining tool must be true to form within small tolerances. This, however, can be achieved only with a very exact dressing tool. The dressing tools which are coated with the diamond grains must therefore be ground with a diamond grinding disk. The material thereby removed from the dressing tool per unit time is naturally very small. SUMMARY OF THE INVENTION For attaining the purpose of the invention, a dressing tool is provided on which the gap between two successive teeth is wider than in a comparable tool which in other respects has similar tooth system dimensions. With the widening of the tooth gaps, applying the coating with diamond grains is easier in the case of tooth systems with a small modulus, and in many cases an even coating without any problems is possible. Pointed and also asymmetrical teeth can also be advantageous on the inventive tool. They are known in different applications, but these applications do not offer any suggestion for the invention. An asymmetrical dressing tool can sometimes be utilized only in one direction of rotation, and thus can dress both the left or right flanks of a tool only if it is turned over at some point. Another advantageous development involves the removal of at least each second tooth. For a continuous numbering of the teeth, reference is made to removal of the teeth 2, 4, 6, 8, etc.; the teeth 2, 3, 5, 6, 8, 9, etc.; or the teeth 2, 3, 4, 6, 7, 8, 10, 11, 12, etc. When every second tooth is removed, then the tooth gaps on the dressing tool are approximately three times as wide as in the case of a comparable tool which otherwise has identical tooth system dimensions. With this, the known problems during coating no longer exist. At the same time, the time which is needed for grinding the dressing tool is reduced by approximately 50%, as is also the case in the dressing tool with asymmetrical teeth. If more teeth are removed, the grinding time is reduced even more. The extra time needed during dressing, due to the reduced number of teeth, is not particularly significant. If, due to an odd number of teeth, in particular a prime number, no regular arrangement of the remaining teeth is possible, and it is advantageous if two of the teeth are spaced only sufficiently far apart so that on one only the left and on the other one only the right flank remains. With this, it is achieved that the number of left and right flanks on the tool is the same, which is advantageous for assuring a uniform amount of material removal from the workpiece per unit of time. In an extreme case, the dressing tool may have only one tooth, which can be manufactured as a separate part and then be inserted into a recess or groove in the base member. The last-mentioned design has the advantage that only a small part of the tool must be coated, and thus the devices needed for coating can be kept small. For holding the inserted tooth, a T-shaped, dovetail or other profile on the tooth, which profiles are known from other toothing tools, is held in a corresponding shape groove in the base member. Certain dressing tools according to the invention can only be used on those machines in which the precision machining tool which is to be dressed is drivingly coupled in some manner with the workpiece which is to be machined by it, for example through guide wheels or an electric shaft. In order to make them also usable for machines with a simple drive effected solely by the meshing teeth of the precision machining tool and the workpiece, it is advantageous if toothed guide wheels can be mounted as narrow toothed disks next to the actual dressing tool. An arrangement for effecting rotary adjustment of the guide wheels permits the left flank of one guide wheel to be aligned with the left flank of the dressing tool and the right flank of the the dressing tool. When the base member, in the region of the removed teeth, is axially set back, the guide wheels can be designed to have only the teeth which correspond with the teeth removed from the dressing tool which, viewed in a peripheral direction, directly follow the teeth of the dressing tool. In this embodiment, the guide wheels do not need any additional axial space next to the actual dressing too, but are fully integrated therein. BRIEF DESCRIPTION OF THE DRAWINGS The invention will be described in detail hereinafter in connection with several exemplary embodiments which are illustrated in FIGS. 1 to 11. In the drawings: FIG. 1 is a diagrammatic side view of a conventional machining tool and of a dressing tool according to the invention, the teeth of the dressing tool having one flank moved; FIGS. 2, 3, 4 and 5 are views similar to FIG. 1 which respectively illustrate four alternative embodiments of the inventive dressing tool of FIG. 1; FIGS. 6 and 7 are respectively a sectional side view and a sectional end view of a further alternative embodiment of the dressing tool of FIG. 1 which has an inserted tooth; FIGS. 8 and 9 are respectively a sectional end view and a sectional side view of a further embodiment of the dressing tool of FIG. 1 which as two guide wheels; and FIGS. 10 and 11 are sectional views similar to FIGS. 8 and 9 which illustrate yet another embodiment of the dressing tool according to FIG. 1. DETAILED DESCRIPTION In a dressing tool 1, teeth 2 and 2' on a metallic base member 3 are designed sufficiently narrow so that the left 4 and the right 5 flanks thereof meet approximately at the addendum circle K (FIG. 1). Thus, the teeth 2 and 2' are pointed teeth. A coating 6 of diamond grains can thus be applied more evenly because of the greater distance between the teeth 2 and 2', namely the wider tooth gaps 7, than in a dressing tool 1' (FIG. 1) with otherwise identical tooth system dimensions. Only some of the teeth of the precision machining tool 9 which is to be dressed with the dressing tool are illustrated. Another way to create wider tooth gaps is illustrated in FIG. 2. Here, the left flanks 14 of all teeth 12 of a toothed metallic base member 13 are removed and only the right flanks 15 are provided with the coating 6 of diamond grains. The dressing tool 11 can thus cooperate only with the flanks 18 of the precision working tool 9 which is to be dressed. For dressing the opposite flanks 19 thereof, the dressing tool 11 must be turned over. This position is indicated by the reference numeral 11'. A still different way to create wider tooth gaps is shown in FIG. 3. Each second tooth 22' is removed from a toothed metallic base member 23 of a dressing tool 21. Through this, the tooth gaps 27 which are provided between the remaining teeth 22 have, compared with the normal tooth arrangement, approximately three times the normal width. The applying of the coating 6 onto the totally exposed tooth flanks 24 and 25 can here be carried out without any problem. It is also possible to remove still more teeth, so that for example only each third, fourth, etc. tooth 22 remains on the metallic base member. Through this, the time which is needed for the grinding of the diamond coating can be very substantially lowered. If the number of teeth does not permit an even distribution of the remaining teeth 22, it is also possible to provide two half teeth 28, 29 (FIG. 4). Namely, it is to be avoided that the dressing tool has a different number of left 24 and right 25 tooth flanks. The removal of teeth can be carried until, in the extreme case, only one tooth is provided on the dressing tool. For this, FIG. 5 and FIGS. 6 and 7 respectively illustrate two examples. A dressing tool 31 (FIG. 5) includes a metallic base member 33 which has only one tooth 32. The flanks 34 and 35 of the tooth 32 are provided with the coating 6 of diamond grains. A precision machining tool which is to be dressed is again identified with reference numeral 9. In place of the base member 33, which is only slightly complicated to manufacture and which is provided with one tooth, it is also possible, as illustrated in FIGS. 6 and 7, to secure a single separate tooth 42 (or if desired several separate teeth) on a base member 43. The fastening can occur by means of a profile on the tooth, for example a T-profile 48 or a differently shaped profile, which is received in a correspondingly formed groove in the base member 43 and is held against axial movement by lateral disks 49 removably secured to each axial end of the member 43. For coating, only the single tooth 42 must be treated, and only the side surfaces and the profile 48 thereon must be covered, while in the other above-described exemplary embodiments the entire dressing tool 1, 11, 21 or 31 will be coated unless large surface areas are covered in order to avoid applying the expensive coating on places where it is not needed. The thus-obtained dressing tool 41 can be utilized in the same manner as the aforedescribed embodiments. The dressing tools 21, 31 and 41 can, however, only be utilized on those machines in which a positive drive between the tool and workpiece spindles exists, since the removed or missing teeth prevent a meshing drive of the dressing tool by the precision machining tool being dressed. Two exemplary embodiments are respectively shown in FIGS. 8 and 9 and FIGS. 10 and 11, which are dressing tools 51 and 61 similar to the tools 21, 31, 41 but with which a meshing drive is possible. The dressing tool 51 is similar in its design, namely, in the arrangement of its coated teeth 22, with the dressing tool 21. Additionally, axially thin toothed disks 58 and 59 are provided which can be adjusted rotationally with respect to one another and with respect to the base member 23. With this, it is possible to adjust for example the left flanks 54 of the disk 58 to be congruent with the coated flanks 25 of the base member 23. This adjustability permits greater manufacturing tolerances on the toothed disks 58 and 59 which serve as guide wheels, and furthermore permits a positional readjusting of the disks 58 and 59 when their teeth 52 have become worn as a result of rolling on the abrasive flanks of the precision machining tool which is to be dressed. The axial width of the dressing tool, which width has been increased by the thickness of the disks 58 and 59, can in some cases result in problems, namely when the guide wheels do not satisfactorily engage the gaps between the teeth of the precision machining tool which is to be dressed. In these cases, the tool 61 according to FIGS. 10 and 11 is to be preferred. The dressing tool 61 also has a tooth arrangement similar to that of the dressing tool 21, but the base member, which is here identified with reference numeral 63, is proivded with lateral recesses, into which toothed disks 68 and 69 which serve as guide wheels are placed. The disks 68 and 69 have only those teeth 62, which correspond with the teeth 22' removed from the base member. The axially outer surfaces of the disks 68 and 69 are approximately flush with those of the teeth 22, so that the width of the dressing tool 61 is, in spite of the guide wheels, no greater than the width of the dressing tool 21. The figures are all somewhat diagrammatic, and are primarily supposed to show as clearly as possible the important parts of the invention. Although particular preferred embodiments of the invention have been disclosed in detail for illustrative purposes, it will be recognized that variations or modifications of the disclosed apparatus, including the rearrangement of parts, lie within the scope of the present invention.
A gearlike tool for dressing abrasive, gearlike, tools used for precision machining gear workpieces has tooth flanks which are coated with diamond grains. The gaps between teeth of the base member which has the diamond coating are enlarged, for example by removing teeth, in order to make the application of the coating easier. In order to assure a fully meshing engagement, the dressing tool can be combined with uncoated guide wheels which have teeth which meshingly engage the teeth of the precision machining tool.
1
FIELD [0001] The embodiments hereby disclosed relate generally to drywall tools, and more specifically to hand-held compound containers used to hold compound in drywall construction. BACKGROUND [0002] Compound containers, also known as mud pans, are available in various sizes, and are used to provide workers with easy access to the compound necessary for drywall construction projects. Workers generally carry a compound container in one hand, and a taping knife in the other. In this way, a worker can use the knife both to remove compound from the container and to mix the compound as necessary. SUMMARY [0003] Some embodiments of a compound container can be constructed to include a hand support member attached to a bottom of the compound container, allowing a user's hand to be extended between the hand support member and the bottom of the compound container and thereby enhancing a holding of the compound container by the user's hand. For example, the hand support member can be an expandable hand support member. When not in use, the hand support member is in a relaxed configuration without being under tension. When in use, the user's hand is extended between the hand support member and the bottom of the container body, and the hand support member can be stretched to an expanded configuration, applying an elastic force on the user's hand and thereby enhancing a holding of the compound container by the user's hand. It is to be understood that the hand support member can be made of materials other than elastic material. In such configuration, the hand support member can include buttons to allow the length of the hand support member to be adjusted to secure the user's hand to the bottom of the container body. [0004] Moreover, the compound container can be constructed with a tool holder including a friction holding tab for holding a taping knife. The friction holding tab can be formed as a part of a side stand located at an end of the compound container such that the taping knife can be secured at the end of the compound container when not in use. [0005] Moreover, the compound container can be constructed with two side stands, allowing the compound container to stand on a flat surface regardless whether the container body has a flat bottom or rounded bottom. The side stands can be spaced away from the bottom of the container body, allowing the compound container to be stackable for economical point of purchase display. [0006] Moreover, the compound container can be constructed with a rounded corner on one side of its bottom and an edged corner on the other side of its bottom. The rounded corner allows easy gripping of the bottom of the container body by the user's hand, while the edged corner allowing a blade of a taping knife to be maintained at the corner when the taping knife is placed inside a spaced defined by the container body. [0007] In particular embodiments, a compound container includes a container body having a side wall and a bottom wall, an interior space defined by the side wall and the end wall, an opening defined by an upper edge of the side wall; and an elongated hand support member having a first attachment section and a second attachment section for attaching the hand support member to a bottom surface of the bottom wall. The hand support member is positioned generally parallel to the opening defined by the upper edge of the side wall. [0008] In some embodiments, a compound container kit includes a container body having a side wall and a bottom wall; an interior space defined by the side wall and the end wall; an opening defined by an upper edge of the side wall; an elongated hand support member having a first attachment section and a second attachment section for attaching the hand support member to a bottom surface of the bottom wall; and instructions for attaching the hand support member to the bottom surface of the bottom wall. The bottom wall is configured generally parallel to the opening defined by the upper edge of the side wall. [0009] Other embodiments may include a method of using a compound container. The compound container in the method includes a container body having a side wall and a bottom wall; an opening defined by an upper edge of the side wall; and an elongated hand support member having a first attachment section and a second attachment section for attaching the hand support member to a bottom surface of the bottom wall. The method includes extending extend a hand between the hand support member and the bottom surface of the bottom wall; and holding on an outer surface of the side wall to manipulate the orientation of the compound container. [0010] The details of one or more embodiments of the invention are set forth in the accompanying drawings and the description below. Other features, objects and advantages of the invention will be apparent from the description and drawings, and from the claims. BRIEF DESCRIPTION OF THE DRAWINGS [0011] The following is a brief explanation of embodiments herein using drawings and embodiments: [0012] FIG. 1 is a bottom perspective view of a compound container with an edged bottom design with a hand support member of FIG. 4 attached. [0013] FIG. 2 is a sectional view of the compound container of FIG. 1 . [0014] FIG. 3 is a perspective view of the compound container of FIG. 1 . [0015] FIG. 4 is a perspective view of a hand support member attachable to a compound container. [0016] FIG. 5 is a sectional view of the compound container of FIG. 1 without a hand support member attached. [0017] FIG. 6 is a sectional view of a compound container with a rounded bottom design on one of the two long edges with the hand support member of FIG. 4 attached. [0018] FIG. 7 is a further sectional view of the compound container of FIG. 1 . [0019] FIG. 8 is a sectional view of a compound container with a rounded bottom design on both of the two long edges without a hand support member attached. [0020] FIG. 9 is a perspective view of two compound containers of FIG. 1 stacked together. DETAILED DESCRIPTION [0021] Embodiments disclosed herein relate to a compound container including an elongated body and a hand support member. The elongated body has an opening, two long edge sides opposing each other, two short edge sides opposing each other, and a bottom. The elongated body of the compound container may have a flat rectangular bottom with two edged corners along the long edges, or it may have a rounded bottom with an edge corner and a rounded corner along the long edges, or it may have a rounded bottom with two rounded corners along the long edges. The hand support member is attachable to the bottom of the compound container, allowing a user's hand to extend between the hand support member and the bottom of the compound container, and thereby enhancing the holding of the compound container by the user's hand. The length of the hand support member can be adjustable. [0022] As shown in FIGS. 1-3 , a compound container 100 includes an elongated body 1 (referring to FIG. 3 ) used to hold drywall compound. The elongated body includes an opening 2 (referring to FIG. 3 ), two long edge sides 4 , 5 opposing each other, two short edge sides 3 , 6 opposing each other, and a bottom 7 . The opening 2 and the bottom 7 are both defined by the long edge sides 4 , 5 and the short edge sides 3 , 6 . The opening 2 may be in a rectangular shape. The bottom 7 may be flat in a rectangular shape. An area of the bottom 7 may be smaller than an area defined by the periphery of the opening 2 . As shown in FIG. 7 , the long edge sides 4 , 5 may be inwardly inclined when extending toward the bottom 7 , forming two edged corners 401 , 501 . As shown in FIG. 2 , the short edge sides 3 , 6 may be straight, inwardly inclined when extending toward the bottom 7 , forming two edged corners. A compound container with a flat, rectangular bottom may be more stable when placed on a flat surface. [0023] Alternatively, in another embodiment as shown in FIG. 6 , a rounded bottom design may be used. A rounded bottom 701 has an edged corner 402 and a rounded corner 502 connecting to the long edge sides 4 , 5 respectively along the long edges of the rounded bottom 701 . The rounded corner 502 allows the elongated body 1 to have a more ergonomic design with more grips. Thus one may hold the compound container more easily and more comfortably for an extend period of time. In the meantime, the edged corner 402 allows a paint tool, such as a taping knife blade, to stay at the edged corner 402 . At the same time the rounded bottom may allow a taping knife blade to be placed along the long edge side 4 connected with the edged corner 402 without flipping over when in use. [0024] Yet in another embodiment as shown in FIG. 8 , the elongated body 1 may have a rounded bottom 702 . The rounded bottom 702 has two rounded corners 403 , 503 connecting to the long edge sides 4 , 5 along the long edges of the rounded bottom 702 , providing more grips and comfort when one is holding the compound container. [0025] As shown in FIG. 5 , two holding members 15 , 16 are placed on the bottom surface of the bottom 7 , in generally parallel with each other along two short edges 301 , 601 of the bottom 7 and near the two short edges 301 , 601 of the bottom 7 respectively. The holding members 15 , 16 allow a hand support member 40 to be attached to the bottom 7 of the compound container 100 . [0026] In an embodiment as shown in FIG. 1 , the holding members 15 , 16 may be in a curved shape, curving away from the short edges 301 , 601 of the bottom 7 . The curved design allows more connection space with a hand support member 40 , while avoiding the hand support member 40 intruding out of the short edges 301 , 601 of the bottom 7 and adversely affecting the stackability of the compound container. Two retaining members 17 , 18 may be placed in the center of each of the holding members 15 , 16 , in order to further secure the hand support member 40 using screws. It is understood that other fastening meanings may be utilized to secure the hand support member. [0027] FIG. 4 shows a hand support member 40 including an elongate body 19 . It is to be understood that the hand support member 40 can be configured in various configurations, as long as it has an elongate body and can be used to support the back of the user's hand when the hand holds on long edge sides 4 , 5 or bottom 7 of the compound container 100 . The hand support member 40 can have a strap shape or a string shape, and in some embodiments, a plurality hand support members 40 can be attached to the bottom surface of the bottom 7 of the compound container 100 . [0028] The hand support member 40 may also include two holding members 20 , 21 to both ends of the hand support member 40 engageable with the corresponding holding members 15 , 16 . The holding members 20 , 21 may be curved away from the short edges 301 , 601 of the bottom 7 . The curved design allows more connection space with the body 1 , while avoiding the hand support member 40 intruding out of the short edges 301 , 601 of the bottom 7 and adversely affecting the stackability of the compound container. Each of the holding members 20 , 21 may have a cavity 201 , 211 , respectively, in a shape which tightly fits the above disclosed holding members 15 , 16 respectively, allowing the holding members 20 , 21 to be able to be plugged in and fixed securely. Two retaining members 22 , 23 may be placed in the center of each of the holding members 20 , 21 , further securing the hand support member 40 on to the bottom 7 using screws. The elongate body 19 has an expansion rib 191 in the center of the elongate body 19 . The expansion rib 191 may use stretchable materials, connecting the two body pieces 19 A, 19 B together. When a hand is placed between the bottom 7 and the elongate body 19 , the two body pieces 19 A, 19 B may bend outwardly, and the expansion rib 191 may be stretched. Thus the expansion rib 191 allows the length of the elongate body 19 to be adjustable to the size of one's hand holding the compound container. In another embodiment, the elongate body may include buttons and buttonholes allowing the length of the elongate body 19 to be adjustable. It is to be understood that the length of the elongate body 19 can be adjusted by other means as long as the intended function is attained. [0029] As shown in FIGS. 1 and 2 , the hand support member 40 is attached to the bottom surface of the bottom 7 of the compound container 100 . When the hand support member 40 is attached to the bottom surface of the bottom 7 of the compound container 100 , the two holding members 20 , 21 tightly hold the two holding members 15 , 16 . To further secure the attachment between the hand support member 40 and the compound container 100 , screws may be placed through the retaining members 17 , 18 of the holding members 15 , 16 and the retaining members 22 , 23 of the holding members 20 or 21 . [0030] When the hand support member 40 is attached to the compound container 100 , the ends of the two holding members 20 , 21 are in a position not extending beyond the two short edges 301 , 601 of the bottom 7 respectively, such that the total length of the hand support member 40 including the two holding members 20 , 21 is no longer than the length of the long edge of the bottom 7 , allowing the compound containers stackable while the hand support members are attached. [0031] As further shown in FIG. 7 , when the hand support member 40 is attached to the bottom surface of the bottom 7 , a distance between the elongate body 19 and the bottom surface of the bottom 7 of the compound container 100 is large enough for holding the compound container 100 comfortably using the hand support member 40 ; however the length added to the bottom surface of the bottom 7 by attaching the hand support member 40 is within a range of distance within which the stackability of the compound containers is not affected by attaching the hand support member 40 . [0032] In another embodiment as shown in FIGS. 1 to 3 , the compound container 100 may also include two side stands 8 , 9 extending from two opposing edges of the opening 2 . The vertical length of the side stands 8 , 9 may be longer than the vertical length from the edges of the opening 2 to the lowest point of the hand support member 40 when the hand support member 40 is attached to the compound container 100 , allowing the side stands 8 , 9 to support the elongated body 1 even when the hand support member 40 is attached. The side stands 8 , 9 may have a leg design to reduce material used for manufacturing and to help keep the compound container 100 in balance when placed on a flat surface. [0033] Still referring to FIGS. 1-3 , in one embodiment, the side stands 8 , 9 may be outwardly inclined when extending toward the bottom 7 , forming an angle relative to the vertical direction. One side stand 8 has a tool holder including a blade slot 12 with a friction holding tab 13 , allowing a taping knife blade to be placed in the blade slot 12 and held tightly when the taping knife is not in use. The friction holding tab 13 is carved out from a convex 24 bulging slightly out of the plane of the side stand 8 , and the top part of the friction holding tab 13 includes a tongue 25 having a free edge 42 extending inwardly toward the elongated body 1 generally parallel to the horizontal surface plane of the compound container 100 . The tongue 25 provides more friction when a taping knife blade is placed into the blade slot 12 . It is to be understood that the blade slot 12 may be placed in either one of, or both of the side stands 8 , 9 . [0034] In another embodiment as shown in FIGS. 3 and 7 , the compound container 100 may further include two lips 10 , 11 extending outwardly from the two long edge sides 4 , 5 of the opening 2 . The lips 10 , 11 may extend from the two opposing long edges of the opening 2 , and further curl downwardly so that there are no sharp edges formed along the periphery of the opening 2 and thus the hands of one who is using the compound container may be protected from being cut. Curled lips may also add strength and stiffness to the long edge sides 4 , 5 . One of the lips 10 , 11 may have a scraping blade slot 14 . The scraping blade slot 14 may have a narrow and deep vertical opening, the width and length of which may be large enough to allow a scraping blade to be placed in the scraping blade slot 14 and to stay stably therein. It is to be understood that the scraping blade slot 14 may be placed in either one of, or both of the lips 10 , 11 . The compound container 100 may further include a scraping blade placed in the scraping blade slot 14 . In some embodiments, the scraping blade can be removed for cleaning after use of the compound container 100 . [0035] As shown in FIG. 9 , two compound containers each with a hand support member attached are stacked together by placing one compound container on top of another. When stacked together, the short edge sides 3 , 6 of the compound container 100 placed atop cling firmly to the short edge sides of the compound container placed underneath, allowing sufficient friction so that during movement stacked compound containers remain firmly stacked without being unintentionally separated. The side stands 8 , 9 and the short edge sides 3 , 6 close to the side stands 8 , 9 respectively may connect with each other at the short edge of the opening 2 in an acute angle. When two compound containers are stacked together, the side stands 9 , 8 of the compound container in below are placed underneath the side stands 3 , 6 of the compound container 100 on top; the side stands 8 , 9 in below are pressed and slightly bent inwardly, producing more friction between the compound containers when stacked together. The elongated body 1 of the compound container 100 including the holding members 15 , 16 may be molded using one or multiple embodiments herein disclosed. Elastroplastic with sufficient strength and durability, or other material with equivalent characteristics may be used for the elongated body 1 including the holding members 15 , 16 , and for the holding members 20 , 21 of the hand support member 40 . Soft materials like vinyl or thermal plastic elastomer may be used for the elongate body 19 of the hand support member 40 . [0036] The above are merely preferred embodiments of this application, and it is understood that by a person skilled in this art, several alternations and improvements are still considered within the scope of this application so long as they do not differ from the structure in this application. Such alternations and improvements shall not affect the practicability and utility of this application.
A compound container includes a container body having a side wall and a bottom wall; an interior space defined by the side wall and the end wall; an opening defined by an upper edge of the side wall; and an elongated hand support member having a first attachment section and a second attachment section for attaching the hand support member to a bottom surface of the bottom wall. The hand support member is positioned generally parallel to the opening defined by the upper edge of the side wall.
4
TECHNICAL FIELD The present invention pertains to regulating the pressure in the work-space of a pressurized engine, such as a Stirling engine. BACKGROUND OF THE INVENTION Stirling cycle machines, including engines and refrigerators, have a long technological heritage, described in detail in Walker, Stirling Engines , Oxford University Press (1980), and incorporated herein by reference. The principle underlying the Stirling cycle engine is the mechanical realization of the Stirling thermodynamic cycle: isovolumetric heating of a gas within a cylinder, isothermal expansion of the gas (during which work is performed by driving a piston), isovolumetric cooling, and isothermal compression. A Stirling cycle engine operates under pressurized conditions. Stirling engines contain a high-pressure working fluid, preferably helium, nitrogen or a mixture of gases at 20 to 140 atmospheres pressure. A Stirling engine may contain two separate volumes of gases, a working gas volume containing the working fluid, called a work-space or working space, and a crankcase gas volume, the gas volumes separated by piston seal rings. The crankcase encloses and shields the moving portions of the engine as well as maintains the pressurized conditions under which the Stirling engine operates (and as such acts as a cold-end pressure vessel). A pressurized crankcase removes the need for high pressure sliding seals to contain the work-space working fluid and halves the load on the drive component for a given peak-to-peak work-space pressure, as the work-space pressure oscillates about the mean crankcase pressure. The power output of the engine is proportional to the peak-to-peak work-space pressure while the load on the drive elements is proportional to the difference between the work-space and the crankcase pressures. FIG. 1 shows typical pressures in the gas volumes for such an engine. The action of the piston rings can raise or lower the mean working pressure above or below the crankcase pressure, substantially mitigating the above-mentioned advantages of a pressurized crankcase. For example, manufacturing marks, deviations and molding details of the rings can produce preferential gas flow in one direction between the work-space and the crankcase. The resulting difference in pressure between the work-space and the crankcase can produce as much as double the load on engine, while peak-to-peak pressure and thus engine power increases only fractionally (see, e.g., FIG. 2 ). In summary, pumping up the workspace mean pressure significantly increases engine wear with only a small attendant increase in power production. SUMMARY OF THE INVENTION In embodiments of the present invention, a device is provided that reduces the mean pressure difference between a work-space and a pressurized engine crankcase of an engine, such as a Stirling engine. The device includes a valve connecting the work-space and crankcase of the engine. The pressure difference between work-space and crankcase is monitored. When the mean pressure of the work-space differs from the crankcase pressure by a predetermined amount, the valve opens, allowing the pressure difference between the two spaces to equalize. When the pressure difference between the spaces is reduced sufficiently, the valve closes, isolating the work-space from the crankcase. This closure maximizing power production, while minimizing wear on drive components. In a specific embodiment of the invention, pressure at which the valve opens is determined by a preloaded spring. In a further specific embodiment of the invention, the mean pressure is monitored by including a constriction in the passageway from the valve to the work-space so that a mean work-space pressure is presented to a pressure monitoring device. In a further specific embodiment of the invention, the device further includes a constriction in the passageway from the crankcase to the pressure monitoring device such that the monitoring device is presented with a mean crankcase pressure. BRIEF DESCRIPTION OF THE DRAWINGS The invention will be more readily understood by reference to the following description, taken with the accompanying drawings, in which: FIG. 1 shows a graph of work-space and crank-case pressure for a Stirling engine with a pressurized crankcase; FIG. 2 shows a graph of pressure between a work-space and a crankcase for a Stirling engine when the work-space is pumped-up; FIG. 3 shows a side view in cross section of a sealed Stirling cycle engine; FIG. 4 shows a pressure regulator for an engine according to an embodiment of the invention; FIG. 5 shows a pressure regulator for an engine according to another embodiment of the invention; FIG. 6 shows a pressure regulator for an engine according to a further embodiment of the invention; and FIG. 7 shows the pressure difference that may develop across a valve according to the embodiment shown in FIG. 6 . DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS In embodiments of the present invention, a device is provided that reduces the pressure difference between a work-space and a pressurized engine crankcase of an engine, such as a Stirling engine. Referring to FIG. 3 , a sealed Stirling cycle engine 50 is shown in cross section. While this embodiment of the present invention will be described with reference to the Stirling engine shown in FIG. 3 , it should be understood that other engines, coolers, and similar machines may likewise benefit from embodiments of the present invention and such combinations are within the scope of the invention, as described in the appended claims. A sealed Stirling cycle engine operates under pressurized conditions. Stirling engine 50 contains a high-pressure working fluid, preferably helium, nitrogen or a mixture of gases at 20 to 140 atmospheres pressure. Typically, a crankcase 70 encloses and shields the moving portions of the engine as well as maintains the pressurized conditions under which the Stirling engine operates (and acts as a cold-end pressure vessel.) A heater head 52 serves as a hot-end pressure vessel. Stirling engine 50 contains two separate volumes of gases, a working gas volume 80 and a crankcase gas volume 78 , that will be called hereinafter, a “work-space” and a “crankcase,” respectively. These volumes are separated by piston rings 68 , among other components. In the work-space 80 , a working gas is contained by a heater head 52 , a regenerator 54 , a cooler 56 , a compression head 58 , an expansion piston 60 , an expansion cylinder 62 , a compression piston 64 and a compression cylinder 66 . The working gas is contained outboard of the piston seal rings 68 . The crankcase 78 contains a separate volume of gas enclosed by the cold-end pressure vessel 70 , the expansion piston 60 , and the compression piston 64 . The crankcase gas volume is contained inboard of the piston seal rings 68 . In the Stirling engine 50 , the working gas is alternately compressed and allowed to expand by the compression piston 64 and the expansion piston 60 . The pressure of the working gas oscillates significantly over the stroke of the pistons. During operation, fluid may leak across the piston seal rings 68 because the piston seal rings 68 do not make a perfect seal. This leakage results in some exchange of gas between the work-space and the crankcase. A work-space pressure regulator (“WSPR”) 84 serves to restore the pressure balance between the work-space and the crankcase. In embodiments of the invention, the WSPR is connected to the work-space by passageway 82 , which may be a pipe or other equivalent connection, and to the crankcase by another passageway 86 . When the work-space mean pressure 80 differs sufficiently from the mean crankcase pressure, the WSPR connects the two volumes via vent, 88 until the differential between the mean pressures diminishes. For example, an exemplary work-space pressure regulator is shown in FIG. 4 . Pipe or passageway 82 connects the pressure regulator 84 to the work-space 80 . A restrictive orifice 92 damps the oscillating work-space pressure applying the mean work-space pressure to one end of the shuttle, 100 . The orifice 92 is sized to be significantly larger than the piston seal ring leak. As used in this specification including any appended claims, the term “constriction” will be used to denote a narrowing in a pipe or passageway, including such a constriction at the end of a pipe or passageway or any place within the pipe or passageway. The other end of the shuttle 100 is exposed to the crankcase pressure via a pipe 86 , which pipe may include a restrictive orifice 93 or other constriction. Orifice 93 may be sized much smaller than orifice 92 , in which case the combination of the shuttle 100 and the orifice 93 act to damp movement of the shuttle from work-space pressure swings applied through orifice 92 . In a specific embodiment of the invention, orifice 92 , from WSGR to work-space is approximately 0.031 inches in diameter, while orifice 93 , from WSGR to the crankcase, is approximately 0.014 inches in diameter. In other embodiments of the invention, the constriction from shuttle to crankcase may be omitted. Note that the crankcase pressure is approximately constant over the piston's cycle, while the work-space pressure swings significantly during the cycle. Two springs 102 , 104 keep the shuttle 100 centered, when the mean work-space and the crankcase pressures are equal. When the mean work-space pressure is higher than the crankcase pressure, the higher pressure moves the shuttle 100 to the right, compressing spring 104 . If the pressure difference is large enough to expose port 88 the work-space and the crankcase become connected. Some of the work-space gas flows into the crankcase until the two mean pressures are equalized, which allows the shuttle 100 to return to the original position, closing the port 88 . Note that orifice from the work-space to the WSGR 92 may be sized to allow the pressure to equalize between work-space and crankcase quickly when port 88 is exposed, while still small enough to present a mean work-space pressure to the shuttle 100 . When the mean crankcase pressure is higher than the work-space pressure, the shuttle will move to the left, compressing spring 102 . If the pressure difference is large enough, port 88 will be exposed to channel 112 , connecting space 94 with the crankcase 78 . Some of the crankcase gas flows into the work-space until the two mean pressures are equalized, which allows the shuttle 100 to return to its centered position, closing port 88 . The shuttle isolates the work-space 80 from the crankcase 78 in its centered position. The seal may be provided by two cup seals 122 located at the end of shuttle nearest the crankcase vent 86 or by equivalent seals as are known in the art. Two ring seals 120 center and guide the shuttle 88 in the WSPR body 114 . Another embodiment of the invention is shown in FIG. 5 and labeled generally 200 . Work-space housing 205 and crankcase housing 210 are bolted together capturing piston 215 , work-space spring 225 , and crankcase spring 230 in their bores. The interface of the two housings creates cup seal gland 260 into which seats a bidirectional cup seal 220 , and an O-ring gland 265 into which seats an O-ring 270 . The O-ring seals the interior of the housings from the crankcase pressure. Two orifices 235 allow the pressures inside the two housings to remain equal to the mean crankcase pressure and the mean work-space pressure, respectively, without large pressure oscillations or large mass flows into/out of the housings. The piston is free to move axially within the housings by sliding on its bearing surfaces 250 . When the two pressures are equal, the springs keep the piston centered such that the cup seal seals against the piston's sealing surface 255 , preventing any flow between the two housings. When the pressure differential between the two housings becomes great enough, the force imbalance on the piston will cause the piston to move away from the region of high pressure, compressing the spring on the low-pressure side and relaxing the spring on the high-pressure side. Equilibrium is reached when the pressure force imbalance equals the spring force imbalance. If the pressure differential is great enough, the piston will be displaced enough that the cup seal 220 no longer contacts the sealing surface and instead loses sealing force against the decreasing diameter of the piston. Once the seal is broken, gas can flow from the high-pressure side, through the vent hole 240 or vent slot 245 , past the cup seal 220 , and into the adjacent housing. Gas will continue to flow until the pressure has equalized enough for the springs to return the piston to a position where the cup seal 220 seals against the sealing surface 255 . Another embodiment of the invention is shown in FIG. 6 and will be referred to as the Preloaded WSPR ( 300 ). This embodiment of the invention uses preloaded springs 302 , 304 connected to an inner piston 340 and an outer piston 342 to control working gas flow into and out of the work-space 80 . The springs are open-coil springs and, thus, gas flows freely through these springs. WSPR 300 communicates with the work-space 80 via an orifice 392 . Likewise, the crankcase volume 78 is connected to WSPR 300 via port 393 . Work-space pressure oscillations are damped out by the constriction of the orifice 392 together with the force of the pre-loaded springs 302 , 304 acting on the pistons 340 , 342 . Seals 370 , 372 provide a compliant seat for pistons 340 , 342 . The orifice 392 is sized to be significantly larger than the piston seal ring leak. WSPR 300 may be mounted on the compression cylinder head of the engine 58 (see FIG. 3 ). The Preloaded WSPR relieves a mean overpressure in the work-space in the following manner. The oscillating work-space pressure, which is partially damped by the orifice 392 , is applied to the face 380 of the inner piston 340 and to the face of the outer piston 342 that are proximate to the work-space. If the net mean pressure on the pistons is enough to overcome the preload on spring 302 , then the inner and outer pistons move to the left and open the valve at 382 . The released gas flows past the open seal at 382 around the outside of the outer piston 342 , through spring 302 and into the crankcase via port 393 . Once the difference between the work-space and the crankcase pressures drops below the preload on spring 302 , the outer piston 342 moves back to the right and seals at 382 . Seal 372 provides a compliant seat for piston 342 . The Preloaded WSPR relieves excess crankcase pressure by a similar method. When the net pressure times the inner piston's 340 area is greater than the preload on spring 304 , the inner piston 340 moves to the right and opens the valve at 370 , which provides a compliant seal for the inner piston 340 . Gas from the crankcase flows between the outer and inner pistons and into the work-space via the orifice at 392 reducing the pressure differential. Once the difference between the work-space and the crankcase pressures drops below the preload on spring 304 , the inner piston 340 moves back to the left and seals at 370 . In another preferred embodiment of the invention, the preloads in springs 302 and 304 may be preloaded to different force levels. The different forces applied by the springs would allow the workspace pressure to “pump-up” (i.e., increase) reaching a higher mean pressure, thereby allow the engine to produce higher mechanical power. This embodiment allows the design to add engine power without raising the crankcase mean pressure. Thus the power can be increased without redesigning or perhaps requalifying the crankcase pressure vessel. The functioning of the Preloaded WSPR can be understood by considering the pressures difference between the two orifices 392 and 393 in FIG. 6 . As an example, consider the pressure across valve 310 , as shown in FIG. 7 . (It should be noted that FIG. 7 is exemplary only and does not represent measured data on a WSPR.) The pressure difference between the two orifices can be better described as the pressure difference across regulator valve 310 where the regulator valve is composed of the two pistons 340 , 342 , the two springs 302 , 304 and the two valve seats 370 , 372 . FIG. 7 shows the pressure across valve 310 for two cases. In one case, the preload on each spring 302 , 304 is the same, and the workspace does not “pump-up,” as shown by graph 402 . The workspace and crank case remain at approximately the same mean pressure. In the second case, the preload on spring 302 is greater than the preload on spring 304 . Graph 404 shows the pressure across the valves, when the workspace has a mean pressure that is 100 psi above the crankcase pressure. In the latter case, the pressure difference may become large enough to overcome the preload on valve 302 , opening valve 310 and allowing gas to flow out of the workspace into the crankcase, reducing the pressure in the workspace. The horizontal line in FIG. 7 shows the pressure at which the preload on spring 304 is overcome. At that pressure, the WSPR opens allowing gas to pass between workspace and crankcase. The devices and methods described herein may be used in combination with components comprising other engines besides the Stirling engine in terms of which the invention has been described. The described embodiments of the invention are intended to be merely exemplary and numerous variations and modifications will be apparent to those skilled in the art. All such variations and modifications are intended to be within the scope of the present invention as defined in the appended claims
A device and method for equalizing the pressure between work-space and crankcase in a pressurized engine, such as a Stirling engine. The device consists of a two-way valve connected between the work-space and the crankcase. The valve is connected to the work-space with a passageway including a constriction to provide an mean pressure for monitoring purposes. The valve connects the work-space and crankcase allowing the pressure to equalize when the mean pressure of the work-space exceeds the crankcase pressure by a predetermined amount.
5
CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This application is related to and claims priority from U.S. Provisional Patent Application No. 60/274,657, filed Mar. 12, 2001,the contents of which are hereby incorporated herein by reference in their entirety. FIELD OF THE INVENTION [0002] The present invention relates to monitoring transport of digital content, particularly but not exclusively for the enforcement of digital copyright, secrecy and confidentiality. BACKGROUND OF THE INVENTION [0003] Modern businesses and industries relay heavily on digital media as primary means of communication and documentation. Digital media can be easily copied and distributed (e.g., via e-mail and peer-to-peer networks), and therefore the hazards of business espionage and data leakage are of major concern: Companies are at daily risk of losing sensitive internal documents, leading to substantial financial losses. Banking, legal, medical, government, and manufacturing companies have much to lose if sensitive internal documents are leaked. The safe distribution of internal documents, memos, blueprints, payroll records, patient medical information, banking and financial transactions etc, is becoming more complex to ensure. In fact, as a consequence of such leaks, the United States federal government was prompted to intervene and has mandated that companies should protect sensitive information such as financial and patient medical records. From the companies and businesses standpoint, potential risks include financial losses, fiduciary risks, legal problems, competitive intelligence, public relations problems, loss of clients and privacy liability. There is therefore a great interest in methods that may mitigate digital espionage in particular and confidential data leakage in general. [0004] In addition, unauthorized and/or illegal copying and distribution of multimedia content, such as audio and video, has become highly prevalent in recent years, especially via the Internet. Such unauthorized copying and distribution is an infringement of copyright protection laws and cause financial damage to the rightful owners of the content. It is therefore of great interest to find methods that may stop or at least reduce illegal copying and/or distribution of multimedia files without interfering with legitimate activities. [0005] Most current computer networks security solutions focus mainly on preventing outside penetration into the organization and do not provide an adequate solution to the transfer of sensitive documents originating from within the company. These solutions are usually based on Firewall or Antivirus models that do not stop negligent or malicious email, Web-based mail or FTP file transfers. [0006] Methods and systems for preventing the sending (i.e. outgoing transport) of digital content exist. Some methods assign a digital signature to each file and do not permit sending of a signed document without adequate authorization. However, such methods can easily be circumvented by transforming the content to another format or otherwise changing the content without altering the actual information content. Other known methods use file extension, file size and key word filtering: for example, a filter is set which searches for a predetermined word such as “finance” and prevents any document containing the predetermined word from being sent. Such a filter may be either too selective or too permissive, since the decision is based on scarce information. [0007] Methods for digital rights management (DRM) and digital copyright protection exist. Some methods are designed to control and monitor digital copying of the content. For example, U.S. Pat. No. 6,115,533 describes authentication of an information signal prior to mass duplication of the signal by analyzing the signal to detect the presence or absence of a security signal therein, inserting a security signal into the information signal, and recording the modified signal only if no security signal was detected. U.S. Pat. No. 6,167,136 describes a method for securely storing analog or digital data on a data storage medium: an analog information signal is then combined with a noise signal. The composite noise and information signal is encrypted with a key, which is derived from the noise signal. In U.S. Pat. No. 6,006,332 a system is provided for controlling access to digitized data. In the system, an insecure client is provided with a launch pad program which is capable of communicating with a secure Rights Management server. The launch pad program provides an indicator to a public browser, used by the unsecured client, which acknowledges when a rights management controlled object is detected. While these methods make illegal copying difficult, it is commonly believed that none of the existing methods is effective against a determined and competent opponent. Furthermore, once a certain protection method is cracked, the cracking tools and methods become available to a large community thereby rendering the protection method ineffective. [0008] Methods for usage rights enforcement of digital media in file sharing systems are also known. Some methods are designed to provide protection against centralized file sharing systems, where searching for the desired file is performed using an index that is located in a central server. e.g., the “NAPSTER” file sharing system. In this case, software on the central server can monitor the indexed file and prohibit illegal usage. Such methods require cooperation from the server operator. However, copyright protection against decentralized, “peer to peer” files sharing networks e.g., “Gnutella” and “FreeNet” and document distribution networks e.g. “Internet Newsgroups”, as well as protection against centralized file sharing networks without the cooperation of the server operator, are much harder, and these problems are not addressed by current methods. [0009] Other methods attempt to use bandwidth management tools in order to reduce the available bandwidth for multimedia transport in places where such transport is suspected of carrying a large proportion of illegal content. The inspection is performed, in general, in the “application layer”. However, such methods are in general not selective enough, that is to say they do not distinguish effectively between legal and illegal (or unauthorized) content, and thus may interfere with legitimate data traffic. [0010] It is foreseeable that as the availability of disk space and bandwidth for data communication increases, unauthorized and illegal distribution of digital content may increase and become more prevalent unless effective counter-measures are taken. SUMMARY OF THE INVENTION [0011] The present invention seeks to provide a novel method and system for the mitigation of illegal and unauthorized transport of digital content, without otherwise interfering with rightful usage and the privacy of the users. Specifically, the current invention provides methods that allow inspection and analysis of digital traffic in computer networks and automatic detection of unauthorized content within the inspected traffic. The detection method is generally based on extraction of features from the transportation itself that carry information about the specific content (or information which can be used in order to gather such information.) A comparison is then performed with a database that contains features that have been extracted from the copyrighted or confidential items that are to be protected. The inspection and analysis may be performed in various layers of the network protocol layers 2 - 7 in the OSI model (an hardware implementation may also utilize layer 1 ) and the coherency between the various layers may be maintained by introducing the concept of an atomic channel, as will be described in more detail below. [0012] Upon detection of illegal transport, the system preferably audits the transport details and enforces transport policy, such as blocking the transport or reduction of the bandwidth available for this transport. To this end, a novel method for bandwidth reduction, that overcomes drawbacks of current methods, is also provided herein. The system may for example be implemented as a firewall or as an extension to existing firewall systems, or in other forms, and can monitor ingoing and\or outgoing transport. [0013] In another embodiment, a database of signatures of confidential, copyrighted, illegal or otherwise restricted materials may be used in order to identify and possibly block the transport of the materials from a restricted zone. Such implementation is important also because the present peer-to-peer networks effectively create an “alternative Internet” that renders many of the current standard firewall techniques ineffective or too untargeted. For example. such a firewall technique may leave the system administrator the option of either completely blocking whole classes of transport or not blocking such traffic as a whole and instead relying on specific data. Specifically, practices based on locating the other party to the communication are often rendered ineffective, due to the pseudo-anonymous nature of particular networks. [0014] The present invention may also be used in combination with certification methods and techniques in order to allow un-inspected, un-restricted or otherwise privileged usage to certificated users. [0015] The present invention can also be used in order to accumulate consumption statistics and/or other useful statistical analysis of the analyzed transport. [0016] According to a first aspect of the present invention there is provided a system for network content monitoring, comprising: [0017] a transport data monitor, connectable to a point in a network, for monitoring data being transported past the point, [0018] a description extractor, associated with the transport data monitor, for extracting descriptions of the data being transported, [0019] a database of at least one preobtained description of content whose movements it is desired to monitor, and [0020] a comparator for determining whether the extracted description corresponds to any of the at least one preobtained descriptions, thereby to determine whether the data being transported comprises any of the content whose movements it is desired to monitor. [0021] Preferably, the description extractor is operable to extract a pattern identifiably descriptive of the data being transported. [0022] Preferably, the description extractor is operable to extract a signature of the data being transported. [0023] Preferably, the description extractor is operable to extract characteristics of the data being transported. [0024] Preferably, the description extractor is operable to extract encapsulated meta information of the data being transported. [0025] Preferably, the description extractor is operable to extract multi-level descriptions of the data being transported. [0026] Preferably, the multi-level description is comprises of a pattern identifiably descriptive of the data being transported. [0027] Preferably, the multi-level description is comprises a signature of the data being transported. [0028] Preferably, the multi-level description comprises characteristics of the data being transported. [0029] Preferably, the multi-level description comprises encapsulated meta-information of the data being transported. [0030] Preferably, the description extractor is a signature extractor, for extracting a derivation of the data, the derivation being a signature indicative of content of the data being transported, and wherein the at least one preobtained description is a preobtained signature. [0031] Preferably, the network is a packet-switched network and the data being transported comprises passing packets. [0032] Preferably, the network is a packet-switched network, the data being transported comprises passing packets and the transport data monitor is operable to monitor header content of the passing packets. [0033] Preferably, the network is a packet-switched network, the data being transported comprises passing packets, and the transport data extractor is operable to monitor header content and data content of the passing packets. [0034] Preferably, the transport data monitor is a software agent, operable to place itself on a predetermined node of the network. [0035] Preferably, the system comprises a plurality of transport data monitors distributed over a plurality of points on the network. [0036] Preferably, the transport data monitor further comprising a multimedia filter for determining whether passing content comprises multimedia data and restricting the signature extraction to the multimedia data. [0037] 18. A system according to claim 1, the data being transported comprising a plurality of protocol layers, the system further comprising a layer analyzer connected between the transport data monitor and the signature extractor, the layer analyzer comprising analyzer modules for at least two of the layers. [0038] Preferably, the layer analyzer comprises separate analyzer modules for respective layers. [0039] Preferably, the system comprises a traffic associator, connected to the analyzer modules, for using output from the analyzer modules to associate transport data from different sources as a single communication. [0040] Preferably, the sources include any of data packets, communication channels, data monitors, and pre correlated data. [0041] Preferably, the system comprises a traffic state associator connected to receive output from the layer analyzer modules, and to associate together output, of different layer analyzer modules, which belongs to a single communication. [0042] Preferably, at least one of the analyzer modules comprises a multimedia filter for determining whether passing content comprises multimedia data and restricting the signature extraction to the multimedia data. [0043] Preferably, at least one of the analyzer modules comprises a compression detector for determining whether the extracted transport data is compressed. [0044] Preferably, the system comprises a decompressor, associated with the compression detector, for decompressing the data if it is determined that the data is compressed. [0045] Preferably, the system comprises a description extractor for extracting a description directly from the compressed data. [0046] Preferably, at least one of the analyzer modules comprises an encryption detector for determining whether the transport data is encrypted. [0047] Preferably, the encryption detector comprises an entropy measurement unit for measuring entropy of the monitored transport data. [0048] Preferably, the encryption detector is set to recognize a high entropy as an indication that encrypted data is present. [0049] Preferably, the encryption detector is set to use a height of the measured entropy as a confidence level of the encrypted data indication. [0050] Preferably, the system comprises a format detector for determining a format of the monitored transport data. [0051] Preferably, the system comprises a media player, associated with the format detector, for rendering and playing the monitored transport data as media according to the detected format, thereby to place the monitored transport data in condition for extraction of a signature which is independent of a transportation format. [0052] Preferably, the system comprises a parser, associated with the format detector, for parsing the monitored transport media, thereby to place the monitored transport data in condition for extraction of a signature which is independent of a transportation format. [0053] Preferably, the system comprises a payload extractor located between the transport monitor and the signature extractor for extracting content carrying data for signature extraction. [0054] Preferably, the signature extractor comprises a binary function for applying to the monitored transport data. [0055] Preferably, the network is a packet network, and a buffer is associated with the signature extractor to enable the signature extractor to extract a signature from a buffered batch of packets. [0056] Preferably, the binary function comprises at least one hash function. [0057] Preferably, the binary function comprises a first, fast, hash function to identify an offset in the monitored transport data and a second, full, hash function for application to the monitored transport data using the offset. [0058] Preferably, the signature extractor comprises an audio signature extractor for extracting a signature from an audio part of the monitored data being transported. [0059] Preferably, the signature extractor comprises a video signature extractor for extracting a signature from a video part of the monitored data being transported. [0060] Preferably, the signature extractor comprises a pre-processor for pre-processing the monitored data being transported to improve signature extraction. [0061] Preferably, the preprocessor carries out at least one of: removing erroneous data, removing redundancy, and canonizing properties of the monitored data being transported. [0062] Preferably, the signal extractor comprises a binary signal extractor for initial signature extraction and an audio signature extractor for extracting an audio signature in the event the initial signature extraction fails to yield an identification. [0063] Preferably, the signal extractor comprises a binary signal extractor for initial signature extraction and a text signature extractor for extracting a text signature in the event the initial signature extraction fails to yield an identification. [0064] Preferably, the signal extractor comprises a binary signal extractor for initial signature extraction and a code signature extractor for extracting a code signature in the event the initial signature extraction fails to yield an identification. [0065] Preferably, the signal extractor comprises a binary signal extractor for initial signature extraction and a data content signature extractor for extracting a data content signature in the event the initial signature extraction fails to yield an identification. [0066] Preferably, the signature extractor is operable to use a plurality of signature extraction approaches. [0067] Preferably, the system comprises a combiner for producing a combination of extracted signatures of each of the approaches. [0068] Preferably, the comparator is operable to compare using signatures of each of the approaches and to use as a comparison output a highest result of each of the approaches. [0069] Preferably, the signal extractor comprises a binary signal extractor for initial signature extraction and a video signature extractor for extracting a video signature in the event the initial signature extraction fails to yield an identification. [0070] Preferably, there is a plurality of preobtained signatures and the comparator is operable to compare the extracted signature with each one of the preobtained signatures, thereby to determine whether the monitored transport data belongs to a content source which is the same as any of the signatures. [0071] Preferably, the comparator is operable to obtain a cumulated number of matches of the extracted signature. [0072] Preferably, the comparator is operable to calculate a likelihood of compatibility with each of the preobtained signatures and to output a highest one of the probabilities to an unauthorized content presence determinator connected subsequently to the comparator. [0073] Preferably, the comparator is operable to calculate a likelihood of compatibility with each of the preobtained signatures and to output an accumulated total of matches which exceed a threshold probability level. [0074] Preferably, the comparator is operable to calculate the likelihood of compatibility with each of the preobtained signatures and to output an accumulated likelihood of matches which exceed a threshold probability level. [0075] Preferably, the system comprises a sequential decision unit associated with the comparator to use a sequential decision test to update a likelihood of the presence of given content, based on at least one of the following: successive matches made by the comparator, context related parameters, other content related parameters and outside parameters. [0076] Preferably, the unauthorized content presence determinator is operable to use the output of the comparator to determine whether unauthorized content is present in the transport and to output a positive decision of the presence to a subsequently connected policy determinator. [0077] Preferably, an unauthorized content presence determinator is connected subsequently to the comparator and is operable to use an output of the comparator to determine whether unauthorized content is present in the data being transported, a positive decision of the presence being output to a subsequently connected policy determinator. [0078] Preferably, the policy determinator comprises a rule-based decision making unit for producing an enforcement decision based on output of at least the unauthorized content presence determinator. [0079] Preferably, the policy determinator is operable to use the rule-based decision making unit to select between a set of outputs including at least some of: taking no action, performing auditing, outputting a transcript of the content, reducing bandwidth assigned to the transport, using an active bitstream interference technique, stopping the transport, preventing printing, preventing photocopying, reducing quality of the content, removing sensitive parts, altering the content, adding a message to the the content, and preventing of saving on a portable medium, [0080] Preferably, the rule-based decision making unit is operable to use a likelihood level of a signature identification as an input in order to make the selection. [0081] Preferably, a bandwidth management unit is connected to the policy determinator for managing network bandwidth assignment in accordance with output decisions of the policy determinator. [0082] Preferably, there is provided an audit unit for preparing and storing audit reports of transportation of data identified as corresponding to content it is desired to monitor. [0083] Preferably, the system comprises a transcript output unit for producing transcripts of content identified by the comparison. [0084] Preferably, the system comprises a policy determinator connected to receive outcomes of the encryption determinator and to apply rule-based decision making to select between a set of outputs including at least some of: taking no action, performing auditing, outputting a transcript of the content, reducing bandwidth assigned to the transport, using an active bitstream interference technique, and stopping the transport. [0085] Preferably, the rule-based decision making comprises rules based on confidence levels of the outcomes. [0086] Preferably, the policy determinator is operable to use an input of an amount of encrypted transport from a given user as a factor in the rule based decision making. [0087] Preferably, the system comprises a policy determinator connected to receive positive outcomes of the encryption determinator and to apply rule-based decision making to select between a set of outputs including at least some of: taking no action, performing auditing, outputting a transcript of the content, reducing bandwidth assigned to the transport, using an active bitstream interference technique, and stopping the transport, the policy determinator operable to use: [0088] an input of an amount of encrypted transport from a given user, and [0089] the confidence level, as factors in the rule based decision making. [0090] According to a second aspect of the present invention there is provided a system for network content control, comprising: [0091] a transport data monitor, connectable to a point in a network, for monitoring data being transported past the point, [0092] a signature extractor, associated with the transport data monitor, for extracting a derivation of payload of the monitored data, the derivation being indicative of content of the data, [0093] a database of preobtained signatures of content whose movements it is desired to monitor, [0094] a comparator for comparing the derivation with the preobtained signatures, thereby to determine whether the monitored data comprises any of the content whose movements it is desired to control, [0095] a decision-making unit for producing an enforcement decision, using the output of the comparator, and [0096] a bandwidth management unit connected to the decision-making unit for managing network bandwidth assignment in accordance with output decisions of the policy determinator, thereby to control content distribution over the network. [0097] Preferably, the decision-making unit is a rule-based decision-making unit. [0098] Preferably, the transport data monitor is a software agent, operable to place itself on a predetermined node of the network. [0099] Preferably, the system comprises a plurality of transport data monitors distributed over a plurality of points on the network. [0100] Preferably, the transport data monitor further comprises a multimedia filter for determining whether passing content comprises multimedia data and restricting the signature extraction to the multimedia data. [0101] Preferably, the transport data comprises a plurality of protocol layers, the system further comprising a layer analyzer connected between the transport data monitor and the signature extractor, the layer analyzer comprising analyzer modules for at least two of the layers. [0102] Preferably, the system comprises a traffic state associator connected to receive output from the layer analyzer modules, and to associate together output of different layer analyzer modules which belongs to a single communication. [0103] Preferably, one of the analyzer modules comprises a multimedia filter for determining whether passing content comprises multimedia data and restricting the data extraction to the multimedia data. [0104] Preferably, one of the analyzer modules comprises a compression detector for determining whether the monitored transport data is compressed. [0105] Preferably, the system comprises a decompressor, associated with the compression detector, for decompressing the data if it is determined that the data is compressed. [0106] Preferably, one of the analyzer modules comprises an encryption detector for determining whether the monitored transport data is encrypted. [0107] Preferably, the encryption detector comprises an entropy measurement unit for measuring entropy of the monitored transport data. [0108] Preferably, the encryption detector is set to recognize a high entropy as an indication that encrypted data is present. [0109] Preferably, the encryption detector is set to use a height of the measured entropy as a confidence level of the encrypted data indication. [0110] Preferably, the system comprises a format detector for determining a format of the monitored transport data. [0111] Preferably, the system comprises a media player, associated with the format detector, for rendering and playing the monitored transport data as media according to the detected format, thereby to place the extracted transport data in condition for extraction of a signature which is independent of a transportation format. [0112] Preferably, the system comprises a parser, associated with the format detector, for parsing the monitored transport media, thereby to place the extracted transport data in condition for extraction of a signature which is independent of a transportation format. [0113] Preferably, the signature extractor comprises a binary function for applying to the extracted transport data. [0114] Preferably, the binary function comprises at least one hash function. [0115] Preferably, the binary function comprises a first, fast, hash function to identify an offset in the extracted transport data and a second, full, hash function for application to the extracted transport data using the offset. [0116] Preferably, the signature extractor comprises an audio signature extractor for extracting a signature from an audio part of the extracted transport data. [0117] Preferably, the signature extractor comprises a video signature extractor for extracting a signature from a video part of the extracted transport data. [0118] Preferably, the comparator is operable to compare the extracted signature with each one of the preobtained signatures, thereby to determine whether the monitored transport data belongs to a content source which is the same as any of the signatures. [0119] Preferably, the comparator is operable to calculate a likelihood of compatibility with each of the preobtained signatures and to output a highest one of the probabilities to an unauthorized content presence determinator connected subsequently to the comparator. [0120] Preferably, the unauthorized content presence determinator is operable to use the output of the comparator to determine whether unauthorized content is present in the transport and to output a positive decision of the presence to a subsequently connected policy determinator. [0121] Preferably, an unauthorized content presence determinator is connected subsequently to the comparator and is operable to use an output of the comparator to determine whether unauthorized content is present in the transport, a positive decision of the presence being output to a subsequently connected policy determinator. [0122] Preferably, the policy determinator comprises the rule-based decision making unit for producing an enforcement decision based on output of at least the unauthorized content presence determinator. [0123] Preferably, the policy determinator is operable to use the rule-based decision making unit to select between a set of outputs including at least some of: taking no action, performing auditing, outputting a transcript of the content, reducing bandwidth assigned to the transport, using an active bitstream interference technique, stopping the transport, not allowing printing of the content, not allowing photocopying of the content and not allow saving of the content on portable media. [0124] Preferably, the rule-based decision making unit is operable to use a likelihood of a signature identification as an input in order to make the selection. [0125] Preferably, the system comprises an audit unit for preparing and storing audit reports of transportation of data identified as corresponding to content it is desired to monitor. [0126] Preferably, the system comprises a policy determinator connected to receive positive outcomes of the encryption determinator and to apply rule-based decision of the rule-based decision making unit to select between a set of outputs including at least some of: taking no action, performing auditing, outputting a transcript of the content, reducing bandwidth assigned to the transport, using an active bitstream interference technique, stopping the transport, reducing quality of the content, removing sensitive parts, altering the content, adding a message to the content, not allowing printing of the content, not allowing photocopying of the content and not allow saving of the content on portable media. [0127] Preferably, the policy determinator is operable to use an input of an amount of encrypted transport from a given user as a factor in the rule based decision making. [0128] Preferably, the system comprises a policy determinator connected to receive positive outcomes of the encryption determinator and to apply rule-based decision making of the rule-based decision-making unit to select between a set of outputs including at least some of: taking no action, performing auditing, outputting a transcript of the content, reducing bandwidth assigned to the transport, using an active bitstream interference technique, stopping the transport, reducing quality of the content, removing sensitive parts, altering the content, adding a message to the content, not allowing printing of the content, not allowing photocopying of the content, and not allowing saving of the content on portable media. [0129] Preferably, the policy determinator is operable to use: [0130] an input of an amount of encrypted transport from a given user, and [0131] the confidence level, as factors in the rule based decision making. [0132] The system may typically be comprised within a firewall. [0133] Preferably, the transport data monitor is operable to inspect incoming and outgoing data transport crossing the firewall. [0134] Preferably, the system is operable to define a restricted network zone within the network by inspecting data transport outgoing from the zone. [0135] Preferably the system provides certification recognition functionality to recognize data sources as being trustworthy and to allow data transport originating from the trustworthy data sources to pass through without monitoring. [0136] The certification recognition functionality may recognize data sources as being trustworthy and thus allow data transport originating from the trustworthy data sources to pass through with monitoring modified on the basis of the data source recognition. [0137] The certification recognition functionality may recognize data sources as being trustworthy and use that recognition to allow data transport originating from the trustworthy data sources to pass through with the decision making being modified on the basis of the data source recognition. [0138] According to a third aspect of the present invention there is provided a method of monitoring for distribution of predetermined content over a network, the method comprising: [0139] obtaining extracts of data from at least one monitoring point on the network, [0140] obtaining a signature indicative of content of the extracted data, [0141] comparing the signature with at least one of a prestored set of signatures indicative of the predetermined content, [0142] using an output of the comparison as an indication of the presence or absence of the predetermined content. [0143] According to a fourth aspect of the present invention there is provided a method of controlling the distribution of predetermined content over a network, the method comprising: [0144] obtaining extracts of data from at least one monitoring point on the network, [0145] obtaining a signature indicative of content of the extracted data, [0146] comparing the signature with at least one of a prestored set of signatures indicative of the predetermined content, [0147] using an output of the comparison in selecting an enforcement decision, and [0148] using the enforcement decision in bandwidth management of the network. [0149] Preferably, enforcement decisions for selection include at least some of taking no action, performing auditing, outputting a transcript of the content, reducing bandwidth assigned to the transport, stopping the transport, reducing quality of the content, removing sensitive parts, altering the content, adding a message to the content, using an active bitstream interference technique, restricting bandwidth to a predetermined degree, not allowing printing of the content, not allowing photocopying of the content and not allowing saving of the content on portable media. [0150] Preferably, the predetermined degree is selectable from a range extending between minimal restriction and zero bandwidth. BRIEF DESCRIPTION OF THE DRAWINGS [0151] For a better understanding of the invention and to show how the same may be carried into effect, reference will now be made, purely by way of example, to the accompanying drawings. [0152] With specific reference now to the drawings in detail, it is stressed that the particulars shown are by way of example and for purposes of illustrative discussion of the preferred embodiments of the present invention only, and are presented in the cause of providing what is believed to be the most useful and readily understood description of the principles and conceptual aspects of the invention. In this regard, no attempt is made to show structural details of the invention in more detail than is necessary for a fundamental understanding of the invention, the description taken with the drawings making apparent to those skilled in the art how the several forms of the invention may be embodied in practice. In the accompanying drawings: [0153] [0153]FIG. 1, is a simplified conceptual illustration of a system for detection of unauthorized transport of digital content using transport inspection, constructed and operative in accordance with a preferred embodiment of the present invention; [0154] [0154]FIG. 2 is a simplified illustration of a part of the embodiment of FIG. 1, for detection of unauthorized transport of digital content, based on binary signatures; [0155] [0155]FIG. 3 is a simplified illustration of an alternative to the part of FIG. 2, for detection of unauthorized transport of digital content, based on the signatures of the audio\video signal; [0156] [0156]FIG. 4 is a simplified illustration of a decision-making subsystem for use in the embodiment of FIG. 1; [0157] [0157]FIG. 5 is a simplified illustration of a part of the system of FIG. 1, for policy enforcement using bandwidth management; [0158] [0158]FIG. 6 is a simplified illustration of a subsystem for automatic detection of encrypted content, for use in the embodiment of FIG. 1; [0159] [0159]FIG. 7 is a simplified block diagram of an alternative embodiment of the present invention that uses a module that filters multimedia content for further inspection; [0160] [0160]FIG. 8 is a simplified schematic diagram of a further alternative embodiment of the present invention, which performs multi-layer analysis of data traffic and maintains coherency between the various transport layers by introducing a concept referred to herein as an atomic channel; [0161] [0161]FIG. 9 is a simplified block diagram of a system for monitoring and control of content flow on a network according to a preferred embodiment of the present invention; [0162] [0162]FIG. 10 is a simplified block diagram, similar to the one illustrated in FIG. 9, which also describes an interface to a photocopying machine according to a preferred embodiment of the present invention; and [0163] [0163]Fig. 11 is a simplified block diagram of another embodiment of the present invention, where at least part of the monitoring and control is performed in a distributed manner. DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS [0164] The present embodiments deal, generally speaking, with protection against unauthorized transport by inspecting the transport in computer networks and applying methods for automatic recognition of unauthorized transport of content, preferably without interfering with rightful usage and the privacy of the users. [0165] Before explaining at least one embodiment of the invention in detail, it is to be understood that the invention is not limited in its application to the details of construction and the arrangement of the components set forth in the following description or illustrated in the drawings. The invention is applicable to other embodiments or of being practiced or carried out in various ways. Also, it is to be understood that the phraseology and terminology employed herein is for the purpose of description and should not be regarded as limiting. [0166] Reference is firstly made to FIG. 1, which is a simplified illustration showing a conceptual view of a system for detection of transport of unauthorized content using transport inspection according to a first embodiment of the present invention. An incoming transport 101 , which can be a packet transport, but may also be of higher level, e.g., an e-mail message or an e-mail attachment, reaches an inspection point 102 , where one or more binary signatures are extracted from an individual packet 1021 of said transport 101 . [0167] The inspection point may receive as inputs transport that may or may be a packet stream or any other kind of network data exchange including any other kinds of transport. Depending on the level of the transport, the complete content may be more or less easily accessible. Thus, an E-mail server may have access to entire E-mails, and in many cases may even access individual attachments directly. In certain cases it may even be able to edit such e-mails.I In cases where directly accessible and editable content exists, handling may include editing and/or removing and/or replacing parts of the content. The above also applies to semi-directly available content. Thus a message may have MIME encoded attachments which constitute content, and which it may be able to treat in the above manner. [0168] In cases of transport where the received transport is not segmented into packets, or is segmented in an unsuitable manner (e.g. bitstream), segmentation into packets may be achieved arbitrarily, and in such cases the packets inspected at inspection point 102 would not be the packets of the received transport. [0169] The extracted signature is compared to previously extracted illegal content signatures, which have been stored in a preferably pre-sorted database 104 . The search and comparison process is performed using a signature search and comparison mechanism 103 . Results of the search are used as an input to unauthorized content detection subsystem 106 , where an accumulated number of matches may be used to decide if the packets comprise illegal digital content. Alternatively a quantitative measure, or an accumulation of quantitative measures of each match may be used. [0170] Results from the unauthorized content detection subsystem may serve as inputs to a policy determinator 107 , which decides, based on the current inputs and a preinstalled set of rules, to enforce a certain policy, such as to block the transport, to reduce the available bandwidth for the transport, to use active methods in order to interfere with the bitstream, only to perform auditing or not to do anything at all. Results from the policy determinator are used to define a policy that is enforced by a policy enforcement subsystem 108 . The policy enforcement subsystem 108 may make use of any known methods and techniques for bandwidth management in order to reduce or to stop the outgoing transport 109 . Results from the policy determinator 107 , the unauthorized content detection subsystem and other relevant data from the inspection point 102 may serve as inputs to an audit generator 109 , which prepares an audit that preferably contains details that may be considered relevant for the purposes of the audit, such as content name, source, destination, statistics on events, time, actions and others. Resulting audit reports may thereafter be stored in an audit database 110 . [0171] The policy determinator may decide, according to related information, usually gathered from the transport or content, how the inspected transport is to be handled for example should it be blocked, should it be logged, and such handling may be applied even if the transport or content is not explicitly recognized from a signature. [0172] Reference is now made to FIG. 2, which is a simplified block diagram showing parts of the system of FIG. 1 in greater detail. FIG. 2 illustrates a subsystem for detection of the presence of unauthorized content, based on extracted binary signatures. The input stream, that may be the incoming packet stream, serves as an input to the payload extractor module 20211 . Content identification is thereafter performed in two different ways. First of all a packet signature extractor 20212 extracts a binary signature from each packet. In a preferred embodiment the signatures are essentially the output of a hash function applied to the binary payload of the packets. The hash function is preferably efficient, but is not necessarily cryptographically secure or collision free. The size of the hashed values is preferably sufficiently large to provide information regarding the content of the packet. A preferred embodiment of the present invention uses a 64 bits CRC as a signature for packets of size 1.5 Kb. [0173] In another preferred embodiment of the present invention a fast hash is used for generating self-synchronized hits. Once a hit is located, a full hash may be calculated on a larger block using the location of the hit as an offset for the middle of a chunk being tested. The full hash should preferably be a true cryptographic hash with at least 128 bits of output. The chunk being tested should be large enough to contain significant entropy even if the file from which it is taken does not have a particularly high entropy density level. A chunk size of 256 bytes ±128 bytes around the hit position yields good results while keeping the chance of losing bits across packet boundaries at reasonable levels. [0174] In some cases, inspection of a small number of packets (or an amount of non packetized data) may not provide enough information to identify the content. For example, the representation of the logo of a certain studio in a video file may be the same for many of the movies produced by that particular studio. It is therefore possible to use information gathered from more than one packet in order to identify the content (or an equivalent significant amount of data). In certain cases a confidence level with which identification can be performed, when based on a sample of small size, may be content dependent. [0175] In another embodiment of the present invention, a sequential decision module 2051 uses a sequential decision test E.g., the Neyman-Pearson test, in order to update successively the probability of certain content. The signatures of each packet are compared with the signatures in the database, and each match with any of the pre-stored signatures belonging to a particular content item that is represented in the database increases the likelihood that the data belongs to the matched content. The increase may be content-dependent and therefore the database may also contain content-dependent rules for likelihood updates. The total a-posteriori probability or confidence level may thereafter be estimated 20512 and the maximum a-posteriori estimator 20513 may detect the content to which the inspected data most likely belongs and output its identity and possibly the corresponding confidence level. In addition, packets can be accumulated in a buffer 20213 , and the signature can thereafter be extracted in batch mode 20214 from larger chunks of data. It is noted that the present method is less sensitive than that described previously, to variations in the parsing of the data. [0176] The signatures thereafter may serve as inputs to the batch decision module 2052 , which estimates the probabilities that the examined data belongs to a certain content that is represented in the database. It is noted that a non-batch decision module can of course be used to replace the batch decision module. [0177] The results from the batch and the sequential decision modules 2051 , 2052 may serve as inputs to a final detection system 2053 , which preferably estimates the total probability that the examined data belongs to certain content that is represented in the database. The results may serve as inputs to the audit generator 209 and policy determinator 206 . [0178] The binary representation of video, audio, still images and other signals depends on the way in which it has been encoded, and therefore the binary signature database preferably includes variations that take into account the different encoding systems, in order to be efficient. However, one cannot expect to have available sample signatures for every content item for every type of encoding. It is therefore preferable to be able to identify the content in a manner that does not depend upon the encoding system. Such an aim may be achieved by decoding the content first and then extracting the signature of the content directly from the decoded video and/or audio and/or still images signal itself. [0179] In some signature schemes it is possible to extract the signature without decoding and/or decompressing the content, or using only partial basic decoding. This is due to the fact that most compression and encoding formats (usually but not always, employing lossy compression. e.g. JPEG, MPEG) are based on the same robust properties as the signature itself may be based upon. In some cases a signature can be designed for easy extraction from a specific format or set of formats. [0180] A similar but in certain respects more complicated case arises from the use of text signatures. With text signatures, (as is often true for other domains), some pre-processing may improve the ability to recognize the signature. The pre-processing may comprise pre canonizing the input. Pre-canonizing may be considered equivalent to filtering, for example filtering out noise, low pass filtering, etc. Pre-canonizing may be applied to audio, video or still content before extracting the signature, which may be included with any the following: removing formatting information (white space, fonts, etc.) whether partly or fully, removing redundancy which may easily be changed, canonizing or correcting spelling, transforming to another (usually more compact) notation (e.g. phonetic) in which closely comparable elements may be equivalent. [0181] A similar case arises with the handling of computer program code or raw data (e.g spreadsheets, data files) The skilled person will appreciate that the significance of changes or alterations in such data is dramatically different than for text. For example a different spelling may cause different program behavior. In the case of such data types, cannonization may for example consist of removing comments and generally consists of semi-intelligently parsing the content. [0182] As discussed above, there are several methods for extracting signatures, and each method may be used alone. In addition it is possible to use different combinations of the extraction methods to extract useful information, and in such a case the most useful result over all the different methods is accepted. In an alternative embodiment, information from the different methods may be combined to produce an overall signature. [0183] Reference is now made to FIG. 3, which is a simplified block diagram showing schematically an arrangement for carrying out content identification based on a video and/or audio signature. The input stream 301 arrives in packet form (or other suitable form), from which the content or payload is extracted by a payload extractor 30211 and is accumulated at a buffer 30213 . The format of the content is thereafter identified at a format identifier 303 , using information from the payload and/or from packet headers. If the content is compressed using a standard compression system e.g., “zip”, the content is first opened or uncompressed using a decompressor 3031 . [0184] Following opening, there are two preferred possibilities for proceeding: A first possibility is to extract parameters directly from the bitstream using a parser 305 . A second possibility is to render the content using a multimedia player 306 . In preferred embodiments both possibilities are provided and a decision as to which of the two to use in any given instance is preferably taken based on the content type. [0185] The content signature is extracted using the relevant signature extraction module, 306 or 307 . The extracted signatures are thereafter compared with signatures in the corresponding databases 310 and 311 using the respective comparison and search modules 308 and 309 . Methods for obtaining signatures of the original content and performing searches are described, e.g., in U.S. Pat. Nos. 6,125,229, 5,870,754 and 5,819,286, the contents of which are hereby incorporated by reference. [0186] Preferably, the signature comparison yields probabilities that the content belongs to any of the contents represented in the database. Such probabilities are thereafter estimated for each of the signatures or for a subset of the signatures by probability estimator 312 and a most likely content item is identified using the maximum likelihood estimator 313 . [0187] Since the extraction and the comparison of binary signatures is far more simple then the extraction and the comparison of audio and video signatures, the above identification method will, in general, be employed only if the suspected content has not been identified using binary signatures as described above in respect of FIG. 1. [0188] Reference is now made to FIG. 4, which is a simplified block diagram of the policy enforcement subsystem 107 of FIG. 1. The policy enforcement subsystem 107 receives as input the identification of unauthorized content that was found in previous stages, together with a corresponding confidence level. Decision system 4061 uses a rule-set 4062 in order to take into consideration various parameters, such as the confidence level. Thus for example a very simple rule based on the confidence level may be as follows: [0189] for low confidence level—take no action, [0190] for intermediate confidence level—allow transport with a reduced bandwidth, where the bandwidth reduction depends on the confidence level, and [0191] for high confidence level, completely stop the transport. [0192] Sometimes it may be possible to only stop part of the transport (e.g. an E-mail attachment) or to edit some of its contents (e.g. reduce the quality of copyrighted material). [0193] Another parameter that may be taken into account is the content identity itself, as certain content items may be of more concern than others. For example, a particular publisher may be highly concerned about distribution of a content item at an early stage of illegal distribution, or may be particularly concerned to stop the distribution of a content item whose production required a large amount of money or has only recently been released. Other factors to be considered may include a desire to give the system of the present embodiments a low profile in order to reduce the probability of counter measures, to protect the credentials of the source and the destination of the transport etc. [0194] One possible final decision of the system may be to completely stop the transport whether immediately or after crossing a threshold such as a time threshold. Another possibility is to allow the transport to continue with reduced bandwidth, and another possible decision is to take no action and to allow the transport to proceed as usual. After the decision, the corresponding allocated bandwidth is preferably attached to the packets, typically in a packet header. The decision, in terms of an allocated bandwidth, may serve as an input to a bandwidth management system 407 and to an audit generator 409 . [0195] Once a bandwidth level or a priority or any other form of decision has been allocated, the system may make use of any one of various bandwidth management tools in order to execute the policy, e.g., the methods described in U.S. Pat. Nos. 6,046,980, 6,085,241, 5,748,629, 5,638,363 and 5,533,009, the contents of which are hereby incorporated by reference. [0196] Reference is now made to FIG. 5, which is a simplified schematic illustration of a subsystem for policy enforcement using a standard bandwidth management tool. Input packets (or an equivalent suitable format in a suitable medium), possibly carrying indications of a corresponding allocated bandwidth, serve as an input to a priority allocator 5071 , which preferably determines either the order in which the packet enters a queue 5073 for output, or the order in which the packets leave the queue 5074 for output. The packets preferably leave the queue at a rate that corresponds to the allocated bandwidth, and reach the interface to the transport layer 5075 and then the transport layer itself - 5076 . [0197] The above-described embodiments provide a solution for content that is not encrypted. However, unauthorized users may easily circumvent the above system using standard encryption methods. Very strong cryptographic software is prevalent on the Internet, and it is practically impossible to decrypt such content without having a respective decryption key. Reference is now therefore made to FIG. 6, which is a simplified block diagram illustrating a subsystem for detection of encrypted content. The subsystem preferably determines the presence of encrypted content on the basis of information in the packet header and on the statistics of the payload. In many cases e.g., SSL and TLS, the headers contain information about the encryption method, and identification of the encrypted content can be done based on the header information alone. A format identifier 703 is accordingly provided to carry out identification of such information in the header. In other cases, the statistics of the payload may be used in order to determine whether the content is encrypted or not. In general properly encrypted data tends to have a statistical distribution of maximal entropy, which is to say minimal redundancy. Thus an entropy measurement can be used as an indication of the presence of encrypted data. In order to carry out an entropy measurement, a portion of the content is accumulated in a buffer/accumulator 70213 . An encoding format, if indicated in the header information, is identified by the format identifier 703 . If the content has been compressed using a standard (usually lossless) compression method, e.g. “zip”, then it may first be decoded using a multi-format lossless compression decoder (or a decoder for the specific format) 7031. The statistics of the content is thereafter analyzed using a statistical analyzer 704 and the entropy of the bitstream is estimated 7041. Detection of encrypted content and a corresponding confidence level for that detection are thereafter estimated using standard statistical tests for randomness, possibly taking into account inputs from the format identifier. [0198] In some cases the above analysis can be done without decompressing the file, usually based on the fact that most lossless compression algorithms are based on entropy considerations for bit allocation and similar concerns. [0199] The policy determinator 706 , which may be the same as policy determinator 106 in FIG. 1, preferably uses inputs including the encrypted content detection decision with the rules in the rule set 7061 in order to determine a corresponding enforcement policy. [0200] In general, encrypted content that corresponds to legitimate transportation between ordinary users is expected be of significantly smaller volume then the transportation volume that is used while exchanging illegitimate video content and multiple audio content. So a reasonable policy, that can reduce transportation of unauthorized multimedia content, with minimal interference to legitimate users, would be to allow a constant quota for encrypted transport, for example a few Mbs for an ordinary user. If the quota is exceeded then the allocated bandwidth may be significantly reduced or, alternatively, an extra charge may be levied. [0201] Note that for many applications a more selective approach may be taken, for example, in the case of sensitive confidential content, bandwidth is not generally a consideration, and the primary decision is whether to allow or to block the transport [0202] Reference is now made to FIG. 7, which is a simplified block diagram of a further embodiment of the present invention. The embodiment of FIG. 7 is similar to that of FIG. 1, but additionally comprises a multimedia detector 70211 that filters arriving packets for multimedia content. As a result of the application of the filter, it is possible to isolate the multimedia content for inspection for binary signatures etc., thereby reducing the load on consequent stages. Detection of multimedia content is preferably carried out on the basis of the information in the file, packet or other entity header. [0203] The multimedia detector 70211 is preferably located at an inspection point 702 . The inspection point 702 is preferably otherwise identical to the inspection point 102 of FIG. 1. The remainder of FIG. 7 is the same as FIG. 1 and will not be described again. [0204] Reference is now made to FIG. 8, which is a simplified schematic diagram showing an arrangement for inspecting traffic content over a variety of protocol layers. In general, network traffic may be addressed in various layers. The standard ISO OSI(open system architecture reference model) introduces seven protocol layers: physical, data-link, network, transport, session, presentation and application. In order to gather more information and to increase the reliability of the analysis, traffic analysis may be performed at several of the protocol layers. However, having analysis results from different layers raises a problem known as the association problem, namely how to gather the different analysis results from the various layers and associate them together to draw conclusions regarding transfer of possibly unauthorized content. [0205] In order to deal with the above-described association, a preferred embodiment of the present invention introduces a concept, which is referred to herein by the term atomic channel. Generally, a single communication between two parties may comprise one or more links and numerous data and control packets. The atomic channel is the single communication comprising all of these parts. Information in the various packet headers, at different levels or layers of the transport protocol allows the different packets (or other elements) of a single communication to be associated together. In order to achieve such an association an atomic channel is given a traffic state which enables it to achieve the above-mentioned association, as will be described in more detail below. A simple atomic channel may, for example, be a single TCP connection. The skilled person will of course be aware that in many current file sharing schemes the TCP connections are considered sub atomic, for example in an FTP transfer, two such connections, DATA and CONTROL, are used, the two connections together forming one atomic channel. More complex examples include file-sharing networks, where monitored connections may contain information pertaining to many transfers, between many users, none of the users being on either end of the connection. Furthermore, multiple unrelated, monitored, connections may contain information about a single transfer. The information in all of the unrelated connections may thus need to be correlated in order to obtain information about the transfer, and such correlation may need to be carried out in an uncertain or untrustworthy environment. The uncertainty may be due to incomplete monitoring, or efforts by the designers or users of the network to thwart monitoring of the network. [0206] In the example of a single TCP connection, the participants' IP addresses may be gathered from layer 3 information. Layer 4 information may be used to determine information about a second stream, that is to say to find signs of use of a two way channel, so that the entire interaction may, according to the situation, be completely reconstructed. In other circumstances, fragments of the streams may be reconstructed. The skilled person will be aware that state information is important, both to construct the streams, and to correlate them with each other. State information may be especially useful as a basis for understanding connection negotiation information, which may be, and preferably often is, analyzed as higher OSI layer information. For example in the case of an FTP transfer, the control information stream may be used to attach a file name and location to the transferred file and may be used to discern between numerous files. In the case of a complex file-sharing network, high-layer state information may be used to correlate between high-layer messages of the network, additional information may be used to discern the contents encoding, or encryption if present. Such additional information may be taken from layers 5 and 6 and sometimes from layer 7 , particularly in the case of a virtual file-sharing network. [0207] In cases such as that of a peer-to-peer network, alternatively or additionally to using the above-described atomic channel, information may be gathered about separable but possibly unrecognizable entities. Thus, over the course of the monitoring, enough information may be gathered to obtain a meaningful notion of the transfer, and/or on the structure and/or of the aforementioned entities. [0208] Returning to FIG. 8, there is illustrated therein an arrangement for carrying out multi-layer inspection of a transport protocol. Two-way or sometimes multi-way traffic 801 may be gathered from a point or agent on the network being monitored. The system preferably makes use of a plurality of monitoring agents situated at strategic locations on the network. The gathered data is analyzed by multi-layer analyzer 802 . The analysis may be performed in OSI layers 1 - 7 or part thereof, using layer specific data analyzers 8023-8027. The skilled person will appreciate that layer 1 may be relevant only in hardware implementations. The skilled person will be aware that the present embodiment is merely exemplary and that different file transfer networks may use other transport models such as an encapsulated transport layer over the application layer. [0209] Results from the layer specific analyzers preferably reach traffic state associator 8020 in disorganized fashion, meaning that results from different layers for different communication channels are all mixed up together. The traffic state associator determines which results belong together with which other results and traffic analysis results that correspond to any given communication channel are associated together by being assigned with a specific state channel. The data, thus arranged channel wise, preferably serves as input to the traffic analysis system 803 which is similar to the traffic analysis systems described above, and results from the traffic analysis system preferably serve as input to decision system 806 to be used in decision making regarding enforcement policy, for carrying out by the traffic control system 807 . [0210] It is noted that many of the elements specified hereinabove, may, , be omitted partially or entirely from any specific implementation. For example: a specific application may omit the rule base or exchange it for a constant behavior logic. [0211] It is pointed out that the above described embodiments, or variations thereof, are applicable to other similar fields, and not only to copyright protection, and protection of other sensitive or confidential material. For example, such a variation may be used to create automatic transcripts of communications over a virtual or high layer messaging network, where other communications which the law enforcement agency is not authorized to intercept i.e. other communication types, modes or communication between law abiding individuals are intercepted by a sniffing or like mechanism. That is to say the system could be used to inspect all transport on the network and report to the law enforcement agency only the information that it is authorized to intercept. [0212] Other fields of application may include analysis of complex distributed system behavior, for example the debugging of shared memory used in a distributed system, or for networking research purposes. [0213] The above embodiments thereby provide a powerful tool that can be used for other purposes as well: e.g., in order to monitor outgoing transport from a restricted zone such as a local area network of a corporate organization. The organization may be concerned that industrially sensitive information is being sent out via the network. In such a case, a system similar to the system illustrated in FIG. 1, with a database of signatures of confidential or otherwise restricted materials may be used in order to identify and possibly block the transport of the materials. Such an implementation is useful since the present peer-to-peer networks effectively create an alternative internet that renders many of the current standard firewall techniques ineffective. [0214] The present embodiments, or variations thereof may also be used in combination with certifications methods and techniques in order to allow un-inspected, un-restricted or otherwise privileged usage to certificated users. Such certification is useful in reducing the load on the system. [0215] The present invention may also be used in order to accumulate consumption statistics and/or other useful statistical analysis of the analyzed transport. [0216] Reference is now made to FIG. 9, which is a simplified block diagram of a series of network elements and showing a system for controlling the distribution of predetermined content over a network, according to a preferred embodiment of the present invention. The system comprises a series of elements, including a central control 910 , and one or more of the following inspection/monitoring points: an internal mail server 920 , an external mail server 930 , a LAN 940 , an external traffic router 950 , a web proxy 960 , a firewall 970 and an FTP proxy 980 . The system is able to monitor passing traffic at various of the above mentioned elements in the network. For example, while monitoring traffic within a corporate network, the system may monitor the traffic in one or more of the following entities: the external mail server 930 the external traffic router 950 , the web proxy 960 , the firewall 970 , the FTP proxy 980 and the print server 990 etc. At each point, extracts of data may be obtained using respective monitors of the entity ( 9201 , 9301 , 9401 , 9501 , 9601 , 9701 , 9801 and 9901 ) Signatures are then extracted from the data in any of the ways explained above and transferred to the central control of the monitoring system 910 . The signatures are then analyzed by the signature analyzer 9101 and compared with stored signatures to determine whether the monitored transport shows any significant level of correspondence with any of the content items represented by the stored signatures. The level of comparison may be determined by the policy manager 9102 . It is pointed out that the correspondence does not have to be determined on the basis of individual signature comparison, e.g., multimedia content items are usually long, and individual parts of entirely unrelated items may be identical. However, in some of the more sensitive content items, even a relatively short portion of the content may be sensitive, and the policy manager should preferably contain information allowing the identification of such portions. Thus the comparison is preferably carried out in batch fashion or in serial cumulative fashion as described above. The output of the analysis and comparison is then used by the policy manager 9102 in order to determine which action will be taken: e.g., blocking transport, not allowing printing of the document, auditing, reducing available bandwidth, automatically sending a message to the offender, instructing, when possible, the monitoring entity (especially in the case of an E-mail server, and the various proxies), to change the content (e.g. to remove sensitive parts, reduce the quality of copyrighted material, to add a textual or other copyright warning, etc.) etc . . . [0217] In a preferred embodiment of the present invention, printer servers 990 and/or printers 9902 may include monitoring and control 9901 of printer jobs, preferably with an ability to block or modify printer jobs, in order to prevent unauthorized printing of sensitive documents. [0218] Note that the concept of the atomic channel described above may consist of utilizing data from several such sources in order to form the information of such a specific channel. For example, peer-to-peer traffic may utilize Web, E-mail or FTP transport facilities for the actual transport, but may use TCP to search for files. [0219] It is also pointed out that control, either direct as described in FIG. 9, or indirect through configuration or otherwise, of the firewall and similar entities (e.g., VPN server, etc.) may consist of instructing it to prevent circumvention of the other monitoring entities, e.g. force Web, E-mail and FTP traffic to use the monitored proxies and servers. Furthermore, encapsulated traffic that tries to circumvent those entities by the usage of encapsulation can be detected, and thereby blocked, monitored or redirected, by the multi-level inspection methods described above. In another embodiment of the present invention, the policy manager 9102 preferably instructs the monitoring entity to attempt to remove hidden messages (steganograms) by using methods that do not require the identification of the hidden messages to be removed. Such methods may be as simple as adding noise or other slight distortions to the content part of the file. A slight distortion of the content part of the file is generally sufficient to destroy the steganogram without affecting the legitimate content. Another method may comprise embedding a possibly random steganogram that renders any underlying original message unreadable. [0220] Reference is now made to FIG. 10, wherein there is illustrated a further embodiment of the system described in FIG. 9, specifically for preventing copying of classified documents using a photocopy machine. In this embodiment, a central control of a monitoring system 1010 is connected to a controller 10951 of copy machine 1095 . Many modem copy machines contain a scanner that transforms the copied document into a digital image. The textual content of the document may be extracted from the digital image using a standard Optical Character Recognition (OCR) technique. After extraction, the textual content or derivatives thereof can be analyzed using a signature analyzer 10101 in order to determine whether the content comprises an unauthorized document. The output of the analysis is then used by a policy manager 10102 in order to determine whether to take action and if so, what action: e.g., not allowing photocopying of the document, auditing, sending a message to the offender, etc. [0221] It is pointed out that signature extraction may be carried out in a centralized manner in the signature analyzer 9101 / 10101 , or may alternatively be carried out in a distributed fashion, for example in the various monitors. The latter may advantageously reduce communications because the extracted signatures are smaller than the original content. Furthermore, signature caching and other similar methods may be carried out in the distributed entities to further reduce communication volume and thereby enhance performance. [0222] Reference is now made to FIG. 11, which is a simplified block diagram illustrating a further embodiment of the present invention which utilizes local monitoring and control located in user stations. The local monitor/control 11971 may be based on a software (or hardware) agent that resides within user stations 1197 . The local monitor/control 11971 may include a local database 119711 . In a preferred embodiment, the monitor may detect events such as printing, saving to portable media (e.g. diskettes), use of the “print screen” command etc . . . , and may analyze content sent (e.g., via the local printer controller 119721 , via the portable media controller 119712 , “print screen” controller etc . . . ). If it turns out that there was an attempt at unauthorized printing or saving of unauthorized material to portable media etc . . . , then the local monitor & control 11971 unit may report the details to the central control 1110 . The policy manager 11102 may thereafter select an action to be taken and may send a message, or other indication accordingly, to the local control 119711 , which thereafter may use the controllers 119712 and 119721 in order to execute the policy. It is noted that in order to prevent malicious tampering with the locally based software agent referred to above, tamper resistance methods may be used. It is further noted that both hardware and software tamper resistance solutions are available. Generally, software solutions are the most easily manageable, however the hardware solutions are usually more robust. [0223] It is noted that the distributed nature of the system may require automatic or pseudo-automatic updating of the distributed components. [0224] It is further noted that encryption and authentication may be used in communications between elements in order to secure the communications. [0225] It is appreciated that one or more steps of any of the methods described herein may be implemented in a different order than that shown, while not departing from the spirit and scope of the invention. [0226] While the methods and apparatus disclosed herein may or may not have been described with reference to specific hardware or software, the methods and apparatus have been described in a manner sufficient to enable persons of ordinary skill in the art to readily adapt commercially available hardware and software as may be needed to reduce any of the embodiments of the present invention to practice without undue experimentation and using conventional techniques. [0227] A number of features have been shown in various combinations in the above embodiments. The skilled person will appreciate that the above combinations are not exhaustive, and all reasonable combinations of the above features are hereby included in the present disclosure. [0228] While the present invention has been described with reference to a few specific embodiments, the description is intended to be illustrative of the invention as a whole and is not to be construed as limiting the invention to the embodiments shown. It is appreciated that various modifications may occur to those skilled in the art that, while not specifically shown herein, are nevertheless within the true spirit and scope of the invention.
A system for network content monitoring and control, comprising: a transport data monitor, connectable to a point in a network, for monitoring data being transported past said point, a signature extractor, associated with said transport data monitor, for extracting a derivation of said data, said derivation being indicative of content of said payload, a database of preobtained signatures of content whose movements it is desired to monitor, and a comparator for comparing said derivation with said preobtained signatures, thereby to determine whether said payload comprises any of said content whose movements it is desired to monitor. The monitoring result may be used in bandwidth control on the network to restrict transport of the content it is desired to control.
7
REFERENCE TO RELATED APPLICATIONS This application is co-pending with application Ser. No. 12/764,797 entitled Determining Landing Sites For Aircraft filed on Apr. 21, 2010, application Ser. No. 13/196,826 entitled Flight Interpreter For Captive Carry Unmanned Aircraft Systems Demonstration and application Ser. No. 13/196,844 entitled Enhanced Delectability of Air Vehicles for Optimal Operations in Controlled Airspace filed substantially concurrently herewith, all having a common assignee with the present application, the disclosures of which are incorporated herein by reference. BACKGROUND INFORMATION 1. Field Embodiments of the disclosure relate generally to the field of controlled flight for manned and unmanned aircraft systems, and more particularly a system and method for using on-board sensors to identify areas in the terrain in proximity to a manned aircraft or unmanned aircraft system (UAS) that have reachable landing site(s). The system manages the UAS or manned aircraft to a safe landing site in engine-out or other emergency conditions, and determines the best landing site taking into consideration the aero-performance and kinematic characteristics of the aircraft in its current operational state, the profile and extent of the terrain, and obstacle avoidance. It then generates and displays and/or implements the best path (course) to the landing site. 2. Background Aircraft, particularly light aircraft and UAS, often fly over terrain in which a requirement for landing at a location other than the intended landing site due to an in-flight emergency or other situation presents a significant challenge. The problem of selecting a suitable emergency landing site is a complex issue that has been exacerbated by the continued growth of previously undeveloped, underdeveloped, and/or unoccupied areas. During an inflight emergency, pilots have previously been limited to using their planning, experience, vision, and familiarity with a given area to select an emergency landing site. During an emergency situation, a pilot may have little time to determine that an emergency landing needs to be executed, to find or select a suitable landing site, to execute other aircraft emergency procedures, to prepare passengers, and to then pilot the aircraft to the selected landing site. Currently there is no method for autonomously determining an adequate landing site for an aircraft in duress or directing the aircraft there. It is therefore desirable to provide a method and system for autonomously identifying areas in the terrain in proximity to an aircraft that have reachable landing site(s) for contingency operations such as engine-out or other emergency conditions, detecting and determining the best landing site taking into consideration the aero-performance and kinematic characteristics of the aircraft in its current operational state, the profile and extent of the terrain, and obstacle avoidance and providing that information for implementation by the pilot or aircraft systems. SUMMARY Embodiments described herein provide a system for autonomous direction of an aircraft to emergency/contingency landing sites which incorporates a terrain mapping sensor and an onboard processor receiving terrain data from the terrain mapping sensor. The processor employs software modules for processing the terrain data to produce a terrain map and for creating a landing profile based on the terrain map. The embodiment allows a method for autonomous direction of an aircraft to emergency/contingency landing sites wherein an onboard sensor is used for selecting potential landing sites and a landing profile is generated based on a selected one of said potential landing sites. In a particular embodiment, the method provides for initiating a terrain mapping sensor and sensing of local terrain in proximity to the aircraft with the terrain mapping sensor receiving actual terrain environment data. The terrain environment data is then processed into a digital terrain map and potential landing sites are determined based on the sensed terrain identified in the map taking into account surface characteristics corresponding to landing site criteria. Landing sites are then loaded into a landing site library. If a forced landing is imminent a landing site best meeting a set of constraint criteria is chosen. A route to the chosen landing site is calculated employing the constraints data and the calculated route is flown to execute a landing. The features, functions, and advantages that have been discussed can be achieved independently in various embodiments of the present invention or may be combined in yet other embodiments, further details of which can be seen with reference to the following description and drawings. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1A is a pictorial view of elements of an example embodiment; FIG. 1B is a terrain map detail; FIG. 2 is a flow chart showing operation of the embodiment; FIG. 3A is a horizontal display of landing path routing; FIG. 3B is a vertical display of landing path routing; FIG. 4A is a selected first routing path; FIG. 4B is a modified selected routing path; and, FIG. 5 is an instrument display of a “fly to” path for pilot direction. DETAILED DESCRIPTION The embodiments described herein provide a system and method for using on-board sensors (such as or Light Detection and Ranging (LIDAR) or a Synthetic Aperture Radar (SAR)) as a means to identify areas in the terrain in proximity to a manned aircraft or unmanned aircraft system (UAS) that have reachable landing site(s) for contingency operations such as engine-out or other emergency conditions. The system detects and determines the best landing site, taking into consideration the aero-performance and kinematic characteristics of the aircraft in its current operational state (e.g. loss of aero performance or loss of engine); the profile and extent of the terrain, and obstacle avoidance. The best path (course to the landing site is then generated and displayed to the pilots, including waypoints and margins. In the case of a UAS, the system will autonomously command and control the aircraft to the optimal landing site. Referring to FIG. 1A , an example embodiment consists of two primary subsystems. First, a terrain mapping sensor 10 (LIDAR, SAR, etc.) is mounted on an aircraft 12 in such a manner that it has 360 degree view of the local terrain 11 . An onboard processor 14 receives and translates raw data streams from returns by the mapping sensor 10 into a terrain map 16 (shown in greater detail discussed subsequently with respect to FIG. 1B ) that can be analyzed for profile, extent and obstructions to determine optimal landing sites given the aero-kinematic performance of the aircraft, as will be described in greater detail subsequently. Second, a Safe Area Flight Emergency (SAFE) algorithm represented as 18 and as described in U.S. Pat. No. 7,689,328 entitled Determining Suitable Areas for Off-Airport Landings issued. on Mar. 30, 2010 and additionally described in U.S. patent application Ser. No. 12/764,797 entitled “Determining Landing Sites For Aircraft” filed on Apr. 21, 2010 is executed by the onboard processor. Depending on the application, appropriate processing and integration to the flight controls by the onboard processor is accomplished through connection to an autopilot 20 , in either a manned aircraft or a UAS application, or alternatively as visual displays in a cockpit instrument system for a manned aircraft with actual flight control input accomplished by the pilot. The processing power required by the onboard processor is dependent on 1) the efficiency of the SAFE algorithm and 2) the grid size chosen for the calculation to be performed. The finer the grid, the more processing is required. SAFE operates by generating spanning trees from the aircraft position to the desired landing site as described in application Ser. No. 12/764,797 entitled Determining Landing Sites For Aircraft. The best route is chosen based on rules such as staying above the minimum altitude required to make it to the site in a contingency operation. The processing sequence for the embodiment described is shown in detail in FIG. 2 . Upon takeoff, step 202 , the terrain mapping sensor 10 is initiated, step 204 . Sensing of local terrain in proximity to the aircraft is accomplished by the terrain mapping sensor receiving actual terrain environment data, 205 , and processing it into a terrain map (e.g., digital terrain map), step 206 . As show in FIG. 1B , the terrain map may be a combination of predetermined geographical data with updates provided by the terrain mapping sensor 10 , General terrain profiles 40 A and 40 B are presented and potential landing sites such as existing airports 42 , 44 , roads 46 , open flat terrain with minimal vegetation such as areas 48 , and man-made obstacles such as power lines 50 . Potential landing sites are determined based on the sensed terrain identified in the terrain map, step 208 , taking into account surface characteristics corresponding to landing site criteria 210 (flatness, length, vegetation or prepared surface, unpaved, paved, etc). The potential landing sites are loaded into a landing site library, 212 , for use by the on-board processor 14 . The landing site library may also include a set of pre-loaded landing sites, 214 , prior to takeoff based on anticipated route or other predetermined criteria. The determination of potential landing sites also employs current aircraft performance data, 216 , for real-time assessment of which landing sites in the library may be reached by the aircraft for landing under an emergency condition. While preloaded data may include some “unprepared or off-field” landing sites, the availability of accurate real-time sensing of data from the terrain mapping sensors allows confirmation of the status of such landing sites which are not normally maintained. Additionally, seasonal or real time changes to terrain such as crop harvesting, deforestation due to logging, newly added roads or other prepared geographic features that may now provide sufficient length, surface composition and accessibility to act as a landing site can be sensed by the terrain mapping sensors for update/verification of the landing sites data. If a forced landing is imminent, step 218 , the processor chooses a landing site, step 220 , best meeting a set of constraint criteria data, 222 . Constraints may include mission defined criteria (security requirements, material hazards or other exposure constraints), communications link continuity for continued communications between the aircraft and ground controllers, battery longevity (life of communications and control capability), actual winds and weather conditions, actual aircraft performance including degradation based on the emergency condition, runway or landing zone type and length, and obstructions proximate the landing zone. Landing site selection from the landing site library includes both preloaded and real-time data from the terrain mapping sensor. Once the landing site has been selected, the processor calculates a route to the chosen landing site, step 224 , again employing the set of constraint criteria data, 222 . Landing route selection may include determinations of overflight issues due to mission defined criteria (as an example: no populated area overflight), and geographical considerations. As shown in FIGS. 3A and 3B , from the air vehicle current position 302 to potential landing sites 304 A or 304 B, ground tracks 306 A and 306 B may be established based on geographical or other constraints data while requirements for vertical profiles 308 A and 308 B may be determined based on air vehicle performance constraints. The route determination may be based on spanning tree calculations as described in application Ser. No. 12/764,797 entitled “Determining Landing Sites For Aircraft”. A selected route 402 A may then be modified as shown in FIGS. 4A and 4B to route 402 B to achieve a specific route point 403 but accommodate requirements imposed by terrain 404 or physical feature avoidance such as a town 406 . Real time terrain mapping sensor data may be employed in the route calculations to update pre-loaded landing site data. The route is then flown, step 226 , by the autopilot 20 in either a UAV or piloted aircraft, or route data may he provided to a cockpit display 500 providing a “fly to” profile 502 with guidance boxes 504 as shown in FIG. 5 for guidance to the pilot of a piloted aircraft. A landing is then executed at the selected landing site, step Having now described various embodiments of the invention in detail as required by the patent statutes, those skilled in the art will recognize modifications and substitutions to the specific embodiments disclosed herein. Such modifications are within the scope and intent of the present invention as defined in the following claims.
A system for autonomous direction of an aircraft to emergency/contingency landing sites incorporates a terrain mapping sensor and an onboard processor receiving terrain data from the terrain mapping sensor. The processor employs software modules for processing the terrain data to produce a terrain map and for creating a landing profile based on the terrain map.
6
TECHNICAL FIELD The present invention is generally directed to an article for the identification of the premature rupture of a membrane during pregnancy. More particularly, the present invention is directed to an indicating article in the form of a multilayered pad that is fitted to the undergarment of a user. The multilayered pad includes a treated component which responds to the presence of amniotic fluid as a discharge. BACKGROUND ART The amnion develops around the embryo during the second week following fertilization. This is the second membrane to appear after the placenta forms around the chorion. The margin of the amnion is attached to the periphery of the embryonic disk. Eventually, as the embryo grows, the amnion fuses with the chorion surrounding it, and the two membranes become a single amniochorionic membrane. Amniotic fluid fills the amniochorionic membrane to provide a watery environment to define a protective space for the growing embryo. Ordinarily the amniochorionic membrane acts as a primary barrier to bacteria and other potentially damaging organisms by providing a protected, substantially sealed environment throughout the development of the embryo until it ruptures subsequent to the onset of labor. However, this environment is occasionally compromised when it is prematurely ruptured prior to the onset of labor. Technically, premature rupture of the membrane can occur at any time during the forty weeks of gestation. Although definitions vary, "premature rupture of the membrane" refers to rupture of the amniochorionic membrane prior to the onset of labor at any time. In either case, a ruptured membrane poses a considerable risk of infection to both mother and fetus. Occasionally, rupturing of the membrane follows invasive techniques such as amniocentesis and may lead to infection of the developing fetus. This rupture occurs in about 1 out of every 200 procedures. For women undergoing an amniocentesis in the second trimester, detection of a rupture of the membrane is critical. A gross rupture of fluid could be potentially catastrophic for the developing fetus, as adequate amniotic fluid is a necessity to assure proper lung development, especially prior to 23 weeks. Beyond the obvious compromise of the membrane caused by amniocentesis, the exact cause of premature rupture is not known. Possible causes include infection, cervical incompetence, and decreased strength of the membrane. Regardless of the cause, with the premature rupture of the membrane, the fetus must be promptly delivered when the mother becomes clinically infected or the fetus shows signs of potential compromise. In either situation, if left untreated, possible death to the fetus and the mother could result. It is noteworthy that chorioamnionitis is present in about 5 to 10 percent of all deliveries and, significantly, is the reason for about 10 percent of all perinatal deaths. In the event of premature rupture of the membrane, the timing for the delivery of the baby becomes critical, as the risk of intrauterine infection increases significantly as more time passes following rupture. Accordingly, it becomes critical to provide a method of early detection of rupture. The problem is that leaking amniotic fluid--the telltale sign of rupture--is frequently confused by the mother with her own urine or vaginal discharge. (The leakage of urine during pregnancy [particularly during the latter stages] is frequent due to increased pressure on the bladder, thus adding to the overall incidence of false positives.) This results in many false alarms and unnecessary trips to either the doctor's office or to the hospital for evaluation of the pregnant woman to rule out possible rupture of the membrane. These trips lead to wasted time and energy on the part of both the patient and the physician as well as considerable expense to the health care system. A hospital audit revealed an average cost of $250.00 per visit to rule out rupture of the membrane. Once the pregnant woman identifies leakage, today she has no practical choice but to visit her physician. Because the presence of leaking urine is fleeting, the attending physician must undertake one or more tests in the office to determine whether or not there has been a rupture of the membrane. The conventional test is for the physician to observe the cervix after employing a speculum in an effort to identify pooling of fluid behind the cervix. The physician then applies a swab of pH paper held by a forceps to the fluid located in the area of the cervix to determine whether or not amniotic fluid is present by observing a change in color. Amniotic fluid is alkaline and the pH paper reacts to its presence by turning purple-blue. While functional, the examination is far more often than not unnecessary. It is also impractical, leading to particular discomfort for the patient and lost time for the physician. Other in-office or in-hospital tests for the presence of amniotic fluid are known. For example, in U.S. Pat. No. 4,357,945, issued on Nov. 9, 1982 to Janko for DEVICE FOR TESTING AND RUPTURING AMNIOTIC MEMBRANE, a finger-mounted medical testing device is disclosed which tests the intactness of the amniotic membrane. The device of Janko is provided with a pH-responsive material. Upon insertion into the cervix, the indicator material is exposed to the local environment. In U.S. Pat. No. 5,425,377, issued on Jun. 20, 1995 to Caillouette for PH MEASUREMENT OF BODY FLUID, a swab is provided which includes a pH indicator for measuring the pH of vaginal moisture. Other techniques for use in-office or in-hospital are provided in: U.S. Pat. No. 5,281,522 issued on Jan. 25, 1994 to Senyei et al. for REAGENTS AND KITS FOR DETERMINATION OF FETAL FIBRONECTIN IN A VAGINAL SAMPLE; U.S. Pat. No. 5,096,830, issued on Mar. 17, 1992 to Senyei et al. for PRETERM LABOR AND MEMBRANE RUPTURE TEST; and U.S. Pat. No. 5,554,504, issued on Sep. 10, 1996 to Rutanen for DIAGNOSTIC METHOD FOR DETECTING THE RUPTURE OF FETAL MEMBRANES. While these various methods provide approaches to testing for amniotic fluid, they do not overcome the basic problem of requiring a professional medical technician to deal in-office or in-hospital with the administration of relevant tests. Further complicating the scenario is the fact that a ruptured amniotic membrane may lead to only a temporary leakage of amniotic fluid, with another leaking episode to occur at a later time. In the meantime, the patient may become infected, with the potential result of great injury to both the baby and the mother. It is therefore an object of the present invention to overcome the disadvantages associated with known techniques for identifying leaking amniotic fluid and possible rupture of the amniochorionic membrane. It is a further object of the present invention to provide an article which allows the early identification of the discharge of amniotic fluid without the necessity of a visit to a doctor's office or a hospital. Yet another object of the present invention is to provide such an article which may be used with minimal inconvenience to the user. Still a further object of the present invention is to provide such an article which is worn like a sanitary napkin or pad and which may also provide the function of such sanitary items. Finally, in these times of cost containment, the potential savings from a device which could eliminate unnecessary visits to the physician's office or to the hospital could be tremendous. An additional object of the present invention is to provide such an article which can minimize false positives and have a substantial impact on and impart an economic benefit to the health care system. SUMMARY OF THE INVENTION The present invention achieves these objectives in an indicating device that comprises a pad having an upper outer layer, a lower outer layer, and an intermediate pH-responsive layer. A double-sided adhesive strip is attached to the lower outer layer. The upper outer layer and the lower outer layer are attached substantially the same size and are attached to one another along their peripheral edges. The upper outer layer and the lower outer layer are preferably composed of a non-woven material, such as a spunbonded material, or may be composed of a webbed construction which provides the device with bulk and loft. Optionally, the lower outer layer, which comprises the lower undergarment contacting surface, is comprised of a polymerized barrier film. The upper outer layer and the lower outer layer define substantially the same width and length. The overall size of the article may be adjusted as desired. The article may or may not be designed to achieve a high absorbency function. (While not necessary directed to absorbency as in a menstrual pad, the article of the present invention may be configured so as to provide this added function.) Intermediate of the upper out layer and the inner outer layer is a pH-sensitive layer. This intermediate layer is a pH-sensitive material and may be one of a variety of such materials, although a preferred material is NITRAZINE® chemical indicator paper (trademark; Bracco Diagnostics, Inc, Eae Princeton N.J. In the presence of an alkaline fluid, such as amniotic fluid, the pH-sensitive material responds by turning to a purple-blue color. The change in color acts as a visual indicator to the wearer. Conversely, a change to the other end of the Color Scale, such as a yellow, indicates acidity, indicating to the wearer that a normal condition is present. Fitted to the lower outer layer is at least one fastening adhesive strip which provides an adhesive attachment means for attaching the article to the underwear of the user. As an alternate embodiment of the present invention, a dropper bottle containing a pH-sensitive liquid may be provided. The liquid is selectively placed on a feminine pad and the pad is worn in its usual manner. As with the article defined above, a change in color to the purple-blue end of the Color Scale indicates that amniotic fluid may be present in the wearer's discharge. Other objects and advantages of the present invention will be made apparent as the description progresses. BRIEF DESCRIPTION OF THE DRAWINGS The various advantages of the present invention will become apparent to one skilled in the art by reading the following specification and appended claims and by referencing the following drawings, in which: FIG. 1 is a perspective view showing the manner of placing the indicating article of the present invention to an undergarment; FIG. 2 is a perspective view of the article of the present invention with its upper outer layer partially peeled away from the lower outer layer to reveal the intermediate pH-sensitive layer; FIG. 3 is a transverse cross-sectional view of the indicating article of the present invention taken along lines 3--3 of FIG. 2 illustrating its multilayered construction; FIG. 4 is a top plan view of the indicating article of the present invention demonstrating to the wearer the presence of an acidic flow; FIG. 5 is a view similar to that of FIG. 4 but demonstrating to the wearer the presence of an alkaline fluid; and FIG. 6 is a perspective view of an alternate embodiment of the present invention in the form of a pH-indicating fluid being distributed on a feminine hygiene pad. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT A preferred embodiment of the indicating article of the present invention for use in an undergarment is shown throughout the figures. With respect first to FIG. 1, the article of the present invention, generally illustrated as 10, is shown in place within an undergarment 12. The article 10 includes an elongated body 14. The undergarment is of the type commonly worn by many women and well-known as a panty. It comprises a front section 16, a back section 18, and a crotch portion 20 which joins the front and back sections 16 and 18, respectively. The article 10 is utilized by removing its release paper (shown in FIG. 3 and discussed below in relation thereto) and thereafter placing it in the undergarment 12. The elongated body 14 of the indicating article 10 is placed in the crotch portion 20 of the undergarment 12 with a first end 22 extending toward the front section 16 and a second end 24 toward the back section 18 of the undergarment 12. The lower outer layer of the article 10 is in contact with the inner surface of the center crotch portion 20 of the panty 12. The adhesive strips maintain the elongated body 14 in position. FIG. 2 is a perspective view of the article 10. The article 10 includes an upper outer layer 26 and a lower outer layer 28. The layers 26 and 28 may be made of a non-woven material, such as a spunbonded material. Alternatively, the layers 26 and 28 may be composed of a webbed construction which provides the device with bulk and loft. The upper outer layer 26 is preferably liquid permeable to allow body fluids to substantially pass. The upper outer layer 26 is also in contact with the wearer's skin. Accordingly, the upper outer layer 26 is preferably composed of a compliant, soft-feeling material that is non-irritating to the parts of the user's skin with which it is in contact. The upper outer layer 26 can be made from any of the materials conventional for this type of use. Non-limiting examples of suitable materials that can be used as the upper outer layer 26 are non-woven cotton, polyester, polyethylene, polypropylene, nylon and rayon and formed thermoplastic films. The preferred type of material is a spunbonded one that is pervious to liquids but is nevertheless non-absorbent. The particular material is selected so that the surface of the upper outer layer 26 remains dry and is thus more comfortable to the wearer. The recommended thickness of the upper outer layer 26 is between 1 and 2 mils with the preferred thickness being about 1 mil. The lower outer layer 28, which comprises the lower undergarment contacting surface, may be comprised of a polymerized barrier film. In this embodiment, the lower outer layer 28 may be composed of a polyethylene film such as that offered by the Clopay Corporation (Cincinnati, Ohio.) under the designation P18-0401 and by Ethyl Corporation (Terre Haute, Ind.) under the designation XP-39385. The upper outer layer 26 and the lower outer layer 28 may be composed of selected materials so as to provide a mere carrier for the pH-sensitive component or may be composed of material such that the article 10 acts additionally as a sanitary napkin, capable of absorption of body fluids. In this situation, the upper outer layer 26 would still be composed of a liquid permeable material. However, the lower outer layer 28 would be entirely or partially composed of an absorbent material or an additional absorbent layer (not shown) would be added between the upper outer layer 26 and the lower outer layer 28 with the pH-sensitive component (discussed below with respect to FIG. 2) fitted adjacent the upper outer layer 26. Where absorbency is desired to allow the article 10 to double as an absorbent pad, a suitable absorbent, hydrophilic fiber intended to absorb and contain liquid may be used. Examples of suitable hydrophilic fiber material include cellulose, modified cellulose, rayon, polyesters such as polyethylene terephtalate (DACRON [trademark]), hydrophilic nylon (HYDROFIL [trademark]), and the like. The selection of the particular material is only controlled by the desired absorbent capacity of the absorbent material. The upper outer layer 26 and the lower outer layer 28 are joined along their peripheral edges by known methods of joining, including chemical bonding and physical stitching. As used herein, the term "joined" encompasses configurations whereby an element is directly secured to the other element by affixing the element directly to the other element, configurations whereby the element is indirectly secured to the other element by affixing the element to intermediate member(s) which in turn are affixed to the other element, and configurations whereby one element is integral with another element, i.e., one element is essentially part of the other element. The article 10 has a pair of opposed sides 30 and 32. The sides 30 and 32 are illustrated as being substantially parallel and linear, but it is to be understood that the sides 30 and 32 may be non-linear and may define any of a variety of curved lines. For example, the sides 30 and 32 may be configured so as to follow the curved, crotch area edges that define the leg holes of an undergarment. The overall dimensions of the article 10 may be varied as necessary depending on the size and style of the undergarment and the intended use of the article 10. For example, when the user is lying in the prone position, there is a tendency for body fluid to gravitate toward either the person's front side or back side, depending on which side the person is lying. The article 10 may accordingly be longer for this purpose, and may accordingly be particularly desirable for use by those at-risk women who are substantially bed ridden during the last weeks of pregnancy. However, with the longitudinal centerline of the article 10 representing the Y-axis and the transverse centerline representing the X-axis as oriented by reference to a planar Cartesian coordinate system, the preferred size of the article 10 is between 150 and 170 mm along the Y-axis (or the long axis) of the article 10 and between 100 and 125 along the X-axis or along the width of the article 10. The article 10 is provided with a pH-sensitive component 34. The component 34 defines a strip of a flexible material, such as a strip of NITRAZINE® chemical indicator paper, which effects a color change in accordance with acidity or alkalinity. The component 34 is fitted between the upper outer layer 26 and the lower outer layer 28. Accordingly, the selection of material for the upper outer layer 26 is limited only by the requirement that the material be selected from those of specific density or composure so as to permit the color of the component 34 to be visualized by the wearer by reference to the upper outer layer 26, that is, without having to disassemble the article 10 to verify the color. While NITRAZINE® chemical indicator paper is the preferred form of material for indicating pH, other pH indicators could be used as well. Such indicators may be selected from the group consisting of bromochlorophenol blue sodium salt, bromocresol green ACS, bromocresol green sodium salt ACS, bromocresol purple, bromocresol purple sodium salt, bromophenol blue ACS, bromophenol blue sodium salt ACS, bromopyrogallol red, bromothymol blue ACS, bromothymol blue sodium salt ACS, bromoxylenol blue, calceinifluroexon, calconcarboxylic acid, calmagite, chlorophenol red, o-cresolphthalein, o-cresolphthalein complexone, o-cresolphthalein complexone disodium salt, m-cresol purple, m-cresol purple sodium salt, cresol red, cresol red sodium salt, erichrome blue black R, ethyl orange sodium salt, fast sulphone black F, litmus powder, methyl orange ACS, methyl red free acid ACS, methyl red HCL ACS, methyl red sodium salt ACS, methylthymol blue, murexide powder, P.A.N., P.A.R., patent blue VF, phenolphthalein ACS, phenolphthalein ACS, phenol red ACS, phenol red sodium salt ACS, pyrocatechol violet, pyrogallol red, quinaldine red, SPADNS, thorin, thymol blue ACS, thymol blue sodium salt ACS, thymolphtahalein ACS, tropaeolin O, and xylenol orange tetrasodium salt ACS. FIG. 3 is a transverse cross-sectional view of the article 10 of the present invention taken along lines 3--3 of FIG. 2. This view illustrates the article 10 in place on the crotch portion 10 of the undergarment 12. The article 10 can be configured such that the upper outer layer 26 and the lower outer layer 28 are mere carriers for the pH-sensitive component 34, or may function simultaneously as a feminine napkin or pad or a panty liner or shield. A plurality of fastening adhesive strips 36 are provided on the underside of the article 10 for removable attachment to the undergarment 10. Any adhesive or glue used in the art for such purpose can be used herein, with pressure sensitive adhesives being preferred. Suitable adhesives are Century A-305-IV manufactured by the Century Adhesives Corporation and Instant Lok 34-2823 manufactured by the National Starch Company. As illustrated, a single fastening adhesive strip 36 is only of a width that is less than that of the elongated body 12 of the article 10. The adhesive strip 36 is covered with a release paper (not shown) to keep the strip 36 from sticking to extraneous surfaces prior to use. Any conveniently available release paper commonly used for such purposes can be used herein. Non-limiting examples of suitable release papers are BL 30 MG-A Silox EI/O and BL 30 MG-A Silox 4 P/O, both of which are manufactured by the Akrosit Corporation. To employ such a devise, the user would first remove a release paper and apply the article 10 with a slight pressure to the crotch area 20 of the undergarment 12. In use, the wearer removes the release tape (not shown) to expose the adhesive strip 36 of the article 10 and places the article 10 in the crotch portion 20 of her undergarment 12. The user then wears the undergarment 12 in the usual manner, adjusting or removing them occasionally as required to observe the color status of the article 10. A yellow color of the pH-sensitive component 34 as indicated in FIG. 4 demonstrates to the wearer the presence of an acidic flow and can be safely disregarded as urine. Conversely, a visualized purple-blue color of the pH-sensitive component 34 as illustrated in FIG. 5 would demonstrate to the wearer the presence of an alkaline fluid. As noted above, the alkaline fluid may be a false positive if seminal fluid or blood. However, the only other alkaline fluid possibly present would be amniotic fluid, indicating to the wearer that there is a possible rupture of the amniotic sac, whereupon a physician should be contacted. In any event, the wearer may dispose of the article 10 after use in a manner consistent with the normal disposal of a feminine pad or napkin. As an alternate embodiment of the present invention, a liquid form of the pH-sensitive component may be used. With reference to FIG. 6, a liquid form of the pH-sensitive component is housed in a bottle 38. The wearer (not shown) would apply a series of drops of the liquid material along the approximate mid-point of the upper, body-facing side of a pad or napkin 40. In this embodiment, the wearer would apply and use the pad or napkin 40 in a manner similar to that of the embodiment of FIGS. 1 through 5 described above. Those skilled in the art can now appreciate from the foregoing description that the broad teachings of the present invention can be implemented in a variety of forms. Therefore, while this invention has been described in connection with particular examples thereof, the true scope of the invention should not be so limited since other modifications will become apparent to the skilled practitioner upon a study of the drawings, specification and following claims.
An article for the identification of the premature rupture of a membrane during pregnancy is disclosed. The article comprises a pad having an upper outer layer, a lower outer layer, and an intermediate pH-responsive component. A double-sided adhesive strip is attached to the lower outer layer. The upper outer layer is composed of a liquid permeable material. Intermediate of the upper out layer and the inner outer layer is a pH-sensitive component. This intermediate layer is a pH-sensitive material and may be one of a variety of such materials, although a preferred material is nitrazine paper. In the presence of an alkaline fluid, such as amniotic fluid, the pH-sensitive material responds by turning to a purple-blue color. The change in color acts as a visual indicator to the wearer of the possible presence of amniotic fluid outside of the amniotic sac.
0
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates generally to communication systems utilizing a frequency shift keyed technique and more particularly, to an improved detection system using a tri-state phase detector. 2. Description of the Prior Art Many communication systems including those which utilize existing power lines use digital modulation techniques in signal transmission. One method of digital transmission is phase shift keyed (PSK) transmission. In PSK systems, the phase of the carrier wave is shifted by 180 degrees to indicate in binary a "mark" or "1" and transmitted without shifting to indicate a space or a "0". Another digital transmission technique which is becoming more important involves frequency shift keyed (FSK) modulation. This is the type employed in the present invention. In this type of a system, one frequency is used to indicate a "mark" or "1" and another distinct frequency to indicate a space or "0". Frequency shift keying involves the modulation of the base or carrier frequency to shift that frequency by predetermined increments in response to particular data to be transmitted. In a frequency shift keying system, the frequency shift phase is continuous, i.e., the transmitted signal is a sinusoidal signal which varies in frequency but has no time phase shift continuity. Normally, a binary "1" or a "mark" signal is transmitted at a frequency above a selected center or carrier center frequency or "carrier Plus" frequency and a space or binary "0" is transmitted at a frequency below the center frequency of the carrier or "carrier minus" frequency. In such systems the differential between a transmitted, and thus received frequency, and the center frequency of the carrier may be made equal to or greater than the modulation rate, also known as the data rate, or bit rate, divided by two. Systems for receiving frequency shift keyed transmission signals are well-known. Such systems must discriminate accurately between the carrier minus and carrier plus frequencies and reject spurious or "noise signals" which also may be transmitted. Many techniques and schemes have been used in the prior art in an attempt to achieve better, more accurate signal discrimination. These include the use of various input logic schemes in conjunction with bandpass filters, or the like to check for the presence or absence of certain frequencies. In the prior art, in order to achieve commercially feasible reliability, most discriminator schemes have had to be quite complicated. There has long been a need for simplification of these systems so that inexpensive reliable units would be available. It would be desirable to employ a system using a tri-state phase detector in conjunction with an integrating circuit, the output of which would be used as the input to a comparator which, in turn, would be utilized to activate a latch or other signal utilization means. In the prior art, however, it has been difficult, if not impossible, to provide reliable FSK discrimination using a tri-state detector in combination with an integrating circuit because of the lack of phase information between the output of the tri-state and the bit time. Thus, if the phase relationship is unknown, at least part of the information fed to the integrating circuit can be wrong and this, of course, can lead to a misinterpretation of the input data signal. SUMMARY OF THE INVENTION By means of the present invention, the problems associated with the use of a tri-state phase detector in conjunction with an integrating circuit to produce reliable FSK signal discrimination are solved by the provision of a method and apparatus which overcomes the drawbacks associated with the tri-state phase detector occasioned by lack of phase information between the input FSK signals and the known or reference signal input to the tri-state phase detector. It has been found that if a reference signal of known frequency, which may be the carrier frequency in an FSK system, and an unknown frequency which may be a carrier plus or carrier minus frequency are used as the inputs to a tri-state phase detector, after the signals undergo a phase crossing the signal confusion will clear. An output consisting of all positive pulses or all negative pulses depending on whether the known input frequency is higher or lower than the known reference frequency will be produced after such a phase crossing by the two input frequencies. If a "worst case condition" is assumed, such a frequency phase crossing occurs at least once in the "worst case time" or minimum clearing time. This time will be as follows: ##EQU1## The present invention provides a method and apparatus for operating the tri-state phase detector in conjunction with an integrating circuit in a manner which assures that the tri-state phase detector has cleared prior to enabling the integrater circuit to integrate the FSK tri-state phase detector output. At the start of each bit period or FSK modulation period, integration is not allowed to begin until the passage of an interval equal to or greater than the minimum clearing time. In this manner, the integrater will always be loaded with "cleared data" from the tri-state phase detector thereby eliminating errors produced by initial undesirable phase relationships between the input frequencies. In the preferred embodiment the output of the integrater is fed to a comparator circuit which determines from the voltage level of that signal whether a digital "1" or a "0" has been transmitted. This, in turn, is fed to a data latch or other signal utilization device for use in a well-known manner. The timing information to operate the system may also be derived in any conventional manner. The data timing, i.e. the Baud rate or bit time of the FSK system is known, and the carrier, carrier plus and carrier minus frequencies are known. Thus, for example, the reference frequency and timing signals may be derived from an oscillator operating on the input from the known sixty cycle power line frequency utilizing frequency synthesizers. BRIEF DESCRIPTION OF THE DRAWING In the drawing wherein like numerals are utilized to designate like parts throughout the same: FIG. 1 is schematic block diagram of the FSK discriminator of the invention; and FIG. 2 is a graphical representation of the waveforms associated with the components of FIG. 1 over a two bit time period. DESCRIPTION OF THE PREFERRED EMBODIMENT FIG. 1 depicts the improved FSK discriminator system in accordance with the present invention in schematic block form. This includes a tri-state phase detector 10, which may be similar to the one used in the well-known integrated circuit, the 4046B which is available from several manufacturers, an integrate and discharge circuit 11, sometimes referred to as an "integrate and dump circuit" with associated input and output controls including switches 12 and 13 and an inverter or NOT gate 14. Which may be a data latch 16. The system is shown using an arbitrarily chosen 120kHz reference signal input to the tri-state together with FSK signals, which may be power line carrier FSK signals, including a 122.4 kHz carrier plus or "mark" signal indicating a binary "1" and a 117.6 kHz carrier minus input frequency of "space" signal indicating a binary "0" to the tri-state phase detector. The 120 kHz reference signal input may be obtained in any well-known manner, as from an frequency synthesized signal derived from normal 60 Hz AC power line input. Likewise the timing signals for the control input to the integrater system (shown as waveform B) and the data latch (shown as waveform A) may be similarly derived as by using frequency synthesized techniques in conjunction with the 120 kHz oscillator system in a well-known manner. In accordance with the present invention, if a reference frequency is used for one input and unknown frequency for the other input, the output of the tri-state phase detector, after it has been cleared, will consist of all positive pulses or all negative pulses, depending on whether the unknown frequency is higher or lower than the reference frequency. Thus, if it is higher, positive pulses will occur and, if lower, negative pulses will appear in the output. Clearing of the tri-state phase detector occurs each time the unknown and reference input waveforms coincide in phase. The time that it takes to clear the tri-state phase detector, then, depends on both the initial phase difference of the two frequencies and the amount of frequency difference or deviation between them. In order to build a reliable FSK detector using a tri-state phase detector, it must allow for the worst case conditions. Thus, the system must assume that the two signals initially are out of phase by almost an entire cycle or 359+ degrees. Based on this assumption, the minimum clearing time can be derived from the frequency differences between the reference frequency and the unknown frequency as follows: ##EQU2## using the input frequency associated with FIG. 1, this yields: ##EQU3## In the case of power line carrier communications, data timing information is known. The Baud rate or digital bit time may be, for example, equal to one-half the frequency difference between the carrier plus or carrier minus signal frequency and the reference frequency of 1.2 kHz. It can readily be seen that the minimum clearing time equals one-half the bit time or Baud rate. Therefore, by controlling the operation of the integrater 11 by means of switches 12 and 13 together with NOT gate 14, the integrater may be caused not to integrate for an amount of time equal to the minimum clearing time at the beginning of each bit time, to assure that only cleared pulses will be integrated. The operation of the system is better illustrated utilizing the waveform diagrams in accordance with FIG. 2. In that figure the integrater circuit is shown to integrate either down or up, depending upon whether negative or positive pulses are received from the tri-state phase detector. Integration takes place only during the last half of the bit period. In other words, any given bit period, then, the output of the tri-state phase detector does not become an input to the integrater during the minimum clearing time. After the minimum clearing time has elapsed, switches 12 and 13 are reversed and the integrater 11 begins to integrate the pulse signals from the output of the tri-state phase detector 10. The integrater output is fed to the comparator 15 which is, in turn, a voltage level detector having a digital 1 or 0 output depending on whether a positive or negative integrated signal above or below a certain level is received from the integrater 11. The output of the comparator 15 is fed to the data latch 16 which latches the appropriate digital 1 or 0. The timing of the output is controlled by waveform A going high at the end of each bit period. Waveform A then goes low and waveform B goes high switching the switches 12 and 13 and disabling the integrater until the end of another minimum clearing time during the ensuing bit period. In the diagram of FIG. 2 during the first bit period the data input represents a 0 and during the second illustrated period a 1 in the FSK logic input. It can readily be seen that the integrator, then, receives only cleared pulses from the tri-state phase detector and therefore the chances of digital error in the output of the integrater and, thus, in the output of the comparator are greatly reduced.
A method of and apparatus for discriminator FSK signals using a tri-state phase detector is disclosed in which an input of known frequency is combined with the unknown FSK signal input and the output is fed to an integrator only after the minimum clearing time of the tri-state during each bit period. The integrator receives only the cleared signal for use in binary data signal determination thereby overcoming problems associated with lack of initial phase information at the tri-state phase detector.
7
BACKGROUND OF THE INVENTION [0001] 1. Field of the Invention [0002] The invention relates to a battery balance circuit, and more particularly, to a battery balance circuit implemented in a battery with a number of cells connected in series and capable of balancing the power between different cells. [0003] 2. Description of the Prior Art [0004] Most electronic devices use rechargeable battery as a power source for its advantageous convenience and capacity, in which batteries using lithium polymer as core substance are regarded as the most mature products with high capacity density specification. A rechargeable battery is primarily charged by a power supply unit or via an AC adapter from an electronic system where the rechargeable battery is installed. [0005] The rechargeable battery is usually made of cells, each with specific capacity and connected the each other in series. During the charging or discharging process of the cells, imbalance between cells often takes place due to the state of each cell, which would shorten the life and decrease the usable capacity of the cells. Conventionally, some measures have been taken to balance the cells in an attempt to extend the life and maintain the usable capacity of the cells: [0006] Series balance circuit in parallel with resistance. In a number of cells connected in series with one another, each cell is connected with a resistance in parallel and during the charging process, cell with higher voltage is made to consume its own power through the connected resistance. It is apparently a simple and low-cost, but far less efficient balance solution. [0007] B. Series balance circuit with switching inductance. A number of inductances are disposed in a rechargeable battery, each connected in parallel with one of the cells. During the charging process, cell with higher voltage is forced to store the power in the inductance by turning on a switch coupled therebetween and the inductance goes on to release the power to a next cell. Given the limitation that electrons in the circuit may only be conveyed to a neighboring cell, more cells in a battery the poorer efficiency the balance solution gets. [0008] C. Series balance circuit with switching capacitance. A number of capacitances is disposed in a rechargeable battery, each connected in parallel with its neighboring cells via two-way switches. The cells are made to balance through fast turning on and off of the switches. Sharing the same disadvantage as the previous solution, since electrons in the circuit may only be conveyed to a neighboring cell, if the power of a first cell is to be conveyed to a very last cell, through a number of middle cells, the power should have gone through repetitive storing and releasing in every intermediate capacitance. Such long path for conveying the power substantially effect the efficiency of the balance solution. [0009] These solutions for balancing cells in a rechargeable battery all have efficiency issue while great unnecessary power loss is inevitable. SUMMARY OF THE INVENTION [0010] To cope with the problem, embodiments of the invention provide a two-way direct balance circuit for series cells that utilizes a flyback converter and takes advantage of electromagnetic transition to convey power between cells, which extensively reduces the power loss during the balance procedure. [0011] An embodiment of the invention provides a two-way direct balance circuit for series cells. The two-way direct balance circuit includes a flyback converter, a first cell, a second cell, a control unit, and a pulse generator. The first cell is coupled to the flyback converter with coil and a first switch is coupled between the first cell and the flyback converter. The second cell is connected in series connection to the first cell and is coupled to the flyback converter with coil and a second switch is coupled between the second cell and the flyback converter. The control unit is coupled to the first switch and the second switch. The pulse generator is coupled to the control unit, the first switch, and the second switch and is utilized for generating a first pulse signal and a second pulse signal complementary to each other. The first pulse signal determines the turn-on frequency of the first switch and the second pulse signal determines the turn-on frequency of the second switch. When the relative state of capacity (RSOC) of the first cell is greater than the RSOC of the second cell, the control unit is utilized to activate the pulse generator such that the first pulse signal turns on the first switch and the flyback converter is utilized to convert electrical energy of the first cell into magnetic energy, and the second pulse signal turns on the second switch and the flyback converter is utilized to convert magnetic energy into electrical energy as a power supply for the second cell. [0012] Another embodiment of the invention provides a two-way direct balance circuit for series cells. The two-way direct balance circuit provides a flyback converter, a first cell set, a second cell set, a control unit, and a pulse generator. The first cell set includes a plurality of first cells in series connection. Each of the first cells is coupled to the flyback converter with coil, and between each first cell and the flyback converter is coupled a first switch. The second cell set is connected in series connection to the first cell set. The second cell set includes a plurality of second cells in series connection. Each of the second cells is coupled to the flyback converter with coil, and between each second cell and the flyback converter is coupled a second switch. The control unit is coupled to the first switch of each first cell and the second switch of each second cell. The pulse generator is coupled to the control unit, the plurality of first switches, and the plurality of second switches and is utilized for generating a first pulse signal and a second pulse signal complementary to each other. The first pulse signal determines the turn-on frequency of the plurality of first switches and the second pulse signal determines the turn-on frequency of the plurality of second switches. When the relative state of capacity (RSOC) of one or more first cells of the first cell set is greater than the RSOC of one or more second cells of the second cell set, the control unit is utilized to activate the pulse generator such that the first pulse signal turns on the first switch of said one or more first cells and the flyback converter is utilized to convert electrical energy of said one or more first cells into magnetic energy, and the second pulse signal turns on the second switch of said one or more second cells and the flyback converter is utilized to convert magnetic energy into electrical energy as a power supply for said one or more second cells. [0013] In the two-way direct balance circuit provided in the embodiment by the invention, the plurality of first switches and the plurality of second switches are high level turn-on switches. The two-way direct balance circuit further includes a charge pump coupled to the control unit and coupled between the pulse generator and the plurality of first switches and the plurality of second switches. The charge pump provides supplementary voltage for turning on the plurality of first switches and the plurality of second switches. [0014] The two-way direct balance circuit provided in the embodiment by the invention further includes a plurality of first check circuits and a plurality of second check circuits. The plurality of first check circuits is coupled between the plurality of first cells respectively and the flyback converter. The plurality of second check circuits is coupled between the plurality of second cells respectively and the flyback converter. Each of the plurality of first check circuits includes a third switch and a diode in parallel connection, and each of the plurality of second check circuits includes a fourth switch and a diode in parallel connection. The control unit is coupled to the plurality of third switches and the plurality of fourth switches. [0015] In the two-way direct balance circuit provided in the embodiment by the invention, the control unit is further utilized for monitoring the RSOC of the plurality of first cells of the first cell set and the plurality of second cells of the second cells, and is utilized for controlling the pulse generator to stop generating the first pulse signal and the second pulse signal when the RSOC of said one or more first cells and said one or more second cells is balanced. [0016] In the two-way direct balance circuit provided in the embodiment by the invention, the first pulse signal and the second pulse signal generated by the pulse generator are high frequency pulse signals with frequency at 100 KHz. [0017] The two-way direct balance circuit for series cells provided by the invention utilizes a control unit to activate a pulse generator to transmit high frequency switch control signals, and utilizes a flyback converter to perform electromagnetic transition between the cells that rapidly conveys power from the cells with high RSOC to the flyback converter and to the cells with low RSOC. The direct energy transfer between cells, either one to one, one to many, many to one, or many to many, provides fast and highly efficient performance. [0018] These and other objectives of the present invention will no doubt become obvious to those of ordinary skill in the art after reading the following detailed description of the preferred embodiment that is illustrated in the various figures and drawings. BRIEF DESCRIPTION OF THE DRAWINGS [0019] FIG. 1 is an illustration of a two-way direct balance circuit for series cells according to an embodiment of the invention. [0020] FIG. 2A , 2 B are illustrations showing energy conversion between two cells through the flyback converter. [0021] FIG. 3A , 3 B are illustrations of cells and flyback converter according to an embodiment of the invention. [0022] FIG. 4A , 4 B are illustrations showing switch and current relation charts corresponding the embodiment in FIG. 3A , 3 B respectively. [0023] FIG. 5A , 5 B, and 5 C are illustrations of the two-way direct balance circuit of the invention implemented with check circuits. [0024] FIG. 6A , 6 B, and 6 C are illustrations showing a number of balance solutions using the two-way direct balance circuit for series cells according to the invention. DETAILED DESCRIPTION [0025] Certain terms are used throughout the following description and claims to refer to particular system components. As one skilled in the art will appreciate, manufacturers may refer to a component by different names. In the following discussion and in the claims, the terms “include” and “comprise” are used in an open-ended fashion. Also, the term “couple” is intended to mean either an indirect or direct electrical connection. Thus, if a first device is coupled to a second device, that connection may be through a direct electrical connection, or through an indirect electrical connection via other devices and connections. [0026] Please refer to FIG. 1 . FIG. 1 is an illustration of a two-way direct balance circuit for series cells according to an embodiment of the invention. The two-way direct balance circuit 1 may be implemented in a plurality of cells in series connection and can balance the cells by use of a flyback converter. The two-way direct balance circuit 1 includes a flyback converter 10 , a battery module 20 , a control unit 50 , a pulse generator 60 , and a charge pump 70 . The battery module 20 includes a plurality of cells, which can be divided into a first cell set 30 and a second cell set 40 in series connection with the first cell set 30 . The first cell set 30 includes a plurality of first cells 31 in series connection and the second cell set 40 includes a plurality of second cells 41 in series connection. Each first cell 31 and each second cell 41 are coupled to the flyback converter 10 with coil. Between each first cell 31 and the flyback converter 10 , and between each second cell 41 and the flyback converter 10 , switches S 0 , S 1 , . . . , S n-1 , S n as shown in FIG. 1 are added to control the energy flow between each cell and the flyback converter 10 . [0027] The control unit 50 , the pulse generator 60 , and the charge pump 70 are coupled with one another. The control unit 50 is utilized for detecting and monitoring the relative state of capacity (RSOC) of each cell of the battery module 20 , and based on which, the control unit 50 determines which cells should be put to the balance procedure. Control lines CB 0 , CB 1 , . . . , CB n-1 , CB n in the control unit 50 correspond to the switches S 0 , S 1 , . . . , S n-1 , S n . For the embodiment in FIG. 1 , the control lines CB 0 , CB 1 , . . . , CB n-1 , CB n are respectively coupled to the switches S 0 , S 1 , . . . , S n-1 , S n through the charge pump 70 . Since the switches S 0 , S 1 , . . . , S n-1 , S n are high level turn-on switches, the charge pump 70 provide a supplementary voltage for turning on each of the switches S 0 , S 1 , . . . , S n-1 , S n . In other embodiments, the charge pump 70 is optional and may be not used in the circuit such that the control unit 50 is directly coupled to and controls the switches S 0 , S 1 , . . . , S n-1 , S n . Additionally, the pulse generator 60 generates a first pulse signal OSC 1 and a second pulse signal OSC 2 complementary to each other and is coupled to control the turn-on duty and frequency of switches S 0 , S 1 , . . . , S n-1 , S n . [0028] Please refer to FIG. 2A , 2 B. FIG. 2A , 2 B are illustrations showing energy conversion between two cells through the flyback converter. A switch S 1 is coupled between the first cell 31 and the flyback converter 10 and a switch S 2 is coupled between the second cell 41 and the flyback converter 10 . When the control unit 50 has detected a larger RSOC of the first cell 31 of the first cell set 30 while the second cell 41 of the second cell set 40 has smaller RSOC, there can be a need for balancing the power between the first cell 31 and the second cell 41 . Hence, in FIG. 2A , the control unit 50 turns on the switch S 1 such that current flows from the first cell 31 to the flyback converter 10 . Coiled on the flyback converter 10 , the current (electrical energy) from the first cell 31 and passing through the flyback converter 10 is converted into magnetic energy. Next, in FIG. 2B , the control unit 50 turns off the switch S 1 and turns on switch S 2 so that the magnetic energy on the flyback converter 10 will be converted into electrical energy (current) and conveyed to the second cell 41 , which means to charge the second cell 41 . It should be noted that in the embodiment, the flyback converter 10 makes it possible that electrical energy is conveyed between cells via energy conversion, instead of via voltage difference between the cells. [0029] Please refer to FIG. 3A , 3 B, 4 A, 4 B. FIG. 3A , 3 B are illustrations of another embodiment of the cells and the flyback converter according to the invention and FIG. 4A , 4 B are switch and current relation charts corresponding the embodiment in FIG. 3A , 3 B respectively. As described, the first pulse signal OSC 1 and the second pulse signal OSC 2 generated by the pulse generator 60 are complementary to each other, and the pulse generator 60 is coupled to the switches S 0 , S 1 , . . . , S n-1 , S n and controls the turn-on duty and frequency of switches S 0 , S 1 , . . . , S n-1 , S n . For example, the first pulse signal OSC 1 may be transmitted to control the turn-on duty and frequency of switches between a plurality of first cells 31 , 32 of the first cell set 30 and the flyback converter 10 , while the complementary second pulse signal OSC 2 may be transmitted to control the turn-on duty and frequency of switches between a plurality of second cells 41 , 42 of the second cell set 40 and the flyback converter 10 . [0030] Referring to FIG. 3A , 4 A, four switches S 1 , S 1a , S 2 , S 2a are disposed as illustrated between the first cell 32 of the first cell set 30 and the flyback converter 10 . During time interval t 0 ˜t 1 , the first pulse signal OSC 1 is high and the switches S 1 , S 1a , S 2 , S 2a are turned on with duty of 26.6%, but not limited to. At this stage, electrical energy (current) from the first cell 32 flows toward the flyback converter 10 and is converted into magnetic energy. Meanwhile, FIG. 4B shows that during the same time interval t 0 ˜t 1 , the second pulse signal OSC 2 is low and the switches S 3 , S 3a , S 4 , S 4a are turned off, which means there is no energy flow between the second cell 42 and the flyback converter 10 . [0031] Next, in FIG. 3B , 4 B, during time interval t 1 ˜t 3 , the first pulse signal OSC 1 is low and the switches S 1 , S 1a , S 2 , S 2a are now turned off. No energy flows between the first cell 32 and the flyback converter 10 . Meanwhile, FIG. 4B shows that during the same time interval t 1 ˜t 3 , the second pulse signal OSC 2 is high and the switches S 3 , S 3a , S 4 are turned on, while the switch S 4a remains turned off for some reason described later. At this stage, magnetic energy of the flyback converter 10 is converted into electrical energy (current) and flows to the second cell 42 . The first pulse signal OSC 1 and the second pulse signal OSC 2 generated by the pulse generator 60 as high frequency pulse signals with frequency at, say, 100 KHz constantly turn on and off the switches S 1 , S 1a , S 2 , S 2a and the switches S 3 , S 3a , S 4 , S 4a and this provides a mechanism of converting the electrical energy of the first cell 32 into magnetic energy via the flyback converter 10 and the magnetic energy being converted into electrical energy conveyed to the second cell 42 to balance the cells. [0032] Please refer to FIG. 5A , 5 B, and 5 C, which are illustrations of the two-way direct balance circuit of the invention implemented with check circuits. Referring to FIG. 5A , a check circuit is composed by transistor and switch. For example, a switch S 1a and a transistor 81 in parallel connection and coupled between the first cell 32 and the flyback converter 10 form a check circuit, and a switch S 2a and a transistor 82 in parallel connection and coupled between the first cell 32 and the flyback converter 10 also form a check circuit. a switch S 3a and a transistor 83 in parallel connection and coupled between the second cell 42 and the flyback converter 10 form a check circuit, and a switch S 4a and a transistor 84 in parallel connection and coupled between the second cell 42 and the flyback converter 10 also form a check circuit. Each of the switches S 1 , S 1a , S 2 , S 2a and switches S 3 , S 3a , S 4 , S 4a are coupled and controlled to turn on or off by the control unit 50 , or through the charge pump 70 . [0033] FIG. 5A shows a state the same as the state in FIG. 3A , i.e., the switches S 1 , S 1a , S 2 , S 2a are turned on and electrical energy (current) from the first cell 32 flows toward the flyback converter 10 and is converted into magnetic energy during time interval t 0 ˜t 1 . FIG. 5B shows a state the same as the state in FIG. 3B , i.e., the switches S 3 , S 3a , S 4 are turned on, while the switch S 4a remains turned off, and magnetic energy of the flyback converter 10 is converted into electrical energy (current) and flows to the second cell 42 during time interval t 1 ˜t 3 . [0034] Please also refer to FIG. 4B . Since the switches S 3 , S 3a , S 4 are turned on with duty of 26.6%, the flyback converter 10 will complete converting the magnetic energy into electrical energy (current) conveyed to the second cell 42 at time t 2 . Hence, as shown in FIG. 5B , 5 C, the switch S 4a remaining turned off during time interval t 1 ˜t 3 prevents possible current discharge from the second cell 42 to the flyback converter 10 . [0035] Please refer to FIG. 6A , 6 B, and 6 C. As described, the control unit 50 determines which switches should be turned on and off alternately according to the RSOC of the cells so that cells corresponding to the switches being turned on and off alternately may be balanced. Furthermore, the structure in the embodiments also provide a variety of balance solutions. For example, in FIG. 6A , a first cell (cell 6 ) of the first cell set 30 and a second cell (cell 14 ) of the second cell set 40 can be balanced. In FIG. 6B , a first cell (cell 6 ) of the first cell set 30 and a number of second cells (cells 12 - 14 ) of the second cell set 40 can be balanced. In FIG. 6C , a number of first cells (cells 5 - 7 ) of the first cell set 30 and a number of second cells (cells 12 - 14 ) of the second cell set 40 can be balanced. It should be noted that the balance can be made bi-directional between cells of the first cell set and cells of the second cell set, which means one or more first cells can not only provide energy for one or more second cells but also receive energy from the second cells. [0036] By monitoring the RSOC of a plurality of first cells 31 , 32 of the first cell set 30 and a plurality of second cells 41 , 42 of the second cell set 40 , the control unit 50 is able to selectively determine which cells in both cell sets to convey energy therebetween, through a high frequency pulse signal generated by the pulse generator 60 and through electromagnetic transition provided by the flyback converter 10 . During the energy exchange, the control unit 50 is able to determine if the balance process is done according to the RSOC of the cells. The pulse generator 60 will be controlled to stop generating the first pulse signal OSC 1 and the second pulse signal OSC 2 by the control unit 50 when the RSOC of the first cells 31 , 32 and the second cells 41 , 42 meets a balanced state. [0037] Those skilled in the art will readily observe that numerous modifications and alterations of the device and method may be made while retaining the teachings of the invention. Accordingly, the above disclosure should be construed as limited only by the metes and bounds of the appended claims.
In a two-way direct balance circuit for series cells, a control unit activates a pulse generator to transmit high frequency switch control signals, and a flyback converter is utilized to perform electromagnetic transition between the cells that rapidly conveys power from the cells with high RSOC to the flyback converter and to the cells with low RSOC. The direct energy transfer between cells provides fast and highly efficient performance.
7
BACKGROUND OF THE INVENTION 1. Technical Field The present invention is directed to an improved method of making starting materials involved in the preparation of an assay for determining the presence and/or amount of the immunosuppressant drug, FK506, in human blood. More specifically the present invention is directed to the preparation of reaction products of FK506 with dicarboxylic acids or anhydrides thereof. 2. Background FK506 is an immunosuppressant useful for the treatment of rejection following transplant surgery, graft versus host disease and autoimmune diseases in humans. FK506 is a macrolide antibiotic isolated from the fungus Streptomyces tsukubaensis by the Fujisawa Pharmaceutical Company of Japan. Cyclosporine, another immunosuppressant (but having a totally different structure from FK506), has also been used to control rejection. During cyclosporine therapy, monitoring the blood concentration of cyclosporine is an important aspect of clinical care. Accordingly, it is expected that monitoring blood concentrations of FK506 will be important for patients receiving this drug. To accurately and precisely measure blood concentrations of FK506, an appropriate analytical method must be available. High performance liquid chromatography (HPLC) is one non-immunological method that could be utilized. A receptor based assay could be configured using FK-binding protein and any number of reagents to generate a signal. Numerous immunological configurations can also be envisioned which could be successfully applied to the measurement of FK506. EP 0 293 892 A2 describes an ELISA methodology to measure FK506 comprised of 1) an ELISA plate coated with anti-FK506 antibodies, 2) an FK506-horseradish peroxidase conjugate which competes with free FK506 and acts as a signal generating reagent and 3) an appropriate substrate for the peroxidase. EP 0 293 892 A2 teaches that an immunogen generally is utilized in the form of a conjugate of FK506 with a carrier such as bovine serum albumin (BSA) by converting the FK506 to a half ester of a dicarboxylic acid such as succinic acid, then reacting the half ester with N-hydroxysuccinimide or the like in the presence of a condensing agent such as dicyclohexylcarbodiimide and further reacting the resulting activated ester with BSA. Pages 6 and 7 of the publication disclose the preparation of the FK506 hemisuccinate utilizing pyridine. However, it has been found that utilization of pyridine tends to result in the formation of disadvantageously low amounts of the product, FK506 half-ester. This tendency has been found, for example, when succinic anhydride has been utilized as the dicarboxylic acid. The achievement of consistently reliable and repeatable yields of reasonable amounts of FK506 half-ester product clearly is desirable. Moreover, the method disclosed in EP 0 293 892 results in undesirable amounts of FK506 being converted into side products thereby reducing the amount of unreacted FK506 that can be recovered following reaction. The production of low yields of FK506 hemisuccinate coupled with the undesirable amount of side reaction products of FK506 is economically disadvantageous when amounts of FK506 hemisuccinate necessary for commercial scale production are contemplated. Accordingly, an object of the present invention is to provide an improved method for producing esters of FK506 and dicarboxylic acids which reliably will yield improved amounts of the product half-esters of FK506 and, at the same time, reduce the amount of FK506 converted into undesirable side products. SUMMARY OF THE INVENTION The invention provides for a method for making a half-ester of FK506 and a dicarboxylic acid (or an anhydride thereof) by reacting a mixture comprising FK506 and the dicarboxylic acid (or anhydride) in the presence of triethylamine. The method of the invention reliably provides for a higher yield of the FK506 half-ester product while minimizing the amount of FK506 converted into undesirable side products. Reaction products of the invention can be utilized in the preparation of components for diagnostic assays for determining the presence and/or amount of FK506 in biological fluids such as from patient samples. DETAILED DESCRIPTION OF THE INVENTION FK506 corresponding to the following structural formula, (I): ##STR1## FK506 generally is theoretically considered to be difunctional in hydroxyl groups (not trifunctional) given the presence of a "masked ketone" moiety in the structural formula. Carboxylic acids suitable for the method of the invention are difunctional in carboxyl.(COOH) groups. However, the relative amounts of FK506 and dicarboxylic acid are chosen and reaction conditions are utilized such that on average one dicarboxylic acid molecule reacts with one FK506 molecule with the consequent formation of one FK506 half-ester molecule. It is to be understood that carboxylic acid anhydrides can be utilized in the method of the invention, and typically are preferred. The acid anhydride of a dicarboxylic acid of course is to be considered difunctional in carboxyl groups. The reaction product of the method of the invention sometimes is referred to herein as a "dicarboxylic acid/FK506 half-ester" or simply as an "FK506 half-ester". The method for making a half-ester of FK506 and a dicarboxylic acid involves reacting a mixture comprising FK506 and a dicarboxylic acid or anhydride thereof in the presence of triethylamine. It has been found that reacting FK506 with a dicarboxylic acid or anhydride in the presence of triethylamine provides a reliably higher yield of the dicarboxylic acid/FK506 half-ester reaction product than reaction in, for example, pyridine as taught in EP 0 293 892 A2 Moreover, the resulting product formed from the method of the invention typically contains less undesirable side products. For example, one undesirable side product minimized by the method of the invention is believed to be one involving extraction of a hydrogen atom of a methylene group followed by elimination of a hydroxyl group on the neighboring carbon atom in that part of the FK506 molecule represented by the following partial structural formula (II) with consequent formation of an olefinic bond shown in the following structural formula (III). ##STR2## Dicarboxylic acids and anhydrides for the method of the invention generally are of relatively low molecular weight, i.e., having a molecular weight in the range of from 90 to 250, preferably in the range of from 100 to 200. Examples of dicarboxylic acids and anhydrides include: oxalic acid, adipic acid, glutaric acid, maleic acid, maleic anhydride, fumaric acid, succinic acid, succinic anhydride, terephthalic acid, terephthalic anhydride, hexahydroterephthalic acid and hexahydrophthalic anhydride, with succinic anhydride being preferred. The reaction of the dicarboxylic acid or anhydride with FK506 is carried out in a temperature range of from 5 to 30 degrees Celsius, preferably from 20 to 25 degrees Celsius, for a period of about 12 hours or longer in the presence of triethylamine. Preferably the reaction is carried out at atmospheric temperature and pressure. Typically, the reaction is carried out by first mixing the dicarboxylic acid or anhydride with FK506 and a catalyst such as dimethylaminopyridine in a solvent such as freshly distilled methylene chloride. Thereafter the triethylamine is added while mixing (stirring) the aforesaid components of the reaction mixture. The amount of dicarboxylic acid or anhydride for the preparation of the FK506 half-ester may vary. However, typically an amount is chosen to provide a ratio of five moles of dicarboxylic acid (or anhydride) to one mole of FK506 so as to provide a molar excess of the acid or anhydride. The amount of FK506 and the amount of triethylamine are selected to provide a ratio of about 1.0 mole of FK506 to about 1 mole of triethylamine, preferably 1.0:1.0. A dicarboxylic acid/FK506 half-ester of the invention is particularly useful as an intermediate in the preparation of various conjugates for utilization in diagnostic assays for FK506. For example, the FK506 half-esters of the invention have been found to be particularly useful as intermediates in the conjugation of FK506 to an enzyme such as alkaline phosphatase. Other enzymes such as peroxidase, β-D-galactosidase, glucose oxidase, acetylcholine esterase, glucose-6-phosphate dehydrogenase, malate dehydrogenase and urease may also be utilized. Also by way of example the FK506 half-esters of the invention can also be utilized as intermediates in the conjugation of FK506 to various poly(amino) acids in the preparation of immunogens for raising antibodies. Examples of such poly(amino)acids include: naturally occuring poly(amino) acids such as bovine serum albumin (BSA), keyhole limpet hemocyanin (KLH), egg ovalbumin, bovine gamma globulin (BGG), thyroxine binding globulin, etc., and synthetic poly(amino-acids) such as polylysine, etc. Dicarboxylic acid/FK506 half-esters of the invention have been found to be especially useful in the preparation of preferred covalent conjugates of FK506 and alkaline phosphatase for utilization in a microparticle capture enzyme immunoassay (MEIA) for FK506 run on the IMx® analyzer available from Abbott Laboratories. Such an assay is illustrated more specifically in the examples which follow. A general description of microparticle capture enzyme immunoassays can be found in "The Abbott IMx™ Automated Benchtop Immunochemistry Analyzer System", by M. Fiore et al in CLINICAL CHEMISTRY Vol. 34, No. 9, 1726-1732 (1988) the disclosure of which is hereby incorporated by reference. In general an analyte such as FK506 is determined in an MEIA by quantifying the rate of fluorescence development when a fluorogenic substrate is converted by the action of an enzyme-labeled conjugate. MEIAs as run on the IMx® analyzer generally utilize a reagent pack containing microparticle reagent, an alkaline phosphatase conjugate, fluorogenic substrate and, optionally, a diluent buffer specific for the FK506 assay. Submicron microparticles coated with a capture molecule specific for FK506 being measured are used as the solid phase. Because the microparticles do not settle out of suspension during the course of the assay, they can be readily pipetted by the IMx® instrument. The effective surface area of these polystyrene latex microparticles, which number in the millions, is several-fold greater than that of a 1/4 inch diameter polystyrene bead commonly used in other commercial immunoassays. Because of this large surface area and the very small diffusion distance between analyte and the capture molecules on the surface of the microparticles, the capture phase of the MEIA typically reaches equilibrium within several minutes, allowing excellent throughput. Unlike homogeneous fluorescent polarization immunoassays, the heterogeneous MEIA requires a separation step. After incubation of the microparticles with specimen, the microparticles are separated from the reaction mixture by transferring it to an inert glass fiber matrix in the MEIA reaction cell. This glass fiber surface provides a precisely located mechanical support for the microparticles during the subsequent optical read phase of the assay. The microparticles and bound analyte adhere strongly to the glass fibers, while the remaining specimen components are washed through the pores of the matrix to an underlying absorbent blotter. Detection of the immune complex on the glass fiber matrix is accomplished using an alkaline phosphatase-labeled conjugate. Conjugate is either incubated with the specimen and microparticles in a typical one step IMx® MEIA or applied to the matrix after the initial wash step. It is contemplated that an MEIA for FK506 run on the IMx® analyzer can be configured either in a "sandwich" or competitive assay format. In a sandwich configuration an alkaline phosphatase-anti-FK506 antibody conjugate is used, while an IMx® competitive assay utilizes an FK-506-alkaline phosphatase conjugate. In either configuration, the specifically bound alkaline phosphatase on the microparticles is detected by addition of a fluorogenic substrate, typically 4-methylumbelliferyl phosphate (4-MUP), to the matrix. The alkaline phosphatase catalyzes hydrolysis of the 4-MUP to inorganic phosphate and fluorescent 4-methylumbelliferone (4-MU). The liberated 4-MU is detected by the IMx® MEIA optics assembly, a front surface fluorometer designed to detect fluorescence of low concentrations of 4-MU without interference by fluorescence of 4-MUP at 367 nanometers (nm). A system of lenses and optical filters focuses filtered light (365 nm wavelength) from a mercury arc lamp onto the surface of the matrix and focuses emitted fluorescence from 4-MU (448 nm wavelength) onto a photomultiplier tube. About 5% of the excitation light is detected by a photodiode, allowing normalization of the fluorescence data and generation of a control signal used by the lamp power supply to maintain the intensity of the excitation light within 5% over the useful life of the lamp. The instrument then uses linear regression analysis to convert the data from 8 successive determinations of 4-MU fluorescence to a rate, which rate is proportional to the concentration of alkaline phosphatase conjugate specifically bound to the microparticles, from which the concentration of FK506 in the sample can be determined. The following examples are provided to further illustrate embodiments of the invention and should not be construed as a limitation on the scope of the invention. EXAMPLE 1 This example illustrates the preparation of polyclonal antibodies directed against FK506. Rabbitt polyclonal antibodies were produced by standard procedures. FK506 immunogen was prepared as described in Fujisawa patent EP 0 293 892 A2 the disclosure of which is specifically incorporated herein by reference. EXAMPLE 2 This example illustrates the preparation of Microparticle Reagent. An antibody directed against FK506 was covalently coupled to carboxylate modified latex microparticles (0.392 microns) by established procedures. These methods are extensively reviewed in Uniform Latex Particles (1987) L. B. Bangs, Seragen Diagnostics, Inc., the disclosure of which is hereby specifically incorporated by reference. In brief, final concentrations of antibody (1 to 3 mg/ml), microparticles (0.5 to 0.7% solids) and EDAC (1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride) (0.2-0.5 mM) are mixed, the pH adjusted to 5.7 and the reaction allowed to proceed for 12-18 hours at 2-8 degrees Celsius. The microparticles are then washed by repetitive centrifugation and re-suspension cycles and the microparticles are diluted to the final working concentration. These methods are applicable to either polyclonal or monoclonal antibodies. Microparticles were prepared using both polyclonal antibodies and a monoclonal antibody produced by Fujisawa (clone 1-60-46, described in Trans Proc, Vol 9, No 5, Suppl. 6, pp 23-29, 1987), the disclosure of which is specifically incorporated herein by reference. EXAMPLE 3 This example illustrates the preparation of FK506-hemisuccinate and its active ester according to the method of the invention. FK506 (250 mg), succinic anhydride (150 mg) and 4-dimethylaminopyridine (61 mg) were dissolved in 6.25 ml of freshly distilled methylene chloride. Upon stirring, triethylamine (4.2 microliters) was added and the reaction mixture was stirred for an additional 20 hours at room temperature. The mixture was diluted to 20 ml with methylene chloride and washed once with 0.1N aqueous HCl, once with distilled water and once with saturated aqueous NaCl. The resulting organic phase was dried over anhydrous MgSO 4 , filtered and concentrated to a slightly yellow foam. This material was chromatographed on silica gel using a 9:1 methylene chloride/methanol mobile phase to give 104.3 mg (39% yield) of the hemisuccinate as a white foam. The FK506 hemisuccinate (35 mg), N-hydroxysuccinimide (5.4 mg) and N,N'-dicyclohexylcarbodiimide (8.8 mg/ml) were dissolved in 5 ml ethyl acetate and stirred for 24 hours at room temperature. The reaction mixture was filtered and dried to give 44.1 mg of a mixture containing the active ester and N,N'-dicyclohexylurea. The material was used without further purification. EXAMPLE 4 This example illustrates the preparation of the FK506-Alkaline Phosphate Conjugate Reagent. One milligram (1 mg) of the active ester described above was solubilized in 0.5 ml of dimethylformamide (DMF). An amount of 0.14 ml of this solution was mixed with 0.62 ml of DMF and added to 10 ml of calf intestine alkaline phosphatase (10 mg). The solution was mixed for 2.5 hours at room temperature and then 1 ml of 1.8M Tris was added. This solution was dialyzed against buffer (0.1M NaCl, 2 mM MgCl 2 , 0.1 mM ZnCl 2 , 0.1% NaN 3 , 0.05M Tris-HCl, pH=7.5) at 2-8 degrees Celsius and then bovine serum albumin was added to a final concentration of 1%. This stock solution of FK506-alkaline phosphatase conjugate was diluted to the working concentrations as necessary. EXAMPLE 5 This example illustrates the preparation of Precipitation Reagent. The whole blood precipitation reagent was prepared with final concentrations of 60 mM ZnSO 4 , 50% (w/v) methanol and 30% ethylene glycol. EXAMPLE 6 This example illustrates the preparation of Blood FK506 Standards. Human whole blood was lyzed by three freeze-thaw cycles and the pH of the blood adjusted to pH 6.0 by the addition of 3M citric acid. FK506 in methanol (10 micrograms/ml) was spiked into this matrix so as to make standards from 10 to 80 nanograms/ml of FK506. This novel matrix for FK506 is described in the copending U.S. patent application Ser. No. 07/752410 filed Aug. 30, 1991 of Frank C. Grenier, Julie A. Luczkiw, Merry E. Bergmann and David R. Blonski and entitled "Stable Aqueous FK506 Standards", the disclosure of which is specifically incorporated herein by reference. EXAMPLE 7 This example illustrates a Microparticle Enzyme Immunoassay (MEIA) for FK506. Whole blood solutions containing 0, 10, 20, 30, 50 and 80 nanograms/ml FK506 were each tested following the assay protocol described below. One hundred (100) microliters of sample was added to 200 microliters of precipitation reagent and the mixture vortexed for 5-10 seconds. The precipitates formed were pelleted by centrifugation and the clear supernatant decanted into the sample well of an IMx® sample cartridge. Forty (40) to 50 microliters of this organic sample was added directly to 50 microliters of the microparticle reagent and 150-160 microliters of IMx® dilution buffer. The reaction mixture was incubated at 33-36 degrees Celsius for 10 minutes and then 175 microliters of this mixture was transferred onto a glass fiber filter. The filter was washed with IMx® dilution buffer and then 40-50 microliters of the FK506-alkaline phosphatase conjugate reagent was added to the filter. Following a second wash step, 50 microliters of alkaline phosphatase substrate, 4-methylumbelliferyl phosphate was added to the filter. Conjugate bound to the filter converted the substrate to a fluorescent product which was quantified by front surface fluorescence measurements. The rate of production of the product was directly proportional to the amount of conjugate bound and thus indirectly proportional to the amount of FK506 bound to the microparticles. The results of the measurements are as set forth in the following Tables 1 and 2. TABLE 1______________________________________Using Microparticles with Monoclonal AntibodyConcentration FK506 (ng/ml) Fluorescent Rate______________________________________ 0 41610 28820 19730 15050 11180 79______________________________________ TABLE 2______________________________________Using Microparticles with Polyclonal AntibodyConcentration FK506 (ng/ml) Fluorescent Rate______________________________________ 0 413 5 26410 20820 15440 11275 85______________________________________ The measurements obtained show that a standard curve can be made to analyze whole blood containing unknown FK506 concentrations. Microparticles made with either polyclonal or monoclonal antibodies function equally well.
Disclosed is an improved method for the synthesis of FK506-hemisuccinate for utilization in the preparation of components for as assay for FK506.
2
FIELD OF THE INVENTION [0001] The present invention relates to a method and apparatus for managing printing solutions in one or more local area networks, in particular in the travel reservation domain but also anywhere where large numbers of work stations and printers which need not be dependant on each other are operated. BACKGROUND OF THE INVENTION [0002] There is a vast number of patents related to the management and the control of peripheral devices such as printers for example, in networks. [0003] WO2000/052601 discloses a system that is capable of booking travel through a computer network by allocating communication links on a dynamic and distributed basis. It does not deal with the generation, storage, or auto adaptation of printer configurations and a management of the same by location or type identifiers. [0004] US2003/145070 discloses a method for configuring a printer device with a specific controller. This controller can determine the physical environment of the printing device and what kind of device is asking for a printer. The controller can then configure the printer depending on the source device and in relation to a printing solution based on location and addresses for a mobile printer. The location of the printer, which is established by a position beacon, is determined in order to establish a link with a work station locally or remotely. It deals with a different set of issues than the current invention. [0005] US2004/156074 discloses a method of printing data using a identification number of a printer instead of a network address. Thus if the network address of the printer is changed the user does not need to reset the printer port in order to update it with the new address of the printer. The port can still process the printing. This type of system is commonly referred to a fixed mode terminal identifier (TID). This fixed mode type of system requires an inventory of fixed work stations and devices. One configuration (including type, set up, TID, etc . . . ) is defined per work station and per application. A device administrator administers this inventory using device administration. This requires continual manual input and activity whenever there are changes to the work stations and other peripheral devices. [0006] In general the systems described in the prior art raise operational issues when dealing with very large number of devices. SUMMARY OF THE INVENTION [0007] An object of the present invention is to overcome at least some of the problem associated with the prior art method of controlling printing management. [0008] Another object of the present invention is to define a manner in which to manage and administrate the logical address and physical configuration of a set of printers and how this may be automated. [0009] According to one object of the present invention there is provided a method of managing printing in an environment with a plurality of work stations and a plurality of printers in one or more networks each work station having a unique identifier (ID) and each printer having a type and a configuration which is dependant on the unique ID, wherein one or more of the printers is connected to a one of the plurality of work stations; and wherein the network also includes a document server and an identity generator, the method comprising: polling a work station when it connects to the network to determine what printers are connected thereto; determining the unique ID of the work station; determining the type of printers; determining the configuration of the printer from the type and work station unique ID; determining an identification code (ID code) for each printer connected to the connected work station using the identity generator; developing a look up table of unique ID of the work station; type and configuration of the printer and ID code; receiving a print request from a client application or user at the document server; identifying the configuration of the printer from the look up table in response to the print request; sending the print request to the printer with the appropriate ID code, as identified by the look up table. [0019] This invention has a number of advantages. It provides an auto registration process which allows retrieving, creating and updating a workstation configuration, including the configuration of its attached devices, without any administration. The storage of work station data in an identity generator data base allows transparent handling of fixed and dynamic addressing as well as configuration. The inventive identity generator can be used in any environment where a work station has a unique identifier and a list of attached devices for each type of workstation is well-known. For example, this may be of used in airports, stations, call centers, and possibly in shops where there are large number of tills and printing devices for printing out receipts etc. BRIEF DESCRIPTION OF THE DRAWINGS [0020] Reference will now be made by way of example to accompanying drawings in which: [0021] FIG. 1 is a high level view of the present invention. [0022] FIG. 2 is a high level view of a second embodiment of the present invention. [0023] FIG. 3 is a block diagram of the system including a terminal identity generator (TID dispenser) in accordance with one aspect of the present invention. [0024] FIG. 4 is a diagram showing the auto registration for a first login to the TID dispenser of a work station. [0025] FIG. 5 is auto registration process for the next login of a work station. [0026] FIG. 6 is an auto registration example with the next login with updated work station configuration. [0027] FIG. 7 are the configuration templates and configuration areas in accordance with one aspect of the present invention. [0028] FIG. 8 is a representation of a work station configuration. [0029] FIG. 9 is a diagram of auto registration configuration example. [0030] FIG. 10 is a flow chart other method steps is associated with the choice between fixed and auto-registration modes. DETAILED DESCRIPTION OF THE INVENTION [0031] Referring now to FIG. 1 , the architecture of the printing solution and the position of the identity generator or TID dispenser is shown. The diagram shows an airport LAN or full IP network 100 which is connected to a GDS LAN 114 by means of a communication module 104 . [0032] The airport LAN includes one or more work stations 106 . A work station may have connected thereto a number of attached devices of different types. In this example, this could be an automatic ticket and boarding pass (ATB) printer 108 , a bag-tag printer (BTP) 110 and an optical character recognition (OCR) reader or printer 112 . [0033] The global distribution system LAN, GDS LAN, includes the following elements: A GDS module 116 , a departure control system (DCS) 118 , a print server or document server (TDS) 120 , and a terminal ID dispenser (TID Dispenser) 122 . There may also be a TID database 124 for facilitating replication of the data in the TID dispenser 122 . This may also include redundancy. [0034] Local communication between the work station and the printing devices is effected by a printer emulator 126 installed on the work station. A printer manager 128 is also shown that manages any printing events. The communication between the printer emulator and printer manager is via a TCP/IP link, for example. The work station also includes a java front end (JFE) 130 or any other type of Graphical User Interface (GUI) or user interface. Auto registered devices in accordance with the present invention do not require any device identity inventory maintained by a device administrator. Instead the device identity inventory is built and maintained automatically by the TID dispenser as the work stations log in. Device address attribution and configuration management is carried out by the terminal identity dispenser (TID) dispenser, and document formatting and delivery is managed by the document server (TDS). [0035] The TID dispenser assigns TIDs to devices according to a work station ID and an application identifier and can review, create, update, retrieve or otherwise determine the configuration of those devices. This will be described in greater below. The print server formats the document requested by the DCS, and then route the print traffic to the identified printer that has been identified by the TID dispenser and the management thereof. The TID dispenser of the present invention can be adapted to different system requirements and is compatible with both fixed and automated TID devices. In the automated TID devices there would no longer be a requirement for device administrators maintaining a full device inventory. Instead an auto registration process will allow a work station to retrieve, create and update configuration without administration. This will now be described in greater detail. [0036] The TID dispenser requires that each work station has an identifier that is unique on the worldwide basis. It would have been appreciate that the worldwide basis in this example relates to the extent of the network over which the invention applies. This may be an individual airport, this may be a number of different airport in different geographic location or maybe genuinely be on a worldwide basis. The identifier must be available on the work station and it is read by the printer emulator on the work station and provided to the TID dispenser. Work station identifier is essential for all work stations. The TID dispenser also uses the full location, i.e. the physical location of the work station. The full location can include for example airport, city, terminal, building, category, index, field etc. Not all fields of the full location are necessarily required. For example, for locations where the index is not meaningful it does not need to be specified. Similarly any other type of location codes could be a use for example building, stage, orientation, etc . . . Any other type of discrimination or definition could be used in addition to (or instead of) the full location for example the function of the device, the level of priority, the year of deployment, company, etc . . . The full location or an other discrimination or definition can be incorporated into the unique identifier of the work station. This means that only a unique identifier needs to be determined in the simplest case. The full location or other discrimination or definition is sent to the TID dispenser. The full location or other discrimination or definition is an essential feature for all auto register devices. [0037] Each printer emulated embedded application may benefits from an application identifier, the application identifier including an application label and an application index field. For example two graphical user interfaces or client application started on a work station will be referred to as App 1 and App 2 respectively. In an embodiment of the invention, the application label is stored in the GUI and the application index is provided to the printer emulator in the start command line. Application label and index are essential in circumstances where multiple applications are running at the same time on a specific work station and if it is required that the printers have different ID and configuration according to the application. The system can work without application identifier in the situation where each printer or device has the same ID and configuration whatever the application running on the workstation. Any different identifier could be used to allocate different IDs and configurations to the same device such as for example a category code, a user identifier instead of the application identifiers mentioned above. [0038] Device set up record gives us some low level parameters of the physical devices. These parameters are used by document servers for formatting and printing. In an embodiment of the invention, the administration of device set-ups is available in a device administration GUI. [0039] In the auto registration mode described below, device set ups are generally homogenous with the full location or any other type of discriminator or definition deployed for a given device type. [0040] Referring now to FIG. 2 a more expansive network set up is shown. Here there are two airport LANs 200 and 202 connected to a GDS LAN 204 . All the LANs may be in the same or different physical/geographic locations. Each airport LAN includes one or more work stations and printers equivalent to work station 106 and printers 108 , 110 and 112 in FIG. 1 . The GDS LAN is substantially similar to the GDS LAN 114 in FIG. 1 . [0041] The manner in which the TID dispenser is connected into the system is shown with respect to FIG. 3 . The TID dispenser 300 is connected to the work station 302 via a bidirectional connection. The work station is also connected to a document server 304 . The work station is shown having two printer ports an automatic ticket and boarding pass ATB printer 306 and a bag-tag printer BTG 308 . [0042] Information is passed from the work station (arrow 1 the information includes work station ID (identifier and full location); application identifier (label and index); and list of detected devices with type. This information is registered in the TID dispenser 300 . The TID dispenser then generates a list of TIDs that may be fixed or auto registered. This information is then returned to the work station by means of communication in the direction of arrow 2 . Similarly, data is communicated with the document server so the document server knows the relevant printers for a specific work station. The information in a line of the database that constitutes the TID dispenser indicates a carrier, a work station ID and an application identifier and the configuration of all printers attached to the work station. Accordingly if there is more than one application on a specific work station each of application will have a different configuration in the TID dispenser data base. [0043] Referring to FIG. 4 when a work station first logs into the system via the TID dispenser, the following sequence of events occurs. The work station 400 is connected to two active application devices 402 and 404 respectively. The work station is connected to the TID dispenser 406 and the document server 408 . Similarly the document server and TID dispenser are connected to one of the other. The TID dispenser generates the configuration for the workstation and its connected devices. This configuration is stored in the TID dispenser database 410 . [0044] A print request may be generated and communicated to the document server. At that point the document server will interrogate the TID dispenser to determine the appropriate configurations templates and printers for the print request. The document server will then transmit the print request directly to the appropriately identify printer. Referring now to FIG. 5 the next time login of a work station is explained. As under the first example the printer emulator requests the TIDs for the work station/application combination. [0045] It is considered as known work station as the work station identifiers are recognized. This step will be referred to as next login in the rest of the document. Again if a printer request is received at the document server, the document server will retrieve the relevant TID and configuration from the TID dispenser and implement the printing action at the required printer. [0046] Referring now to FIG. 6 a new printer PRT 600 has been added to the work station 602 . At this time when the work station connects to the TID dispenser it is recognized as a known work station but that new device is identified. This causes an additional a TID to be provided by the TID dispenser for that work station and included in the work station configuration. The update is communicated with the work station and the document server as has been described with reference to FIG. 4 . These changes are stored and maintained until such time as the work station changes again. Similarly, if the work station reconnects in the next log in the new printer 600 will already identified and recognize and the actions will be equivalent to those shown with reference to FIG. 5 thereafter. [0047] Further detail of the auto registration mechanism is now described. The auto registration of a work station is authorized on the basis of its full location or other discrimination or definition. A device administrator or an external application defines the locations where work stations can auto register. It is the role of the administrator to define two objects, configuration templates and configuration areas. Configuration templates store the links between device types and device set-ups. It is expected the configuration templates list all the possible device types that could be provided by a work station. This is the only role played by the device administrator. A configuration area associates a configuration template with a full location or other discriminator or definition. In the example shown in FIG. 7 , configuration template have been attributed to NCE/T 2 /G/ 3 and NCE/T 1 where NCE stands for Nice airport, T 1 stands for Terminal 1 , T 2 stands for Terminal 2 and G stands for a gate number. NCE/T 1 is considered as a full location distinct from for example NCE/T 1 /G/ 20 or NCE/T 1 /LNG. A wild card functionality is available to attribute a configuration template to several full locations. For example LHR/T 1 /G/* includes all the gates in terminal 1 of LHR airport whatever the index. That is a work station on LHR/T 1 /G/ 20 will use the configuration template, configuration T_ 2 . Looking more closely at FIG. 7 , it can be seen that configuration T_ 1 , 700 shows the device type and the device set up. The configuration template name is identified in the top row and the whole of the table 702 constitutes one configuration templates. Dealing with the configuration areas, the full location is shown in the left column and the configuration template is in the right column. One configuration area is equivalent to one row of the table 704 . In an embodiment, these configuration areas and templates can be created using a device administration GUI. [0048] FIG. 8 shows an extract from the TID dispenser table which identifies the work station name and the application identifier along with the type, set up and TID indicator for the same. It can also be seen in FIG. 8 that each column constitutes one device attached to a specific work station. [0049] FIG. 9 shows a configuration generated with the auto registration process. It also shows the information used by the auto registration process. [0050] Referring now to FIG. 10 , the process for determining whether the devices, workstations and printers etc are operated in fixed mode or auto registration mode is explained. The decision as to which mode should be selected is made in order to deal with the situation where certain workstations connected to one or more of the LANs is unable to operate in an auto registration mode. The steps carried out to achieve this selection are shown in FIG. 10 and starts with the retrieval of identity of a certain work station step 1000 . A determination is made as to whether the application label for the workstation is a known organization (step 1002 ) and if the full location details are valid (step 1004 ). In each case if the answer to this question is no the process stops (steps 1006 and 1008 respectively). If the answer to each question is yes the process continues. [0051] The next determination at step 1010 is to determine whether the workstation ID is known in the TID dispenser database. If the answer to this question is no this equates to a first login step for the workstation and an auto registration mode is entered. A determination is then made as to whether the full location match is a configuration area (step 1012 ) if the answer is yes the configuration template is retrieved from the configuration area (step 1014 ). A determination is then made as to whether the full location matches an office identifier (step 1016 ) and then a determination as to whether there are enough TIDs in the pool (step 1018 ). If the answers to all of these questions are yes then a workstation configuration is created (step 1020 ). After the workstation configuration has been created the identity of the workstation is returned to the workstation, the TID dispenser, and any other media that needs to know ( 1028 ). In each case if the response to the question is no the process is exited ( 1022 , 1024 , 1026 ). [0052] At step 1010 if the workstation ID is known to the TID dispenser database this equates to next login step ( 1030 ). A determination is then made as to whether the application identifier is known in the database (step 1032 ). If no, there may be a new application ( 1034 ). If there is a new application or not as the application identifier is not known in the database the process returns to step 1012 and determination of whether the full location matches configuration area is made. On the other hand, if the application identifier is known in the database workstation configuration is retrieved at step 1036 . At step 1038 a determination is made as to whether the type list is compliant with the workstation configuration. If yes the identity is returned as above at step 1028 . [0053] If the answer is no at step 1038 a determination is made as to whether the workstation is in an auto registration or fixed mode (step 1040 ). If the workstation is in a fixed mode the identity of the workstation is returned and a warning is sent step 1042 . The identify has the format as described in FIG. 8 . The warning shows any discrepancy between stored identity and information received from the workstation. If the workstation is an auto registration mode a determination is made at step 1042 as to whether there are enough TIDs in pool. If yes, the workstation configuration is updated (step 1044 ) and any updates are registered (step 1046 ). The identities are then returned as above in step 1028 . If at step 1042 , there are not enough TIDs in the pool the process is exited ( 1048 ). [0054] In this way the system according to the present invention can operate for all workstations in a given environment. The ability to identify whether the workstation is in a fixed or auto registration mode enables greater flexibility in the system and method of the present invention. In addition, it enables the gradual transfer of workstations from a fixed mode to an auto registration mode in a controlled and managed fashion. [0055] At the stage of next log in, if the list of device types provided to the TID dispenser changes (in other words is different from the list provided at the previous login) the TID dispenser will automatically adapt the work station configuration by reusing the configuration template. Devices can thus be removed from or added to the work station configuration without any manual update from the device administrator. Device set ups of all the devices located in a location can be updated by changing the configuration template. [0056] As has been indicated this invention relates to many different environments. The airport scenario described above, is just by way of example and it is clear that the invention can be used in any contexts. It will also be appreciated that the scenario described can have many variations and still remain within the spirit and scope of the present invention.
A method of managing printing in an environment with a plurality of workstations and a plurality of printers in one or more networks. Each workstation has a unique ID and each printer has a type and a configuration which is dependent on the unique ID. One or more of the printers is connected to a one of the plurality of workstations. The network also includes a document server and a identification generator. The network polls a workstation when it connects to the network to determine what printers are connected thereto; determines the unique ID of the workstation; determines the type of printer; determines the configuration of the printer from the type and workstation location; determines an identification code (ID code) for each printer connected to the connected workstation using the identification generator; develops a look up table of unique ID of the workstation, type and configuration of the printer and ID code; receives a print request from a workstation at the document server; identifies the configuration of a printer from the look up table in response to the print request which can receive the print request; and sends the print request to the identified printer with the appropriate ID code, as identified by the look up table.
7
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink jet print head used in an ink jet recording system for performing a recording operation to a recording medium by flying a small ink droplet, and an ink jet printing device using this head. 2. Related Background Art There are a method utilizing an electrothermal converting element (heater) as a discharging energy generating element used to discharge an ink droplet and a method utilizing a piezoelectric element as this discharging energy generating element in an ink discharging method of an ink jet recording system widely generally used at present. In each of these methods, discharging of the ink droplet can be controlled by an electric signal. For example, in the principle of the ink droplet discharging method using the electrothermal converting element, ink in the vicinity of the electrothermal converting element is instantaneously boiled by giving the electric signal to the electrothermal converting element, and the ink droplet is discharged at high speed by growing a sudden bubble caused by a change in phase of the ink at this time. In contrast to this, in the principle of the discharging method of the ink droplet using the piezoelectric element, the piezoelectric element is displaced by giving the electric signal to the piezoelectric element and the ink droplet is discharged by a pressure at a time of this displacement. Here, with respect to merits in the former method, it is not necessary to arrange a large space for the discharging energy generating element, and the structure of an ink jet print head is simple and ink flow paths are easily integrated, etc. However, in this method, the air dissolved within the ink is eluted by heat generated from the electrothermal converting element and a residual bubble is caused within the ink jet print head. When this residual bubble is left as it is, the residual bubble has bad influences on discharging characteristics of the ink droplet and an image. The influences of the residual bubble within the ink jet print head caused by the air dissolved within this ink on the ink droplet discharging characteristics and the image will next be explained in detail. The air is normally dissolved into the ink within the ink jet print head in a saturation state. When the electrothermal converting element is operated in this state, there is a case in which the air dissolved into the ink suddenly appears within the ink as a dissolved bubble having a diameter equal to or smaller than about 1 μm in repetitions of adiabatic contraction of foaming and a sudden bubble by a change in phase of the ink. It is also known that such a bubble is again dissolved into the ink for a time determined from a bubble diameter, surface tension of the ink, a saturated vapor pressure of the air, etc. For example, if the bubble diameter is equal to smaller than 1 μm, a time required for the dissolution is an order equal to smaller than 1 μs. However, when plural electrothermal converting elements are continuously operated at high frequency, a plurality of such bubbles appear within the ink and are mutually collected and grown before these bubbles are again dissolved. It is known that a time required for the redissolution is greatly increased when the bubble diameter is increased. As a result, plural residual bubbles from several tens of μm to several hundred μm in diameter are stored within the ink jet print head. In such a case, no such residual bubbles are almost again dissolved into the ink so that these residual bubbles have a bad influence on discharging characteristics of the ink droplet. Namely, if an ink flowing path is blocked by the residual bubbles, the ink flowing path is not filled with sufficient ink so that a discharging defect is caused. Further, when a great residual bubble (about several hundred μm in diameter) is caused within the ink jet print head and is accidentally communicated with the external air, the external air enters the ink flowing path so that a meniscus is broken. Therefore, the ink within the ink jet print head is sucked-up to an ink tank by a negative pressure for sucking-up the ink of the ink tank so that no ink is discharged from the ink flowing path in a certain case. As a most effective solving means for avoiding such a bad influence of the residual bubbles, there is a method for externally discharging the residual bubbles together with the ink from an ink discharge port by suction, pressurization, etc. before the residual bubbles are grown to such an extent that the residual bubbles have the above-described bad influence. This method is a method for performing so-called suction (pressurization) restoring processing. However, in this case, a consuming amount of the ink is greatly increased and throughput is naturally reduced if this method is executed during a printing operation. There is another method in which the air dissolved into the ink is discharged from the ink (deairing) by a certain method, and such ink is used in the ink jet print head. A most effective operating time of this solving method is about several tens of minutes from the deairing of the ink, and a device for deairing the ink is relatively large-sized so that usage of this technique is limited to a printing system, etc. on a large scale. Therefore, in consideration of such a problem of the residual bubbles, in an ink jet print head described in Japanese Patent Application Laid-Open No. 10-146976, as shown in FIGS. 7A and 7B, plural projections 7 are arranged at a certain interval just above an ink supplying port 8 on the inner surface of a discharging port plate 5 so that growing of a bubble attached to the inner surface of the discharging port plate 5 is restrained. Further, a common ink flowing path portion common to electrothermal converting elements 1 as adjacent discharging energy generating elements 1 is arranged to stably supply ink so that supplying interruption of the ink caused by flowing a bubble 11 attached to an end tip of a projection 7 and grown to about φ150 μm in diameter into the ink flowing path is restrained. However, in the above conventional examples, the bubble itself exists near the ink supplying port as it is. Therefore, when the ink is printed to an elongated recording medium as in banner printing, textile printing, etc. there is a case in which restoring processing must be intermediately performed. However, when a restoring operation is performed during printing of one sheet, a color tone is changed in this restoring portion and this change has a bad influence on printing quality. Therefore, it is not desirable to perform the restoring operation during the printing. Such a situation can be avoided by performing the restoring operation at any time every time the recording medium is changed. However, when the restoring operation is often performed, the throughput of a printed matter is reduced. Further, a problem exists in that a useless ink amount is increased. SUMMARY OF THE INVENTION In consideration of the above problems, an object of the present invention is to provide an ink jet print head for relaxing the bad influence of a bubble left within the ink jet print head on ink liquid discharge, and discharging a stable ink droplet with high reliability. Another object of the present invention is to provide an ink jet printing device having an excellent throughput and reducing an ink consuming amount by controlling a residual bubble and further reducing the number of restoring times. To achieve the above objects, in the present invention, an ink flow is made near a through port of a substrate of an ink jet print head by a hydrodynamic action of ink so that a bubble attached to a wall face of a common liquid chamber is easily separated therefrom or the bubble is not easily attached to this wall face. In the construction of the present invention, an ink jet print head comprises plural electrothermal converting elements for generating energy used to discharge an ink droplet; plural ink discharge ports arranged above the electrothermal converting elements and discharging the ink droplet; plural ink flowing paths respectively communicated with the plural ink discharge ports and internally including the electrothermal converting elements; a substrate for arranging the plural electrothermal converting elements in a columnar shape and having an ink supplying port constructed by a through port which is connected with the ink flowing paths and extends along an arranging direction of the electrothermal converting elements; and a discharging port plate having the ink discharge ports; the ink jet print head being constructed such that the ink flowing paths are formed between the substrate and the discharging port plate by junctioning the discharging port plate onto the substrate; and the ink jet print head further comprising fluid resisting means of the ink flowing paths in which a side of the ink supplying port is opened in the vicinity of a communication portion of the ink flowing paths in an ink supplying port projecting area of the discharging port plate. In accordance with the ink jet print head having the above construction of the present invention, a speed component in a direction of the common liquid chamber can be given to the ink flow parallel to the discharging port plate near the ink supplying port at an ink discharging time. Therefore, the bad influence of a bubble left within the ink jet print head on ink liquid discharge is relaxed. Accordingly, it is possible to provide an ink jet print head in which an ink droplet is stably discharged with high reliability. It is also possible to provide an ink jet printing device in which throughput is excellent and an ink consuming amount is reduced by further reducing the number of restoring times. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1A is a perspective plan view of an ink jet print head in accordance with a first embodiment of the present invention. FIG. 1B is a cross-sectional view taken along line 1 B— 1 B of FIG. 1 A. FIG. 2A is a perspective plan view of an ink jet print head in accordance with a second embodiment of the present invention. FIG. 2B is a cross-sectional view taken along line 2 B— 2 B of FIG. 2 A. FIG. 3A is a perspective plan view of an ink jet print head in accordance with a third embodiment of the present invention. FIG. 3B is a cross-sectional view taken along line 3 B— 3 B of FIG. 3 A. FIG. 4A is a perspective plan view of an ink jet print head in accordance with a fourth embodiment of the present invention. FIG. 4B is a cross-sectional view taken along line 4 B— 4 B of FIG. 4 A. FIG. 5 is an appearance perspective view showing one example of an ink jet printing device to which the ink jet print head applying the present invention thereto is mounted as an ink jet cartridge. FIGS. 6A, 6 B, 6 C, 6 D, 6 E, 6 F and 6 G are explanatory process views showing one example of a manufacturing method of the ink jet print head of the present invention. FIG. 7A is a perspective plan view showing the construction of a conventional ink jet print head. FIG. 7B is a cross-sectional view taken along line 7 B— 7 B of FIG. 7 A. FIG. 8A is a perspective plan view of an ink jet print head in accordance with a fifth embodiment of the present invention. FIG. 8B is a cross-sectional view taken along line 8 B— 8 B of FIG. 8 A. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The embodiments of the present invention will next be explained with reference to the drawings. [First Embodiment] Contents of the present invention will next be explained in detail with reference to the drawings. FIG. 1A is a typical view of an ink jet print head in accordance with a first embodiment of the present invention. A discharging port is directed downward in FIG. 1 B. In FIGS. 1A and 1B, a substrate 4 has an ink supplying port end 3 constructed by a through port formed in a long groove shape. Electrothermal converting elements 1 as discharging energy generating elements are arranged in a zigzag shape every one column on both sides of the ink supplying port end 3 in its longitudinal direction. A covering resin layer 6 as an ink flowing path wall for forming an ink flowing path is arranged on this substrate 4 . A discharging port plate 5 having a discharging port 2 is arranged on this covering resin layer 6 . Further, a long projection 7 in an arranging direction of the electrothermal converting elements is arranged just above the ink supplying port end 3 on an inner surface of the discharging port plate 5 . Here, an edge of the ink supplying port end 3 is shown by a straight line in FIGS. 1A and 1B, but there is also a case in which this edge is actually more or less curved (by about several μm) from the problem of a manufacturing method. Since the projection 7 has a tapering shape, no wall of the projection 7 is strictly perpendicular to the discharging port plate 5 and the projection 7 has the same height h as the covering resin layer 6 . It is preferable that the projection 7 is longer. However, the length of the projection 7 may be also set to be short. Further, the covering resin layer 6 and the projection 7 are shown as separate members, but can be simultaneously formed as the same member by forming this covering resin layer 6 on the substrate 4 by a technique such as spincoat, etc. The substrate 4 is fixed by a supporting member 9 and an ink supplying port 8 is arranged between the ink supplying port end 3 of the substrate 4 and the supporting member 9 . An unillustrated round hole flowing path for supplying ink to the ink supplying port 8 is formed in the supporting member 9 . The movement of a residual bubble in each of the ink jet print head of the present invention and a conventional ink jet print head will next be explained. First, in the conventional construction (FIGS. 7 A and 7 B), when an electrothermal converting element 1 is heated by applying an electric signal to this element and a bubble is generated, an ink droplet 10 is discharged from the discharging port 2 and a high speed ink flow is simultaneously generated from the ink flowing path to the ink supplying port end 3 . A fine residual bubble is included in this ink flow and is conveyed to the ink supplying port. When this ink flow reaches a portion of the ink supplying port end 3 , an eddy is caused in a corner portion of the ink supplying port and this eddy portion tends to be stagnated. When the bubble stays in this stagnant portion, this bubble is attached to an ink supplying port wall face 12 so that this bubble is not easily removed from the ink supply port wall face 12 . Then, this bubble is grown every time the fine residual bubble is attached to this bubble. A bubble having several hundred pm in diameter is finally formed. When a plurality of such bubbles having several hundred μm in diameter exist within the ink supplying port 8 , the bubbles block the ink supplying path in a wide range so that the effect of a common ink flowing path portion is greatly reduced and the ink supply becomes insufficient. In contrast to this, in the construction of the present invention, a high speed ink flow directed from the ink flowing path to the ink supplying port end 3 hits against a wall face of the projection 7 so that the direction of the high speed ink flow is changed to a downward direction in FIGS. 1A and 1B (an arrow mark in these figures). Thus, a speed component in a common liquid chamber direction is given to the ink flow. This ink flow includes small bubbles such as a residual bubble generated by cavitation caused by the high speed ink flow and a bubble, etc. discharged from the discharging port at an ink discharging time. These small bubbles are collected and grown within the ink supplying port 8 so that a bubble 11 is formed. Upward force in FIGS. 1A and 1B is applied to the bubble near the supplying port by the high speed ink flow near the ink supplying port. As a result, the bubble 11 pushed and flowed by the high speed ink flow is attached to a wall portion separated from the supplying port and is grown. Accordingly, an influence of bubbles on the ink supply is small even when many big bubbles exist. Therefore, no ink supplying defect is caused even when the size of a bubble is increased in comparison with the conventional case. When the distance L between a longitudinal wall of the projection 7 and the edge of the ink supplying port end 3 is excessively increased, the speed of the ink flow is reduced and hydrodynamic force applied to the bubble is reduced so that the above effect is weakened. When the distance L is extremely smaller than the height h, this small portion becomes a resistance so that this resistance has a bad influence on refill characteristics. Accordingly, it is not preferable that the distance L is extremely smaller than the height h. In FIGS. 1A and 1B and subsequent figures, an electric wiring for operating the electrothermal converting element 1 , etc. are not illustrated. In this embodiment, a silicon substrate (wafer) is used as a material of the substrate 4 , but the present invention is not particularly limited to this case. Glass, ceramics, plastic, or a metal, etc. may be also used as the substrate if the electrothermal converting element 1 as an ink discharging generating element is constructed by this substrate and this substrate constitutes a supporting body of the discharging port plate 5 as a material layer forming the ink discharge port 2 , and this substrate can function as one portion of an ink flowing passage constructional member. FIGS. 6A to 6 G (cross-sectional views taken along line 6 A— 6 A of FIG. 1A) show a manufacturing method of the ink jet print head in the present invention. In this embodiment, a desirable number of electrothermal converting elements 1 are first arranged on the substrate 4 shown in FIGS. 1A and 1B. Next, as shown in FIG. 6B, a soluble resin layer 13 is formed on the substrate 4 including the electrothermal converting elements 1 . As shown in FIG. 6C, an ink flow path pattern is formed in this resin layer 13 . At this time, a pattern for providing a rib structure is formed on an upper face of the resin layer 13 corresponding to a forming portion of the ink supplying port 8 (see FIG. 6 E). Further, a covering resin layer 6 is formed on the above soluble resin layer 13 as shown in FIG. 6 D. An ink discharge port 2 is formed in the covering resin layer 6 (see FIG. 6 E). It is sufficient to form the ink discharge port 2 by a conventional technique. For example, the ink discharge port 2 can be formed by any technique such as etching using O 2 plasma, excimer laser boring, exposure using an ultraviolet ray, a deep-UV ray, etc. The ink supplying port 8 is next formed in the substrate 4 . The ink supplying port 8 is formed by chemically etching the substrate. More concretely, a silicon (Si) substrate is used as the substrate 4 , and the ink supplying port 8 is formed by anisotropic etching using a strong alkali solution such as KOH, NaOH, TMAH, etc. (see FIG. 6 G). At this time, the ink supplying port can be also formed before an ink flowing path pattern and a pattern for providing the rib structure are formed as shown in FIGS. 6B and 6C and the ink discharge port is formed as shown in FIGS. 6D and 6E. However, the rib structure as shown in the present invention can be achieved by forming a soluble resin layer on a flat face and forming a pattern and further forming a covering resin layer on this pattern as shown above. After the ink flowing path pattern, the pattern providing the rib structure and the ink discharge port are formed, it is considered to use a mechanical means such as a drill, etc. and light energy such as a laser, etc. as a means for forming the ink supplying port. However, there is a possibility of damaging the previously formed ink flowing path pattern, etc. in these techniques. Accordingly, it is difficult to adopt these techniques. Therefore, it is optimal to form the ink supplying port by chemical etching, especially, anisotropic etching of the silicon substrate. Subsequently, as shown in FIG. 6G, the ink flowing path can be formed by eluting the soluble resin layer 13 . At this time, the rib structure is formed on the ink supplying port end 3 . Finally, the ink jet print head is completed by making an unillustrated electric junction for operating each of the electrothermal converting element 1 . The present invention has excellent effects in the recording head of a bubble jet system among the ink jet print head. The present invention is particularly optimal for a recording head manufactured by a method described in each of Japanese Patent Application Laid-Open Nos. 4-10940, 4-10941 and 4-10942. In each of these publications, a driving signal corresponding to recording information is applied to an electrothermal converting element and thermal energy providing a sudden rise in temperature exceeding nuclear boiling of ink is generated from the electrothermal converting element. Thus, a bubble is formed within the ink and is communicated with the external air and an ink liquid droplet is discharged. In the above method, a small ink liquid droplet (equal to or smaller than 50 pl) can be discharged and the ink liquid in front of a heater is discharged. Therefore, the ink liquid droplet is stabilized in volume and speed without any influence of temperature so that an image having a high quality can be obtained. The present invention is also effective as a recording head of a full line type capable of simultaneously recording an image over the entire width of a sheet of recording paper. Further, the present invention is effective in a color recording head in which the recording head is integrally formed or plural recording heads are combined with each other. Next, an ink jet print head having the following construction is manufactured as the ink jet print head corresponding to the above first embodiment. Namely, the ink jet print head has an ink supplying port 8 constructed by a through port formed in the shape of a long groove having 155 μm×11 mm in size. A substrate 4 has 128 electrothermal converting elements 1 as discharging energy generating elements on both sides of the ink supplying port 8 in its longitudinal direction. These electrothermal converting elements 1 are arranged in a zigzag shape at a pitch of 300 DPI every one column. A covering resin layer 6 having a height H=12 μm and a discharging port plate 5 having a thickness of 9 μm are formed on the substrate 4 . Thus, the ink jet print head in this embodiment is made. The distance L between the ink supplying port end 3 and a wall of the above projection 7 in its longitudinal direction is changed to 12, 16.5 and 27.5 μm so that three kinds of ink jet print heads are made. First, a solid black printing operation is performed by using these three kinds of ink jet print heads. Thereafter, a collecting situation of bubbles is observed from a front face of the discharging port plate after the full black printing operation. In a conventional example, bubbles exist only near the ink supplying port. However, in each of the three kinds of ink jet print heads in the first embodiment, bubbles exist in a deep portion of a common liquid chamber so that bubble separating effects obtained by the projection can be confirmed. A continuation time of the solid black is measured at a discharging frequency of 10 kHz, and the ink jet print head in this embodiment and the conventional ink jet print head are compared with each other and are evaluated. Table 1 shows measured and evaluated results. TABLE 1 L 12 μm 16.5 μm 27.5 μm Ratio of continuation time 3.0 2.3 2.2 of solid black in the times times times invention to that in conventional case The continuation time in the ink jet print head in this embodiment is twice or more in any case in comparison with the conventional case. Further, it is preferable to set the distance L to be shorter. [Second Embodiment] FIG. 2A is a typical view of an ink jet print head in accordance with a second embodiment of the present invention. A discharging port is directed downward in FIG. 2 B. The ink jet print head in this embodiment differs from that in the first embodiment only in the shape of a projection 7 in FIGS. 2A and 2B. The projection 7 has a length of 70 μm in a longitudinal direction B and a thickness T of 15 μm. One projection 7 is arranged with respect to each ink flowing path. The distance L between an ink supplying port end 3 and a wall coming in contact with an ink flow at a discharging time is set to 27.5 μm. A longitudinal length of the ink flowing path is set to be equal to or greater than a width of the ink flowing path such that a direction of the ink flow generated at the discharging time can be effectively changed. Thus, effects similar to those in the first embodiment can be obtained even when the shape of the projection 7 is different from that in the first embodiment. [Third Embodiment] FIG. 3A is a typical view of an ink jet print head in accordance with a third embodiment of the present invention. In FIG. 3B, a discharging port is directed downward. The ink jet print head in this embodiment differs from that in the first embodiment only in the shape of a projection 7 in FIGS. 3A and 3B. The projection 7 is entirely parallel to a ridgeline of an ink supplying port end 3 , but is not parallel to the ridgeline in each ink flowing path unit. For example, a shift in parallel with the ridgeline is 20 μm in a near portion and 35 μm in a far portion. Thus, a clearance required to supply ink can be secured even when the ridgeline of the ink supplying port end 3 is not a straight line, but is locally vibrated. Here, it is preferable that the area S of a portion shown by an oblique line is larger than the cross section of an ink flowing path. Thus, effects similar to those in the first embodiment can be obtained even when the shape of the projection 7 is different from that in the first embodiment. [Fourth Embodiment] FIG. 4A is a typical view of an ink jet print head in accordance with a fourth embodiment of the present invention. In FIG. 4B, a discharging port is directed downward. In the ink jet print head in this embodiment, the shape of an ink flowing path differs from that in the first embodiment in that two ink flowing paths are arranged with respect to one discharging port. An outlet of each ink flowing path onto an ink supplying port side has an angle with respect to an ink supplying port. Further, the shape of the projection 7 differs from that in the first embodiment in FIGS. 4A and 4B. As shown in FIGS. 4A and 4B, the projection 7 is perpendicular to a central axis of the ink flowing path. Since the projection 7 is perpendicular to the central axis of the ink flowing path, an ink flow generated from an electrothermal converting element to the ink supplying port side at a discharging time is received from a front face so that the ink flow can be efficiently directed and guided to a wall face side of the ink supplying port. Thus, effects similar to those in the first embodiment can be obtained even when the shape of the projection 7 is different from that in the first embodiment. [Fifth Embodiment] In this embodiment, the surface of a projecting portion is set to have a lyophilic ink property so as to further preferably prevent the attachment of a bubble in a state in which the surface of the projection portion includes the surface of a discharging port plate (an ink supplying port projecting area of the discharging port plate) on an ink flowing path side just above the ink supplying port. Since this portion is set to have the lyophilic ink property, it is greatly reduced that the bubble is attached to the discharging port plate and an end tip of the projection. If the bubble is attached, the bubble is separated from an end tip portion of the projection and stays in the ink supplying port of the ink jet print head or is again dissolved into ink in an intermediate growing process of the bubble in which no bubble yet has an influence on ink droplet discharge. Namely, in the construction in this embodiment, no residual bubble is easily attached to the discharging port plate and the projecting portion in comparison with the conventional case. Further, even if the residual bubble is grown, the residual bubble is sucked into an ink flowing path so that no ink within the ink flowing path is divided into pieces. Accordingly, this construction does not easily cause a phenomenon in which the supply of the ink to the ink flowing path becomes insufficient and the ink within the ink jet print head becomes empty by communication with the atmosphere. In the ink jet print head in this embodiment, for example, an inner surface of the discharging port plate 5 and the projecting portion 7 can be formed by lyophilic ink processing through the supplying port 3 from a rear face of the substrate 4 in the first embodiment. Concretely, as shown in FIGS. 8A and 8B, a lyophilic ink coating 20 can be formed on the inner surface of the discharging port plate 5 including the projection 7 by using a suitable means such as oxidizing processing of the inner surface of the discharging port plate 5 including the projection 7 using an ozone gas, or sputtering of an inorganic oxide (SiO 2 , Al 2 O 3 , etc.) having the lyophilic ink property, etc. Since the lyophilic ink coating 20 is thus formed on the inner surface of the discharging port plate 5 including the projection 7 , it is possible to obtain further excellent effects of the bubble attachment prevention in comparison with the first embodiment. In this embodiment, the lyophilic ink coating is applied to the construction of the first embodiment as an example. However, this embodiment is not limited to this case. This embodiment also includes that the lyophilic ink coating is applied to the ink jet print head having another projecting shape. [Other Embodiments] FIG. 5 is a schematic perspective view of an ink jet printing device to which the ink jet print head of the present invention can be mounted. In FIG. 5, a lead screw 52 having a spiral groove 53 is rotatably pivoted in a body frame 51 . The lead screw 52 is moved in association with normal and reverse rotations of a drive motor 59 and is rotated through driving force transmission gears 60 , 61 . Further, a guide rail 54 for slidably guiding a carriage 55 is fixed to the body frame 51 . An unillustrated pin engaged with the spiral groove 53 is arranged in the carriage 55 . The carriage 55 can be reciprocated in the directions of arrows a and b in FIG. 5 by rotating the lead screw 52 by rotation of the drive motor 59 . A paper pressing plate 72 presses a recording medium 90 against a platen roller 73 in a moving direction of the carriage 55 . An ink jet print head cartridge 80 is mounted to the carriage 55 . The ink jet print head cartridge 80 is constructed by integrating one of the ink jet print heads described in the above first to fifth embodiments with an ink tank. This ink jet print head cartridge 80 is fixedly supported by the carriage 55 through a positioning means and electric contacts arranged in the carriage 55 , and is detachably attached to the carriage 55 . Photocouplers 57 , 58 constitute a home position detecting means for confirming the existence of a lever 56 of the carriage 55 in this area and reversely rotating the drive motor 59 , etc. A cap member 67 for capping a front face (an opening face of a discharging port) of the ink jet print head is supported by a supporting member 62 . Further, a sucking means 66 is arranged to perform a sucking restoring operation of the ink jet print head through an opening 68 within the cap. A supporting plate 65 is attached to a body supporting plate 64 . A cleaning blade 63 slidably supported by this supporting plate 65 is moved in forward and backward directions by an unillustrated driving means. No shape of the cleaning blade 63 is limited to the illustrated one, but a well-known shape can be applied. A lever 70 is arranged to start the sucking restoring operation of the ink jet print head. The lever 70 is moved in accordance with the movement of a cam 71 coming in contact with the carriage 55 , and driving force from the driving motor 59 is controlled by well-known transmission means such as a gear, latch switching, etc. These capping, cleaning and sucking restoring processings are performed in respective corresponding positions by an operation of the lead screw 52 when the carriage 55 is moved to a home position side area. If desirable operations are performed in well-known timing, each of these operations can be applied to this embodiment. The ink jet printing device explained above has a recording signal supplying means for giving a recording signal for operating an electrothermal converting body of the mounted ink jet print head to the ink jet print head. The ink jet printing device also has a control section for controlling an operation of this ink jet printing device. Since one of the ink jet print heads described in the above first to fifth embodiments is mounted to the ink jet printing device in this embodiment, a discharging direction of ink is stabilized. As a result, a shift in attaching position of an ink droplet to a recording medium is reduced so that an image having a high quality, etc. can be recorded. In this embodiment, the ink jet print head cartridge 80 is detachably mounted to the carriage 55 as an example. However, this embodiment is not limited to this case. For example, only an ink tank may be detachably mounted by integrating the ink jet print head with the carriage 55 . As explained above, in accordance with the present invention, the bad influence of a bubble left within the ink jet print head on ink droplet discharge is relaxed. Accordingly, it is possible to provide an ink jet print head in which the ink droplet is stably discharged with high reliability. Further, since it is not necessary to often perform restoring processing, throughput is improved and an ink consuming amount is reduced.
An ink jet print head has plural electrothermal converting elements for generating energy used to discharge an ink droplet, plural ink discharging ports arranged above the electrothermal converting elements and discharging the ink droplet, plural ink flowing paths respectively communicated with the plural ink discharge ports and internally including the electrothermal converting elements, a substrate for arranging the plural electrothermal converting elements in a columnar shape and having an ink supplying port constructed by a through port which is connected with the ink flowing paths and extends along an arranging direction of the electrothermal converting elements, and a discharging port plate having the ink discharge ports. The ink flowing paths are formed between the substrate and the discharging port plate by junctioning the discharging port plate onto the substrate. The ink jet print head further has a fluid resisting device of the ink flowing paths in which a side of the ink supplying port is opened in the vicinity of a communication portion of the ink flowing paths in an ink supplying port projecting are of the discharging port plate.
1
FIELD OF THE INVENTION The invention relates to a revolving card flat with a card-flat bar which has a card-flat foot and a web lying above the card-flat foot, and with a flexible clothing in the form of a clothing strip and with at least one fastening element in the form of a clip, the clip being attached with a first portion to the clothing strip, being led with a second portion along one longitudinal side of the card-flat bar and partially looping with a third portion around the card-flat foot with a looping angle. The looping angle is defined as the angle between the perpendicular, touching the side face of the card-flat foot, to the clothing bearing face of the card-flat foot and that face of the card-flat foot onto which the third portion of the clip is integrally formed. BACKGROUND OF THE INVENTION Various types of construction of revolving card flats are known from the prior art. Revolving card flats are used in carding. The revolving card flats employed currently consist essentially of a card-flat bar with a clothing. The card-flat bar is composed of a card-flat foot and web lying above the latter. The clothing is fastened to the card-flat foot with the aid of clips. The clothing itself is used in the form of clothing strips, on the underside of which a multiplicity of clothing needles in the form of small wire hooks are fastened. At the two ends of a card-flat bar, devices are provided which makes it possible to fasten the card-flat bar to a chain or a belt. U.S. Pat. No. 581,749 discloses a revolving card flat and a corresponding tool for fastening the clothing strip to the card-flat foot. In this case, first, the clips are connected to the clothing strip. In a further step, the clothing strip is joined together with the card-flat bar, and subsequently the free portions of the clips are bent around the card-flat foot, so that the clothing strip comes to lie, free of play, on the card-flat foot. The card-flat foot is in this case surrounded by the clips in a bracket-like manner. To make the connection between the card-flat foot and clothing strip by means of clips, a complicated movement of the two used is necessary. DE 128 552, likewise, discloses the fastening of a flexible clothing in the form of a clothing strip to the card-flat foot of a card-flat bar. The clip used in this case, on the one hand, engages into the foundation of the clothing strip and, on the other hand, engages around or surrounds the card-flat foot. This makes it possible for the lining material of the foundation of the clothing strip to lie firmly on the card-flat foot. Here, too, the disadvantage is that clips bent on both sides have to be manufactured. FIG. 1 shows a device, such as is used for drawing clothing strips onto card-flat bars. The card-flat bar 1 is built onto a clothing strip 10 previously laid into a holding device 8 , so that the card-flat foot 3 comes to lie on the clothing strip. The clips 5 are already fastened to the clothing strip 10 on longitudinal sides of the latter. The card-flat bar 1 is consequently introduced with the card-flat foot 3 between the clips 5 . With the aid of prebending rollers 6 , the clips 5 are performed. In a second step, by means of the form rollers 7 , the clips 5 are integrally formed onto the card-flat foot 3 . The prebending rollers 6 and form rollers 7 are moved in the longitudinal direction of the card-flat bar 1 for the integral formation of the clips 5 , while the rollers rotate and are pressed against the card-flat foot 3 . The device shown has the disadvantage that only a specific shape of the card-flat foot 3 fits together with the predetermined form rollers 7 . Also, complicated movement and clamping mechanisms are necessary so that the operation described above can be carried out. WO 2006/039829 discloses a further example of a device for attaching a clothing strip to a card-flat bar. A prepared clothing strip, in which the clips are already fastened with a first portion on both sides, is introduced into the device. The card-flat bar is subsequently introduced into the device with the card-flat foot against the clothing strip so that the clips lead with a second portion along the longitudinal sides of the card-flat foot. The bending cheeks of the device are then pivoted inwards against the card-flat bar, with the result that the third portion of the clips is integrally formed onto the card-flat foot. To generate the necessary holding force, in addition, a deformation of the clips along the longitudinal sides of the card-flat foot is generated by means of press battens. One disadvantage of the device is that a plurality of movements of pressing tools and bending cheeks are necessary in order to achieve a fastening of the clothing to the card-flat bar. Also, there is the risk that, in the case of excessive deformation of the clip, a change in shape of the overall card-flat bar may occur, because various elements of the card-flat foot are spanned by the clips. The prior art for fastening clothing strips to card-flat bars with the aid of clips likewise entails the disadvantage that the card-flat foot has to be subjected over its entire length and width and also its height to a narrow manufacturing and dimensional tolerances. In order to achieve a reliable fastening of the clothing strips, an exact coordination of the pressing tool, form rollers, dimensions, and shape of the card-flat foot with the dimensions of the clips and their material properties is necessary. This leads to a cost-intensive production of the individual parts and also of the equipment necessary for assembling them. An object of the present invention, then, is to avoid the disadvantages of the prior art and to provide a simple connection between the card-flat foot and clothing, without having to allow for any loss of holding force. SUMMARY OF THE INVENTION Objects and advantages of the invention are set forth in part in the following description, or may be obvious from the description, or may be learned through practice of the invention. Objects are achieved by means of the type of construction of a revolving card flat of the type mentioned in the Field of the Invention and by means of the method and the tool necessary for this, in accordance with aspects of the invention as set forth herein. Certain objects are achieved in that the clip loops with a third portion around the card-flat foot with an angle of between 90° and 30° (degrees of angle). A revolving card flat according to the invention has a card-flat bar. The card-flat bar is composed of the card-flat foot and of a web lying above the card-flat foot. Card-flat bars are currently produced mostly from one piece from steel, cast iron, or in the form of hollow profiles consisting of light metal or light metal alloys. Card-flat bars consisting of plastic or of composite materials may also be envisioned. A clothing is attached to that side of the card-flat foot which lies opposite the web, the clothing bearing face of the card-flat bar. In this case, mostly, flexible clothings are used. A flexible clothing comprises a foundation which is constructed from a plurality of fabric layers and which is pierced by needles. The clothing is produced in the form of strips, the width and length of these clothing strips corresponding to the dimensions of the card-flat foot. The clothing strips and the card-flat foot are held together along the longitudinal sides of the card-flat foot with the aid of fastening elements, which are known as clips. The clips have a first portion which is connected to the clothing strip. This takes place mostly by pricking into the foundation and by subsequently bending round the clips, so that a second portion of the clips leads along the lateral longitudinal edges of the clothing strip, parallel to the side faces of the latter or the longitudinal edges of the card-flat foot, in the direction of the web. A third portion of the clips then projects away from the clothing strip beyond the card-flat foot. There has previously been the belief that a sufficiently high holding force for operational requirements between the card-flat foot and the clothing strip can be achieved only by a crimping of the clip. This meant bending the third portion of the clip around through more than 90°, thus resulting in a looping around of the card-flat foot of more than 90°. Thus, bending resulted in a bracketing of the card-flat foot, which was intended to prevent the clip from slipping off laterally. According to the invention, however, by the clip being integrally formed onto the contour of the card-flat foot, a holding force sufficient for the requirements can be achieved even in a case of a looping around of less than 90°. Fastening the clothing strip simultaneously from both sides gives rise in the clothing strip to a tension which assists the frictional connection achieved by the clip fitting snugly against the card-flat foot. The frictional connection is achieved by the card-flat foot being looped around by the third portion of the clip. In this case, it was shown that a looping around of less than 90° leads, between the card-flat foot and the clip, to a frictional connection which fulfills the requirements to be met during operation by the connection of the card-flat foot and clothing strip. As regards the production and releasability of the connection, a looping angle of less than 70°, in particular of 60°, proved to be advantageous. In order to obtain a sufficiently high holding force via the frictional connection, a looping angle of more than 30°, preferably of more than 50°, is advantageous. In a preferred version of the invention, the clip is manufactured from light metal or a light metal alloy. The necessary forces for integrally forming the clip onto the card-flat bar are thereby reduced. In particular, the use of clips consisting of aluminium or of an aluminium alloy has proved appropriate. The card-flat bars, too, may be produced from light metal or light metal alloy. In particular, the card-flat bars may be designed as hollow profiles. The use of aluminium or of an aluminium alloy is also advantageous. The method for integrally forming the clips onto the card-flat foot is characterized by the use of simple press rams. The press rams in this case act simultaneously from both sides of the card-flat bar on the clips to be integrally formed. The press rams are in this case to be moved towards one another transversely to the longitudinal direction of the card-flat bar. The movement of the press rams takes place linearly in a plane which is parallel to the plane of the clothing strip. The press rams may be provided with a drive. The drive may take place electrically, pneumatically or hydraulically. A purely mechanical drive which can be actuated by hand may also be envisioned. In a preferred version, the card-flat bar has an additional rib above the card-flat foot which leads along, parallel to the card-flat foot, over the length of the card-flat bar. The rib in this case forms, together with the card-flat foot, a guide for the press rams. The press rams are guided by this rib in their movement in such a way that they cannot avoid the clip. The press rams are preferably manufactured from an elastic material, preferably from a thermoplastic, in particular polyethylene or polyamide. As a result, that part of the press ram which slides along on the card-flat foot and the third portion of the clip is deformed. Owing to this deformation, the press ram adapts to the contour of the clip and of the card-flat foot, thus leading to the clip being integrally formed onto the card-flat foot. By the clip being integrally formed exactly onto the contour of the card-flat foot in this way, unevenesses in the card-flat foot can be compensated. A compensation of production or dimensional tolerances on the card-flat bar is also possible. Already used and therefore slightly damaged card-flat bars may be reequipped with a clothing strip by means of the proposed method. When pressing operation has ended, the rams are retracted and resume their original shape. The tool used for carrying out the method makes it possible to receive a card-flat bar. The clothing strip, together with the clips already fastened to it, and the card-flat bar are introduced into the tool. The clothing strip and the card-flat bar are subsequently retained in their position with respect to one another. For this purpose, means are provided which, on the one hand, make it possible to position the clothing strip and card-flat bar, for example guides, and, on the other hand, fix this position, for example cramp it or clamp it. Advantageously, the card-flat bar is attained during the following pressing operation by means of a holding-down device. The press rams moving forward simultaneously from both sides may be manufactured from one piece and extend over the entire length of the clothing strip to be fastened. A division of the press ram into individual segments may also be envisioned, in which case the drive for the press ram may likewise be apportioned to individual segments. BRIEF DESCRIPTION OF THE DRAWINGS The invention is explained in more detail below with reference to exemplary embodiments and by means of drawings in which: FIG. 1 shows a diagrammatic illustration of a device for assembly of a card-flat bar and clothing according to the prior art. FIG. 2 shows a diagrammatic illustration of a cross section of a first revolving card flat according to the invention. FIG. 3 shows a diagrammatic illustration of a cross section of a second revolving card flat according to the invention. FIG. 4 shows a view of a detail of the fastening of a clothing strip to the card-flat foot. FIG. 5 shows a diagrammatic illustration of the tool for producing a revolving card flat according to the invention. FIG. 6 shows a diagrammatic illustrations of a cross section of a revolving card flat according to the invention during a pressing operation. DETAILED DESCRIPTION OF THE INVENTION Reference will now be made to embodiments of the invention, one or more examples of which are shown in the drawings. Each embodiment is provided by way of explanation of the invention, and not as a limitation of the invention. For example features illustrated or described as part of one embodiment can be combined with another embodiment to yield still another embodiment. It is intended that the present invention include these and other modifications and variations to the embodiments described herein. FIG. 1 shows an arrangement, conventional according to the present-day prior art, of a device for assembly of a card-flat bar and clothing strip to form a revolving card flat. The figure was discussed in detail under the prior art, and therefore a further description is dispensed with at this juncture. FIG. 2 shows a cross section of a revolving card flat according to an embodiment of the invention. The clothing strip 10 consists of the foundation 9 and of the needles 4 which are held in the latter and which constitute the actual clothing. The clothing strip is held on the card-flat foot 23 on each of the two sides by means of a clip 25 . The card-flat foot 23 and the web 22 located above it form the card-flat bar 21 . This card-flat bar 21 is provided (not illustrated) at its outer ends with a card-flat end head in each case. FIG. 3 shows a cross section of a further revolving card flat according to another embodiment of the invention. The card-flat bar 31 is designed as a hollow profile, the hollow profile increasing in width towards the clothing strip 10 and forming the web 32 . A card-flat foot 33 is formed at the lower end of the hollow profile. The slender part of the hollow profile in this case forms the web 32 . A rib 11 is integrally formed on the web 32 on both sides above the card-flat foot 33 and runs over the entire length of the card-flat bar 31 . A clothing strip 10 is attached on that side of the card-flat foot 33 which lies opposite web 32 , the clothing bearing face. The clothing strip 10 is held on the card-flat foot 33 by means of clips 35 attached to the longitudinal sides of the card-flat bar 31 . FIG. 4 shows a view of a detail from FIG. 3 . The clothing strip 10 consisting of the foundation 9 and of the clothing 4 is fastened to the card-flat foot 33 by means of the clip 35 . The web 32 is laid, opposite the clothing strip 10 , against the card-flat foot 33 . The card-flat bar 31 is produced in one piece, so that the card-flat foot 33 and the web 32 merge one into the other without any visible parting line. The clip 35 is illustrated, laid out, in a side view in the further part of FIG. 4 . In this case, the region A constitutes a first portion of the clip 35 . This is provided at the outer margin with serrations which, in the fastened state, engage into the foundation 9 of the clothing strip 10 . The region B designates a second portion of the clip 35 which, in the installed state, is led along the longitudinal side of the clothing strip or of the card-flat foot. The region C constitutes a third portion of the clip 35 . This is integrally formed onto the card-flat foot 33 and loops around the latter at the angle α. The looping angle α is defined as the angle between the perpendicular, touching the side face of the card-flat foot 33 , to the clothing bearing face of the card-flat foot 33 and that face of the card-flat foot 33 onto which the third portion (region C) of the clip 35 is integrally formed. The third portion (region C) of the clip 35 is bent away at the looping angle α out of alignment with the second portion (region B) of the clip 35 , so that this third portion (region C) bears against the card-flat foot 33 . FIG. 5 shows diagrammatically the tool for fastening the clothing strip 10 to the card-flat bar 21 , 31 . The half, designated by L, of FIG. 5 illustrates a card-flat bar 21 according to FIG. 2 . The half, designated by R, of FIG. 5 illustrates a card-flat bar 31 according to FIG. 3 . Irrespective of the differences between the two card-flat bars 21 , 31 , the procedure is the same for fastening the clothing strips 10 to the card-flat bars 21 , 31 or card-flat feet 23 , 33 . The clothing strip 10 is introduced into a receptacle 14 in the tool. In this case, a depression is arranged centrally in the receipt 14 over the length of the card-flat bar 21 , 31 , so that the clothing strip 10 is not damaged during the fastening operation. The clips 25 , 35 have in this case already been attached to the clothing strips 10 beforehand. The regions B and C ( FIG. 4 ) of the clips 25 , 35 are located in a plane which runs (not illustrated) advantageously perpendicularly to the clothing strip foundation. The card-flat bar 21 , 31 is introduced from above between the regions B and C of the clips 25 , 35 (see FIG. 4 ). By means of holding-down device 13 , the card-flat bar 21 , 31 , together with the clothing strip 10 lying beneath it, is pressed against the receptacle 14 and thus fixed. The card-flat bar 21 , 31 and clothing strip 10 are thus tension-mounted between the receptacle 14 and the holding-down device 13 engaging on the web 23 , 33 . In a next step, the two press rams 12 are led simultaneously up to the card-flat bar 21 , 31 from both sides of the latter. The press ram 12 presses the third portion (region C) of the clip 25 , 35 against the card-flat foot 23 , 33 upon further movement. As a result, the third portion of the clip 25 , 35 is integrally formed against the card-flat foot 23 , 33 by the press ram 12 . The press ram 12 is preferably manufactured from an elastic material, so that is slides over the third portion of the clip 25 , 35 , while the press ram 12 adapts to the contour of the card-flat foot 23 , 33 . As a result of this type of “bending” of the third portion of the clip 25 , 35 , the second portion of the clip 25 , 35 is drawn upwards against the ram 12 . Since this effect occurs on both sides of the card-flat foot 23 , 33 , the clothing strip 10 is drawn apart and tensioned. In the half, designated by R, of FIG. 5 , in a preferred version of the invention, the rib 11 is formed above the card-flat foot 33 . The rib 11 is shaped in such a way that its inclination gives rise to a preferably symmetrical depression between the rib 11 and the card-flat foot 33 , together with the inclination of the surface of the card-flat foot 33 . The middle of the press ram 12 preferably runs congruently with the middle of this depression. The connecting line between the middle of the depression and the middle of the press ram 12 corresponds at the same time to the direction of linear movement of the press ram 12 . In the half, designated by L, of FIG. 5 , there is no rib 11 present in the version of the card-flat bar 21 , as shown. As a replacement for the absent rib 11 , but with the same function, to be precise that of avoiding an evasion of the press ram 12 , a ram guide 15 is attached to the ram 12 itself. The ram guide 15 is advanced together with the press ram 12 . As a result, the insertion of the clothing strip 10 and of the card-flat bar 21 is not impeded when the press rams 12 are in their initial position, as illustrated in FIG. 5 . Owing to this measure, the application of the method does not depend on a type of construction of the card-flat bar which is specifically coordinated with it. The press rams 12 may be moved by means of mutually independent linear drives. The drive may be of the electrical, pneumatic or hydraulic type of construction. A connection of the press rams 12 may also be envisioned, for example by means of a linkage, in order to move both press rams 12 by means of the same drive. A mechanical drive actuated by hand may likewise be provided. If the holding-down device 13 , too, is provided with a drive, an automatic flow of the overall method may be envisioned. FIG. 6 shows a detail of the cross section of a revolving card flat according to the invention from the right half, designated by R, of FIG. 5 during the pressing operation, the press ram 12 being shown in the foremost position. The press ram 12 is pressed against the card-flat foot 33 with the force F. On account of its elasticity, the front part 16 of the press ram 12 which has penetrated into the depression between the card-flat foot 33 and the rib 11 is deformed. The deformed part 16 of the press ram 12 fills the entire depression, adapts to the contour and is partially upset. With the press ram 12 being adapted with is front part 16 to the contour of the depression by pressing with the force F, the card-flat bars 31 can be manufactured with greater tolerance in terms of the shape of that side of the card-flat foot 33 which lies opposite the clothing strip 10 and of the rib 11 . Also, after being used more than once, the card-flat bars 31 can be reused without any remachining of the faces and shapes against which the clip 35 bears. The force F to be applied is to be coordinated with the selected elasticity of the press ram 12 , with the contour of the card-flat bar 31 to be filled and with the clip 35 selected for fastening the clothing strip 10 . Modifications and variations can be made to the embodiments illustrated or described herein without departing from the scope and spirit of the invention as set forth in the appended claims.
A method for fastening a clothing strip to a card-flat bar by a fastening means in the form of clips is presented. In this case, the clips are integrally formed onto the card-flat foot by press rams guided simultaneously from both sides of the card-flat bar and parallel to the plane of the clothing strip. The clip is integrally formed onto the card-flat foot and loops around the latter with a looping angle of less than 90° and more than 30°. A corresponding tool for carrying out the method and also a revolving card flat are likewise proposed.
3
BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a photodetector for use in light output monitoring devices of semiconductor lasers, receiving devices of optical communication systems, etc. 2. Related Background Art FIG. 1A is a top view of the structure of a conventional light detecting element, and FIG. 1B is a sectional view along the line X--X' in FIG. 1A. As shown, the conventional light detecting element comprises a first conduction-type semiconductor substrate 1 with a first electrode 8 formed on the underside; a first conduction-type semiconductor crystal layer 2 including a light absorbing layer; and a second conduction-type first region 3 formed in the first conduction-type semiconductor crystal layer 2 by selectively diffusing a dopant. Thus formed is a pin photodiode structure. This pin photodiode structure includes an n-layer (or a p-layer) provided by the semiconductor substrate 1, a p-layer (or an n-layer) provided by a first region 3, and a light detecting region 10 provided by the pn junction (the depletion layer or the i layer). A second electrode 5 is provided on the first region 3 in the semiconductor crystal layer 2. The top of the first region 3 inside the electrode 5 is covered with a reflection preventive film 6, and the top of semiconductor crystal layer 2 outside the electrode 5 is covered with a device protective film 7. In the semiconductor device of the above-described structure, when an reverse bias is applied, an electric field is generated in the depletion layer. Electrons and holes generated by incident light on a light detecting region 10 are divided respectively to the first conduction-type region 3 and are accelerated. Thus a photocurrent can be taken outside, and an optical signal can be detected. In the above-described structure of FIG. 1A and 1B, when light is incident on the light detecting region 10, photo-carriers are generated in the depletion layer, and a good response characteristic can be obtained. But when light is incident outside the light detecting region 10, due to a density gradient, the generated carriers are diffused to reach the depletion layer, and are taken out in a photocurrent. The transfer of the diffused carriers is slow. When the carriers reach the light detecting region 10, adversely a tail is generated at the last transition of a light-pulse-responding waveform as shown in FIG. 2. In using such light detecting element in photodetectors for use in optical communication, etc., a lens 11, such as a spherical lens, a SELFOC lens or others, is disposed at the light incident part of the cap of the package as shown in FIG. 3 so as not to affect the response characteristic. This arrangement enables all the signal light emitted from an optical fiber or others to be focussed to be incident on the light detecting region 3. But this condensation increases an incident light intensity per a unit area of signal light incident on the light detecting region 3, and accordingly more carriers are generated in the depletion layer 10. Resultantly because of the space-charge effect produced by an increase of a carrier density in the depletion layer 10, the intensity of an electric field in the depletion layer 10 is decreased, and a drift rate of the carriers in the depletion layer 10 is lowered. Also tails occur at the falls of light pulse response waveforms. In view of this, the light amount to be incident on the light detecting element 20 has to be limited, and it is a problem that a maximum incident light amount on the semiconductor photodetector cannot be increased. This effect is more conspicuous especially when the reverse bias voltage is low, which makes it difficult to operate the semiconductor photodetectors at low bias voltages. In controlling a light output of a laser diode to be constant, the light emitted from the rear end surface of the laser diode is detected by a light detecting element, and an operating current of the laser diode is feed-back controlled. But because the light output of the laser diode is so intense that when light is focussed and incident on the light detecting region 3, the space-charge effect occurs, and as described above, the drift of the carriers is increased, and tails occur at the falls of response waveforms. The feed-back control of the laser diode is affected. SUMMARY OF THE INVENTION An object of this invention is to provide a semiconductor photodetector which can solve the above-described problems. To this end, a photodetector according to the present invention comprises a package in which a window is provided in a light incident portion, and a light detecting element is located within the package, the light detecting element comprising: a first region formed of second conduction-type semiconductor and embedded in a first conduction-type semiconductor layer; a second region formed of second conduction-type semiconductor and embedded so as to be spaced from and surround the first region; and a conductor layer provided both on at least one part of top surface of the first conduction-type semiconductor layer and on at least one part of top surface of the second region. In the semiconductor photo-detecting device, a window provided in the package is a simple through hole and any lens is not used in the package. A signal light, therefore, is not concentrated in a light receiving region of the photo-detecting element and the signal light is also incident on an outside of the light receiving region. As a result, the intensity of the signal light incident on the light receiving region decreases degrade the response characteristics due to space charge effect may be prevented. Further, it may be to make signal light having a large intensity incident into the photo-detecting device without limiting the amount of the signal light. Further, the similar effect may be also realized in using a transparent plate in the light incident portion. According to the above-described light detecting element, even if incident light leaks outside the light detecting region which is the pn junction formed between the first conduction-type semiconductor layer and the first region and adversely generates carriers, the carriers are absorbed by the second region with the result that the flow of the diffused carriers into the light detecting region can be prevented. Consequently a necessary photocurrent alone can be taken out to an outside circuit. Decrease of a response speed of the device can be prevented. The first conduction-type semiconductor layer and the second region are short-circuited by a conductor layer of a metal, a semiconductor or others formed over their top surfaces, and carriers absorbed by the second region can be recombined or extinguished. Accordingly carriers are not accumulated in the second region. Even when a light pulse of very high intensity is incident, no tail is generated at the last transition of a response waveform for the light pulse. Thus, electric and optical characteristics of the device can be improved. The present invention will become more fully understood from the detailed description given hereinbelow and the accompanying drawings which are given by way of illustration only, and thus are not to be considered as limiting the present invention. Further scope of applicability of the present invention will become apparent from the detailed description given hereinafter. However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1A is a plan view of a light detecting element used in a conventional photodetector for explaining the structure thereof. FIG. 1B is a sectional view of the light detecting element along X--X'. FIG. 2 is a graph of the light pulse characteristic of the conventional light detecting element. FIG. 3 is a sectional view of the conventional photodetector for explaining the structure thereof. FIG. 4A is a plan view of a light detecting element for use in the photodetector according to a first embodiment of this invention. FIG. 4B is a sectional view of the light detecting element along X--X'. FIG. 5 is a sectional view of the photodetector according to a second embodiment of this invention. FIG. 6A is a plan view of a light detecting element for use in the photodetector according to the second embodiment of this invention. FIG. 6B is a sectional view of the light detecting element along X--X'. FIG. 7A is a plan view of a light detecting element for use in the photodetector according to a third embodiment of this invention, which explains the structure thereof. FIG. 7B is a sectional view of the light detecting element along X--X'. DESCRIPTION OF THE PREFERRED EMBODIMENTS A first embodiment of this invention will be explained with reference to FIGS. 4A and 4B, and FIG. 5. FIG. 4A is a top view of the light detecting device according to the first embodiment, and FIG. 4B is a sectional view along the line X--X'. On an n + InP (Indium-Phosphide) semiconductor substrate 21 with an n-electrode 28 formed on the underside, there are formed a non-doped InP buffer layer 22a (carrier concentration: n=2×10 15 cm-3, thickness: 2 μm), a non-doped InGaAs (Indium-Gallium-Arsenide) light-detecting layer 22b (n=3×10 15 cm -3 , thickness: 3.5 μm), and a non-doped InP window layer 22c (n=1×10 15 cm -3 , thickness: 2 μm) for decreasing a dark current. In the light detecting layer 22b and the window layer 22c, there are formed a p-type first region 23 and a p-type second region 24 by selectively diffusing Zn. The first region has a 200 μm-diameter, and the second region 24(charge trapping region) has a 40 μm-width. The n-type region between the first region 23 and the second region 24 around the first region 23 has a 10 μm-width. A p-electrode 25 is formed on the first region 23, and a reflection reducing film or antireflection film 26 is formed on that part of the region 23 inside the electrode 25, and a device protecting film or passivation film 27 is formed on that part of the first region 23 outside the electrode 25 and the window layer 22c including the second region 24. In this structure, electrons and holes generated by incident light on the light detecting region 30 are divided respectively toward the semiconductor substrate 21 and the first region 23, and are accelerated. Consequently a photocurrent can be taken outside, and an optical signal can be detected. If light is incident on parts other than the light detecting region 30, generated unnecessary carriers are captured by a built-in potential formed in the second region 24 embedded in the semiconductor crystal layers 22a, 22b, 22c and are hindered from entering the light detecting region 30. Eventually a photocurrent necessary for detecting an optical signal can be taken out. But a part of the carriers absorbed and trapped by the second region 24 is recombined and extinguished in the semiconductor crystal layer, but the other part accumulates in the second region 24. Especially when a light pulse of high intensity is inputted, a ratio of carriers extinguished by recombination is low, and most remaining carriers are accumulated in the second region 24. Resultantly a built-in potential formed in the second region becomes weak, and a ratio of carriers trapped by the second region is lowered. Diffused carriers having a lower transfer speed flow into the light detecting region 30, and a tail is generated at the last transition of a response waveform for the light pulse. Thus, electric and optical characteristics of the device are affected. The above-described affection is more remarkable especially in the case that the second region 24 is not exposed at the end surface of the second region 24. In this case, recombinations and extinctions of the carriers hardly take place, and carriers are accordingly accumulated in the second region 24. In this state, as described above, electric and optical characteristics are affected. In the case that the second region 24 is exposed at an end surface of the device, carriers tend to leak at the end surface and to be recombined. Consequently most carriers are not accumulated in the second region 24, and accordingly a built-in potential in the second region 24 does not tend to be lowered. Consequently a ratio of carriers trapped by the second region 24 does not lower with the result that electric and optical characteristics are not seriously affected. However, in applying the light detecting device according to this embodiment to various optical devices, it is necessary to extinguish generated carriers more quickly to maintain a state in which no carriers are accumulated in the second region 24 even when light of high intensity is inputted. Here to eliminate the above-described influence, in addition to the above-described structure, as shown in FIGS. 4A and 4B, a metal film 31 is formed on the semiconductor crystal layers 22a, 22b, 22c so as to be in contact both with the p-type second region 24 and with the n-type region outside the second region 24. This metal film 31 is formed by alloying Au/Zn/Au and is in contact over a 10 μm-width both with the second region 24 and with the n-type region outside the second region 24. The area of the metal film 31 is 20 μm×40 μm. It is preferable that the light detecting layer 22b has a thickness of 2˜7 μm for good absorbing efficiency of incident light, but the width is not necessarily limited to this range. The n-type region between the p-type first region 23 and the p-type second region 24 preferably has a width of 2˜40 μm, but the width is not necessarily limited to the range. The shape and width of the metal film 31 in contact with the n-type region and with the p-type second region 24 are not necessarily limited to the above. In the above-described structure, when light is incident on regions other than the light detecting region 30, unnecessary generated carriers are captured by the second region 24 which is a charge trapping region. Consequently no tail is generated at the last transition or the fall of a light pulse, and only a photocurrent necessary for the detection of an optical signal can be taken out. The captured carriers are recombined and extinguished by the metal film 31 short-circuiting the window layer 22c and the second region 24 and are not accumulated in the second region 24. Accordingly a ratio of carriers captured by the second region 24 is not lowered, and electric characteristics and optical characteristics are not affected. In terms of the structure, it is not necessary to provide an extra electrode and connect the same to the electrode 28 in order to take out accumulated carriers. The device can have a simplified structure. The diameter of the region 23, etc. is not limited to this embodiment. FIG. 5 shows a photodetector using the above-described light detecting element. In this photodetector the light detecting element shown in FIGS. 4A and 4B is mounted on a constituent member 52 covered with a cap 53 of a package. A window of a light transmitting plate 54 is disposed at a required position so that light can be incident on a light detecting region 23 of the light detecting element 50. Because this photodetector uses no lens, signal light emitted from an optical fiber 55 is not focussed onto the light detecting region 23 but is incident on the light detecting element 50 divergently outside the light detecting region 23. In this structure, even when light is incident outside the light detecting region 23, unnecessary generated carriers are trapped in a second region 24 and extinguished. Accordingly it is not necessary to focus signal light so that the signal light is incident only on the light detecting region 23, and to restrict, to this end, a light amount to be incident on the photodetector. The photodetector according to a second embodiment of this invention will be explained. The mounting of the light detecting element on the package in the second embodiment is the same as in the first embodiment, and will not be explained here. The structure and function of the light detecting element will be explained with reference to FIGS. 6A and 6B. FIG. 6A is a top view of the light detecting element according to this embodiment, and FIG. 6B is a sectional view along the line X--X'. On a Fe doped InP substrate 21 (specific resistance: ρ=1MΩ.cm), there are formed a non-doped InP buffer layer 22a (n=1×10 15 cm -3 , thickness: 1 μm), a non-doped InGaAs light detecting layer 22b (n=1×10 15 cm -3 , thickness: 4 μm), and a non-doped window layer 22c (n=2×10 15 cm -3 , thickness: 3 μm). In the light detecting layer 22b and the window layer 22c there are formed a p-type first region 23 and a p-type second region 24 by selectively diffusing Zn by ampul or sealed tube method. The first region has a 300 μm-diameter. Because of this region 23, a structure including the pn junction as the light detecting region 30 can be provided. The n-type region between the first region 23 and the second region 24 has a 20 μm-width. On the first region 23 there is provided a p-electrode 25. An antireflection film 26 is provided on that part of the region 23 inside the electrode 25, and a device protecting film 27 is formed on that part of the region 23 outside the electrode 25 and on the second region 24 in the window layer 22c. An n-electrode 48 for the light detecting device is formed on that part of the InP window layer 22c outside the second region 24 and on a part of the second region 24. The n-electrode 48 has a 330 μm-inner diameter and is over the second region 24 by 5 μm. In the above-described structure, the electrode 48 formed in contact with both the p-type second region 24 and the n-type window layer 22c can function as the n-electrode 28 (FIG. 4B) for taking out a photoelectric current, and as the metal film 31 (FIGS. 4A and 4B) for recombining carriers captured by the second region (charge trapping region) 24. The second embodiment has a simple structure but can produce the same advantageous effect as the first embodiment. The photodetector according to a third embodiment of this invention will be explained. The mounting of the photodetecting element on the package in the third embodiment is the same as in the first embodiment, and will not be explained here. The structure and function of the light detecting element will be explained with reference to FIGS. 7A and 7B. FIG. 7A is a top view of the light detecting element according to the third embodiment of this invention, and FIG. 7B is a sectional view along the line X--X'. As shown, on the surface of an n-type (first conduction-type) semiconductor substrate 21 with an n-electrode 28 formed on the underside, there is formed an n-type semiconductor crystal layer 22. A p-type (second conduction-type) first region 23 is formed on the semiconductor crystal layer 22 by diffusing a dopant by ampul method. The first region 23 has a 300 μm-diameter. The first region 23 forms a pn junction which is a light detecting region 30. This first region 23 is surrounded by a p-type second region 24 which is formed as a charge trapping region by diffusing a dopant. The second region 24 is spaced from the first region 23 by 20 μm. A p-type (second conduction-type) electrode 25 is provided on the first region 23. An antireflection film 26 is formed on that part of the first region 23 inside the electrode 25, and a device protecting film 27 is formed on that part of the first region 23 outside the electrode 25 and on the semiconductor crystal layer 22 including the second region 24. A metal film 31 is provided in contact with the semiconductor crystal layer 22 and with the second region 24. In this embodiment, the metal film 31 contacts over a 5 μm-width respectively with the semiconductor crystal layer 22 and with the second region 24 so that carriers captured by the second region can be recombined and annihilated. The metal film 31 has an area of 10 μm×50 μm. In this structure as well as that according to the first embodiment, unnecessary carriers are collected in the second region further to be recombined and extinguished by the metal film 31. Accordingly diffused carriers never affect electric characteristics of the device, such as response speed etc., and optical characteristics thereof. But a disadvantage of this embodiment is that because of the location of the metal film 31, whose reflectance is high, near the first region 23, in comparison with the first embodiment light tends to leak to the surroundings. The semiconductor materials and their dimensions referred to above are merely exemplified and can be varied in accordance with applications, wavelengths to be used, etc. For example, the materials of the semiconductors may be compound semiconductors, such as GaAs (Gallium-Arsenide), InGaAsP (Indium-Gallium-Arsenide-Phosphide), AlGas (Aluminium-Gallium-Arsenide), CdTe (Cadmium-Telluride), HgCdTe (Mercury-Cadmium-Telluride), InSb (Indium-Antimonide). etc., or Si (Silicon), Ge (Germanium), etc. In the case that AlGaAs is used for the light absorbing layer, GaAs or others, for example, can be used for the window layer. As dopants, Be (Beryllium), Cd (Cadmium), etc. may be used. The dopants may be added by ion implantation or others. The second region and the semiconductor crystal layer is not necessarily short-circuited by a metal film, but may be short-circuited by a semiconductor layer. The metal film may be formed e.g., by vacuum evaporating an AuGeNi alloy or by depositing Au/Ge/Ni on the semiconductor crystal layer and alloying the same. The semiconductor layer may be provided by, e.g., amorphous silicon. From the invention thus described, it will be obvious that the invention may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications as would be obvious to one skilled in the art are intended to be included within the scope of the following claims.
This invention relates to a photodetector including a package having a window disposed in a light incident part, and a light detecting element installed in the package. The light detecting element includes a first region formed of a second conduction-type semiconductor and embedded in a first conduction-type semiconductor layer; a second region formed of second conduction-type semiconductor and embedded so as to be spaced from and to surround the first region; and a conductor layer provided both on at least one part of top surface of the first conduction-type semiconductor layer and on at least one part of top surface of the second region. The first region is surrounded by a second conduction-type second region. On the surface of the semiconductor crystal layer, an electrode is formed on the first region, and a reflection preventing layer is formed on that part of the first region inside the electrode, and a device protecting film is formed on that part of the first region outside the electrode. On the semiconductor crystal layer, a metal film is formed in contact both with the semiconductor crystal layer and with a second region. This structure enables the second region to capture unnecessary charges and further to recombine and extinguish them.
8
BACKGROUND The invention relates to a variable valve drive of an internal combustion engine for actuating a gas-exchange valve. Its motion follows a lift of a cam and also a lift of a piston of a hydraulic force-applying device superimposed on the lift of the cam and independent of the lift of the cam. This is connected to a hydraulic medium line with adjustable hydraulic medium pressure and has a pressure chamber charging the piston and also a hydraulic valve lash compensating device with a work chamber limited radially by a housing. Valve drives according to this class are known in the state of the art. For example, DE 43 18 293 A1 discloses a hydraulic force-applying device on a finger lever drive with a pivot support, which pivotably supports a finger lever actuated by a cam in the actuation direction of the gas-exchange valve. The hydraulic force-applying device here expands the functionality of a hydraulic valve lash compensating device by a hydraulic lift, which is variably adjustable and which is superimposed on the mechanical lift given by the cam on the gas-exchange valve. Through this superimposition, on one hand, a reduction of the gas-exchange valve lift in terms of maximum lift and/or opening period up to complete standstill of the gas-exchange valve is possible. On the other hand, by superimposing the hydraulic and the mechanical lift, an expansion of the lift generated by the cam in the sense of an earlier opening time or a later closing time or an increased maximum lift or combinations of the like are possible. For realizing this functionality, the publication noted above proposes an essentially conventional pivot support common for someone skilled in the art with hydraulic valve lash compensation. This pivot support is guided so that it can move longitudinally in an additional outer housing, which is supported in a recess of the internal combustion engine. Here, a bottom side of the pivot support, together with an inner wall of the outer housing, comprises a pressure chamber, which is connected to a pressure-adjustable hydraulic medium line. Although the use of a conventional pivot support, which is to be modified, if necessary, based on changed movement and installation relationships, promises acceptable production costs of the hydraulic force-applying device, on one hand the increased installation requirements in terms of diameter and length are disadvantageous due to the addition of additional wall thickness. Such an extension of the diameter and length is to be viewed as critical for modern installation-limited internal combustion engines, because the wall thickness between the receptacle bore is already small for supporting the pivot support and adjacent hollow spaces, for example, charge changing and cooling water channels or spark plug shafts, and permit less play for an extension of the diameter or length of the receptacle bore. Another disadvantageous aspect given with the use of such a pivot support is the increase in the mass of the moving valve drive components. Thus, it is necessary for a hydraulic force-applying device according to the cited publication that the pivot support must be incorporated completely in the hydraulic lift that is sometimes characterized by high acceleration values. The mass of the pivot support moved at the same time thus requires either a limitation of these acceleration values to values that worsen the quality of the charge change or a high hydraulic drive output is necessary for achieving high acceleration values of the hydraulic lift. The latter must be applied, however, in a direct or indirect way by the internal combustion engine itself and is to be limited to a minimum with respect to a tolerable increase in the frictional output of the internal combustion engine. The described disadvantages incidentally do not apply just for the cited finger lever drive, but instead also for other valve drive constructions. This applies to a greater degree for valve drives, in which the components of the hydraulic force-applying device also follow the mechanical lift of the cam, as is the case, for example, for cup-tappet drives. In this respect, an increase in the moving mass would have a disadvantageous effect, in particular, on the achievable acceleration values of the valve drive. SUMMARY Therefore, the present invention is based on the objective of improving a valve drive of the type noted above, such that the listed disadvantages are avoided. The hydraulic force-applying device should be distinguished, first, through minimal installation requirements, so that it can also be used in modern installation-limited internal combustion engines. Second, its moving components should have the smallest possible mass, in order to actuate the gas-exchange valve with the highest possible acceleration values. The force-applying device should finally be able to be manufactured as economically as possible with lower complexity. The objectives are met using the features of the invention, while advantageous improvements and constructions can be taken from the following description. Accordingly, the objectives are met in that the housing is simultaneously used for radially limiting the pressure chamber. In the valve drive according to the invention, the hydraulic force-applying device is constructed, such that the work chamber of the hydraulic valve lash compensating device and the pressure chamber are limited radially by a common housing. Therefore, the necessity for a separate outer housing, whose wall thickness would lead to a considerable addition to the diameter and length of the force-applying device, is eliminated. Its minimal installation requirements thus allow excellent adaptability of the valve drive according to the invention in already existing internal combustion engines. Simultaneously, through the low complexity of the hydraulic force-applying device, cost-effective manufacturability is given. Moreover, due to the small number of components in the force-applying device, the mass of the moving components is small, so that good acceleration values can be achieved for the actuation of the gas-exchange valve. Simultaneously, the expense for generating the hydraulic drive power with reference to good efficiency of the internal combustion engine can be kept to a low level. One especially advantageous construction of the valve drive according to the invention provides that the pressure chamber is limited axially by the piston and a first end side facing the piston in a compensating piston of the hydraulic valve lash compensating device guided so that it can move longitudinally in the housing. In this way, the work chamber of the hydraulic valve lash compensating device is arranged separate from the pressure chamber and is limited axially by a second end side of the compensating piston facing away from the piston. So that the work chamber is not expanded by the volume of the hydraulic medium line, outstanding stiffness is given for the hydraulic valve lash compensating device. Finally, proven components of conventional mass-production technology can be used. For example, it is possible to further use the restoring spring of the hydraulic valve lash compensating device designed for the relatively small lift of the compensating piston. A preferred construction of the valve drive constructed according to a further preferred embodiment that the compensating piston is constructed as a hollow body. In this way, a sufficiently large reservoir for hydraulic medium is created, which must be recirculated into the work chamber in a correspondingly large amount, in particular, when the compensating piston moves out of its lowered position into its work position, as can occur when the internal combustion engine starts up. As an alternative embodiment it can also be useful, however, that the pressure chamber is identical to the work chamber of the hydraulic valve lash compensating device. An advantage of this construction is that, first, the piston can be used as a large-volume hydraulic medium reservoir for supplying the work chamber of the hydraulic valve lash compensating device. Second, it can be advantageous, depending on production, to produce the piston in one piece together with the compensating piston. For a hydraulic force-applying device according to this embodiment, the hydraulic valve lash compensating device should be connected to a hydraulic medium supply independent of the hydraulic medium line. Such a partitioning of the hydraulic supply is then free from additional expenses especially when no gas-exchange valves of the internal combustion engine are also actuated by a hydraulic force-applying device and a hydraulic medium supply already exists anyway for supplying adjacent and exclusively cam-actuated valve drives. According to another embodiment of the invention, the valve drive should allow at least one secondary lift of the gas-exchange valve during a lift-free base-circle phase of the cam. This produces advantageous possibilities for recirculating exhaust gas internally in high quantities and precisely adjustable doses. This form of exhaust gas recirculation is the basis, in particular, for an operation of the internal combustion engine for homogeneous and self-igniting charging. Such a combustion process, also designated as the HCCI process (Homogeneous Charge Compression Ignition) can be used both for self-ignited diesel combustion engines and also for externally ignited Otto combustion engines at least in the partial load operation of the internal combustion engine mainly for the purpose of reducing emissions. The combustion sequence is set in the HCCI process essentially through the control of the charge composition and the charge temperature profile. For this combustion process, it has been shown that a high charge temperature is desired for controlling the ignition time. A very effective means for increasing the charge temperature is increasing the residual gas content, i.e., increasing the content of non-flushed exhaust gas and flushed exhaust gas recirculated back into the cylinder from the preceding combustion cycle into the cylinder charging for the next combustion cycle. Here, the residual gas content must be able to be adapted completely variably to the operating point of the internal combustion engine, wherein residual gas percentages of 60% of the cylinder charge and more can be necessary. Residual gas percentages at this level can no longer be provided by means of internal exhaust gas recirculation through conventional valve overshooting or by means of a device for external exhaust gas recirculation. Moreover, the HCCI process reacts with unacceptable combustion sequences in an extremely sensitive way to changes in the charging properties, so that, in addition to providing residual gas in the necessary amount, a combustion cycle-consistent, highly precise, and cylinder-specific dosing of the residual gas percentage is also necessary. The secondary lift takes place according to another embodiment of the invention preferably for an exhaust valve. In the case of the exhaust gas recirculation explained above, exhaust gas already displaced into the outlet channel is recirculated into the combustion chamber via the then still open exhaust valve during the suction cycle of the internal combustion engine. In contrast, however, there is also the possibility to operate the valve drive according to the invention as an engine brake, in particular, for air-compressing internal combustion engines as a safety-related expansion of the operating brake. Such engine braking is typically used for long-duration braking in commercial vehicles and is based on the principle that the drag moment of the internal combustion engine in engine-braking and coasting mode can be considerably increased by increasing the charge changing work and the vehicle is therefore braked. In this case, the exhaust valve is still open during the compression phase, so that the cylinder charge is not compressed like a pneumatic spring action, but instead is pushed into the outlet channel under the application of displacement work. In terms of the exhaust gas recirculation, however, it can also be useful that the secondary lift takes place on an intake valve. In this alternative construction, exhaust gas is displaced into the inlet channel in the thrust cycle of the internal combustion engine for a still open intake valve and recirculated into the combustion chamber during the suction cycle. A combination of these previously mentioned possibilities of exhaust gas recirculation is also possible. Accordingly, for setting the amount and temperature of the residual gas it can be advantageous to recirculate this gas both from the inlet channel and also from the outlet channel. Another preferred construction of the valve drive provides that wherein the valve drive is constructed as a finger lever drive and the hydraulic force-applying device is constructed as a pivot support. For the sake of simplicity, preferably the lubricating oil of the internal combustion engine is used as the hydraulic medium. In contrast, however, the use of any other suitable fluid in a hydraulic medium circuit, which would then be separated from the lubricating oil circuit of the internal combustion engine, is also conceivable. BRIEF DESCRIPTION OF THE DRAWINGS Additional features of the invention emerge from the following description and from the drawings, in which the valve drive according to the invention is illustrated as an example with reference to a cam follower drive with two differently constructed pivot supports of the hydraulic force-applying device. Shown are: FIG. 1 a view of the cam follower operation for a closed gas exchange valve with a first longitudinally sectioned pivot support, FIG. 2 an enlarged representation of the pivot support according to FIG. 1 , FIG. 3 a view of the cam follower operation for a closed gas-exchange valve with a second longitudinally sectioned pivot support, FIG. 4 an enlarged representation of the pivot support according to FIG. 3 . DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS In FIGS. 1 and 2 , the valve drive 1 according to the invention is disclosed using the example of a finger lever drive 2 with a pivot support 3 a as a component of a hydraulic force-applying device 4 a . A gas-exchange valve 5 , which is actuated via a finger lever 6 by a cam 7 in the opening direction, is shown. The finger lever 6 is supported on the pivot support 3 a in the actuation direction of the gas-exchange valve 5 and provides a rotatably supported roller 8 as a low-friction contact surface 9 to the cam 7 . The cam 7 has a cam lifting phase 10 , which generates a lift on the gas-exchange valve 5 , and a lift-free base-circle phase 11 . A piston 14 with an outer casing surface 15 and also a compensating piston 16 with an outer casing surface 17 are guided so that they can move longitudinally in an inner casing surface 12 of a hollow cylindrical housing 13 a . A first end section 18 of the piston 14 is turned towards a first end side 19 of the compensating piston 16 , while a second end section 20 of the piston 14 has a spherical construction for supporting the cam follower 6 so that it can pivot. A second end side 21 of the compensating piston 16 facing away from the piston 14 limits a work chamber 22 a of a hydraulic valve lash compensating device 23 a . The piston 14 can be spaced away from the first end side 19 of the compensating piston 16 and, together with this, limits a variable-volume pressure chamber 24 a of the hydraulic force-applying device 4 a. The valve lash compensating device 23 a connects to a hydraulic medium supply “S-LA”. The compensating piston 16 is usefully constructed as a hollow body 25 , in order to separate the pressure chamber 24 a from the work chamber 22 a of the valve lash compensating device 23 a and simultaneously to create a hydraulic medium reservoir 26 for the work chamber 22 a. The pressure chamber 24 a is connected via at least one passage opening 27 in the housing 13 a to a hydraulic medium line “S-P”, whose hydraulic medium pressure is adjustable. In FIG. 1 , the pivot support 3 a assumes a base position “A”, in which the piston 14 contacts with its first end section 18 the first end side 19 of the compensating piston 16 for low hydraulic medium pressure in the hydraulic medium line “S-P”. The gas-exchange valve 5 is here closed, because the cam 7 simultaneously contacts the roller 8 in its base-circle phase 11 . The hydraulic force-applying device 4 a generates a lift of the gas-exchange valve 5 superimposed on the lift of the cam 7 , in that the volume of the pressure chamber 24 a is enlarged by increasing the hydraulic medium pressure in the hydraulic medium line “S-P”. Simultaneously, the piston 14 distances itself away from the compensating piston 16 and actuates the cam follower 6 independent of the lift of the cam 7 in the opening direction of the gas-exchange valve 5 . This situation is shown in FIG. 2 for a lift position “B” of the piston 14 . A subsidence of the lift of the gas-exchange valve 5 generated by the hydraulic force-applying device 4 a is introduced by the return of the piston 14 into its base position “A”. For this purpose, the hydraulic medium line “S-P” is operated as a discharge line for reducing the volume of the pressure chamber 24 a. A prerequisite for a large time cross section of the lift generated by the hydraulic force-applying device 4 a on the gas-exchange valve 5 is the quickest possible movement of the piston 14 between the base position “A” and the lift position “B” and thus a quick volume change of the pressure chamber 24 a . As already mentioned, the piston 14 is located in its base position “A” with its first end section 18 in contact with the first end side 19 of the compensating piston 16 . In this respect, for a low-resistance feed and discharge of the hydraulic medium into or out of the pressure chamber 24 a it is useful that the piston 14 has on its first end section 18 at least one passage 28 for hydraulic medium. This passage 28 can be constructed according to the drawing as a depression 29 , which breaks an end surface 30 of the first end section 15 of the piston 14 essentially parallel to the first end side 19 of the compensating piston 16 . It is alternatively or additionally also possible to connect the pressure chamber 24 a via a passage with closed contours opening into the outer casing surface 15 of the hollow cylindrical piston 14 . FIGS. 3 and 4 disclose the valve drive 1 according to the invention with a pivot support 3 b , which differs in comparison with the pivot support 3 a of FIGS. 1 and 2 essentially by grouping a work chamber 22 b of a valve lash compensating device 23 b with a pressure chamber 24 b of a hydraulic force-applying device 4 b . The following description is therefore limited to the representation of the essential feature differences between the two embodiments. In FIG. 3 , the pivot support 3 b is shown in a base position “C”. The base position “C” corresponds to an installation position of the hydraulic valve lash compensating device 23 b and is therefore characterized in that an end surface 31 of a piston 32 facing away from the cam follower 6 is slightly distanced away from a shoulder 33 of a housing 13 b . Here, the piston 32 is used for the axial limiting of the work chamber 22 b that is identical to the pressure chamber 24 b . Thus, the work chamber 22 b is also connected to the hydraulic medium line “S-P” via a passage opening 27 in the housing 14 b for the purpose of changing the volume of the pressure chamber 24 b. The piston 32 is shown in FIGS. 3 and 4 as a one-piece piston 32 , which is simultaneously used for supporting the cam follower 6 so that it can pivot. However, the use of a multiple-piece piston is also equally possible, wherein an upper part supports the cam follower 6 and a lower part is used for limiting the pressure chamber 24 b in common with the work chamber 22 b. In FIG. 4 , the pivot support 3 b is shown for a lift position “D” with significantly increased distance of the end surface 31 of the piston 32 to the shoulder 33 of the housing 13 b . For the return of the piston 32 from this lift position “D” the hydraulic medium line “S-P” is operated, in turn, as a discharge line. The hydraulic medium line “S-P”, however, is then to be closed for the pivot support 3 b at the latest when the cam lifting phase 11 comes in contact with the roller 8 , in order to maintain the function of the valve lash compensating device 23 b. The valve lash compensating device 23 b can finally be supplied in a known way via a non-return valve 34 , which connects the hydraulic medium supply “S-LA” to the work chamber 22 b independent of the hydraulic medium line “S-P”. The valve drive 1 according to the invention has been explained using the example of a finger lever valve drive 2 as a preferred embodiment. The concept according to the invention, however, can be transferred equally to other valve drive constructions, for example, for cup tappet drives or tappet rod drives. Furthermore, the scope of protection of the invention should also include valve drives with a switchable construction through coupling means, in order to be able to transfer lifts of several cams as a function of the coupling state selectively to the gas-exchange valve 6 . This applies equally for valve drives that continuously vary the lift of the gas-exchange valve 6 by means of a cam and other adjustment elements. LIST OF REFERENCE NUMBERS AND SYMBOLS 1 Valve drive 2 Finger lever drive 3 a Pivot support 3 b Pivot support 4 a Force-applying device 4 b Force-applying device 5 Gas-exchange valve 6 Finger lever 7 Cam 8 Roller 9 Contact surface 10 Cam lifting phase 11 Base-circle phase 12 Inner casing surface 13 a Housing 13 b Housing 14 Piston 15 Outer casing surface 16 Compensating piston 17 Outer casing surface 18 First end section 19 First end side 20 Second end section 21 Second end side 22 a Work chamber 22 b Work chamber 23 a Valve lash compensating device 23 b Valve lash compensating device 24 a Pressure chamber 24 b Pressure chamber 25 Hollow body 26 Hydraulic medium reservoir 27 Passage opening 28 Passage 29 Recess 30 End surface 31 End surface 32 Piston 33 Shoulder 34 Non-return valve A-LA Hydraulic medium supply S-P Hydraulic medium line A Base position B Lift position CBase position D Lift position
A variable valve drive ( 1 ) of an internal combustion engine is provided which is used to actuate a gas exchange valve ( 5 ). Displacement thereof takes place via a cam ( 7 ) generated lift and via a lift generated by a piston ( 14, 32 ) of a hydraulic force applying device ( 4 a, 4 b ), which is superimposed on the cam lift and which is independent thereof. The hydraulic force applying device is connected to a hydraulic fluid line (S-P) which provides an adjustable hydraulic pressure medium and includes a pressure chamber ( 24 a, 24 b ) which is limited on one side by the piston ( 14, 32 ), in addition to a hydraulic valve lash compensation device ( 23 a, 23 b ) which includes a working chamber ( 22 a, 22 b ) which is radially defined by a housing ( 13 a, 13 b ). The housing ( 13 a, 13 b ) is also used to radially define the pressure chamber ( 24 a, 24 b ).
5
BACKGROUND OF INVENTION (a) Field of the Invention The present invention relates to a process or a method for preparing alloys and eventually alloyed negative electrodes. The invention also relates to new industrial products, the alloys and alloyed negative electrodes thereby obtained as well as a device making use of such negative electrodes. More specifically, the present invention is directed to electrochemical generators having high densities of energy, which generally include lithium, and is more particularly directed to alloyed negative electrodes, i.e. where lithium is present in a host structure, which is generally metallic, whose activity is lower than that of metallic lithium. (b) Description of Prior Art In most of the generators, utilizing alkali metals with organic, liquid or polymeric electrolytes, it has been observed that lithium has a tendency to form passivating films. The formation of such films, which is discussed in detail in J. P. Gabano, "Lithium Batteries", Acad. Press, N.Y. 1983, does not generally prevent the necessary ionic exchanges needed for the discharge of the lithium electrode because these films are generally thin and ionic conductors. This is particularly the case of non-rechargeable batteries. However, it has been realized that such films can electronically insulate an important fraction of the lithium when the latter is present in particulate form or has been electrochemically redeposited. One then observes an important decrease of the utilization of the negative electrode, which decrease must then be compensated by an excess capacity of the negative electrode. This problem is substantially reduced in the case of rechargeable systems by using lithium alloys having a high rate of diffusion of lithium and which are not thermodynamically favorable to the electrochemical depositing of pure metallic lithium during recharge. This will result in preventing the formation of dendrites of lithium and the electrical insulation of freshly deposited lithium. However, these alloys are generally hard and brittle intermetallic compounds which are generally prepared by pyrometallurgy and are consequently hard to convert into thin shapes such as by lamination. They are therefore used more often in particulate forms, pressed with a binder, as fritted substances or they can be prepared by electrochemical means, such as in the form of accumulators mounted in discharged state. These various processes designed for liquid electrolytes are not well adapted to polymeric electrolytes which make use of large surfaces and thicknesses of the order of some tens of microns. A partial solution to these problems has been proposed in the case of polymeric electrolytes formed of complex made of polyethers combined with an alkali salt, by utilizing composite electrodes where the alloy is dispersed in particulate form in a polymeric electrolyte which also acts as a binder between the particles, and in the presence of a carbon additive which has been added to improve the electronic and ionic exchanges at the interfaces. References will particularly be made to U.S. application Ser. No. 430,696 now U.S. Pat. No. 4,517,265 in the name of Hydro-Quebec, filed Sept. 30, 1982. This solution enables to prepare thin electrodes with large surfaces which are particularly well adapted to thin film generators operating with polymeric electrolytes. However, it has been observed that such electrodes can present in certain cases, particularly at operating temperatures higher than 80° C., a progressive decrease of utilization of the alloys during successive cycles. Moreover, such electrodes remain costly to prepare in view of the high cost of the starting alloys generally prepared by pyrometallurgy, for examples about $500/lb for LiAl. It should also be remembered that these alloys should then be crushed, screened and mounted in the form of electrodes under strictly inert atmosphere. SUMMARY OF INVENTION It is an object of the present invention to provide a process for the preparation of alloys in which one of the components is an alkali or alkali-earth metal. Another object of the present invention consists in providing a process which is economical, easy to operate for preparing alloyed electrodes with high surfaces and particularly well adapted with respect to electrochemical properties, such as cycling, to be associated with electrochemical generators with thin films, such as those utilizing polymeric electrolytes. Another object of the present invention consists in providing a process of preparing alloys of a host metal with an alkali or alkali-earth metal, alloyed negative electrodes prepared from these alloys and electrolytes which are preferably solid and based on polymers, and devices using the electrodes so produced in electrochemical generators which generally but not necessarily are based on lithium. Another object of the present invention concerns the preparation of alloys of a host metal, for example selected among aluminum, magnesium, silicon, zinc, boron, mercury, silver, alloys and mixtures thereof with an alkali or alkali-earth metal such as lithium, intended to give thin electrodes with high surface area. Another object of the invention relates to the preparation of thin negative electrodes having large surface area, which are particularly well adapted to thin film polymeric electrolytes. Another object of the present invention relates to the preparation, preferably near ambient temperature, of special compounds of alkali or alkali-earth metals with metals which can react to form intermetallic compounds, alloys or solid solutions. Another object of the present invention relates to the control of the composition of alloys prepared according to the present invention as well as their final shape. Another object of the present invention resides in the carrying out of treatments, which are more or less superficial, after the shaping of a host structure, such as for example, the formation of solid solutions of lithium in aluminum Li.sub.ε Al where ε represents a few percentage of Li with respect to Al. According to the present invention, these alloys are obtained by reacting a host element of the final alloy having the intended shape and structure, with an organic solution of an alkali or alkali-earth metal, preferably metallic lithium, generally in free radical form, also in contact with a source of said metal, such as lithium, so as to form alloys whose shape is determined by the starting host element. The activity of the alkali or alkali-earth metal, such as lithium can be controlled by the choice of the host metal and by the chemical composition of the solution, for example one whose free radical activity is generally lower than +600 mVvsLi° in the case of the preparation of negative electrodes. In other words, in its broad aspect, the invention relates to a method for the preparation preferably at room temperature, of metallic alloys containing an alkali or alkali-earth metal as well as a host metal, which comprises preparing an active organic solution of said alkali or alkali-earth metal as well as a source of said alkali or alkali-earth metal, and bringing said solution and said source of metal together, separately preparing a metallic structure containing said host metal, bringing the metallic structure together with the organic solution which is kept in contact with the source of metal, until there is formation of an alloy of the host metal and of the alkali or alkali-earth metal with the metallic structure, and the alloy has an activity which is determined by that of the organic solution, said organic solution then act as a transfer agent of the alkali or alkali-earth metal towards the metallic host structure. The invention also concerns a method of preparing alloyed metallic electrodes, which comprises contacting the alloys whose preparation has been described above with an electrolyte, such as a polymeric electrolyte for example those described in the French Patent Applications of Michel Armand and Michel Duclot, Nos. 78.32976, 78.32977 and 78.32978, now published under Nos. 2442512, 2442514 and 2442513. The organic solution of alkali or alkali-earth metal comprises for example a mixture of liquids including at least a polar aprotic solvent which is compatible with the alkali or alkali-earth metal and which is also capable of solvating ions of this metal. Examples of such solvents include ether type solvents, such as THF, dioxolan, glymes, crown ethers as well as substituted amine base solvents, for example N,N,N',N'-tetramethyl 1,2-ethane diamine (TMED), N,N,N',N'-tetramethyl 1,3 propane diamine (TMPD) and N,N',N",N"-pentamethyl diethylene triamine (PMDET). The organic solution also generally includes a compound having conjugated double bonds usually aromatic, such as naphthalene, biphenyl, anthracene and benzophenone which can delocalize the electrons of the metal and an organic liquid diluting agent, for example benzene, toluene, alkanes or mixtures thereof. The organic solution should be capable of controlling the activity of the alkali or alkali-earth metal preferably at values lower than +600 mVvsLi°. To do this, the molar ratios of the components of the organic solution which include the polar solvent, the compound having a conjugated double bonds and the liquid organic diluting agent, are preferably the following: polar solvent: from 10 -5 to <1 compound having conjugated double bonds: <from 10 -5 to 0.2 organic diluent: <1. More particularly, these ratios can be the following: polar solvent: 10 -3 to 0.2 compound having conjugated double bonds: 10 -4 to 0.1 organic diluent: <1. For example, in the case where the organic solution is made of THF, naphthalene and benzene, the molar ratios could be the following: TMED or THF: about 9×10 -2 biphenyl or naphthalene: about 7×10 -2 benzene: about 0.84. With respect to the source of alkali or alkali-earth metal, it is generally made of the pure metal which is intended to be alloyed with the host metal. Of course any source of lithium whose activity in lithim is superior to the activity of the solution at equilibrium may also be used. According to a preferred embodiment of the invention, the metallic alloy or electrode obtained has a predetermined shape, and to obtain this, the originating structure is constituted so as to be a precursor of the final shape of the metallic alloy or electrode. According to another preferred embodiment of the invention, the organic solution has a high benzene content which contains little addition of aromatic compounds and polar solvents capable of solvating lithium ions and compatible with the lithium, which enables to obtain electrodes which are not or slightly chemically passivated. The host metal normally but not necessarily comprises aluminum. For example, other host metals could be used which could form alloys or intermetallic compounds with said alkali or alkali-earth metals, such as magnesium, silicon, zinc, boron, mercury, silver, alloys or the like. The host structure can obviously vary to a large extent, but it is understood that its configuration and its constitution, therefor its specific shape, should be adapted to the alloy and eventually to the negative electrode which is intended to be obtained. Many possibilities could be considered of which some examples will be discussed below. There is a case where the host structure is made of a metallic sheet for example of copper, molybdenum or nickel, which comprises a plain layer of host metal, such as aluminum, on at least one and preferably on the two faces of the metallic sheet. The thickness of the metallic sheet can preferably vary between 1μ and 20μ, while the thickness of the layer of host metal can vary between 5μ and 50μ, preferably about 25μ. In this case, the formation of the alloy will be carried out by transfer of the alkali or alkali-earth metal, preferably of lithium towards the host metal, thereby obtaining a more or less extended penetration of the layer of host metal, depending on the conditions of operation. According to another possibility, similar to the preceeding one, the layer(s) of host metal have a dendritic aspect. In this case, the entire thickness of the host metal on the metallic sheet varies between 5 and 50μ, and is preferably about 25μ. Another possibility resides in the fact that the host structure is essentially made of a sheet of the host metal. In this case, there could be formation of a layer of alloy on one or two faces of the metallic sheet. In certain conditions, where the transfer of the alkali or alkali-earth metal is carried out to a limited extent, the so-called penetration of the alloy on the metallic sheet stops at a certain level, leaving the host metal intact. The host structure can be made of a metallic sheet, such as aluminum whose thickness normally varies between 1μ and 200μ in one case and between 5μ and 500μ, preferably between 50μ and 300μ in the other case. This choice of thickness enables to obtain, after formation of the alloy, in the first case, alloyed electrodes which are entirely converted throughout, or if need be, in the second case, having two alloyed faces with a zone of non reacted aluminum at the center. This last case has the advantage of improving the mechanical properties of the alloy in addition to ensure the control of the activity of lithium in the alloy (about +380 mVvsLi°) in view of the coexistence of non reacting aluminum and the alloy. If, on the other hand, as stated above, the alloy is allowed to be formed in depth, the metallic sheet becomes completely alloyed. This integral formation of alloy can go to the extent of modifying the voluminal and mechanical properties of the resulting product so that the sheet is desintegrated into particles of alloy which can be used to prepare alloys or electrodes. For example, these particles could be used to prepare flexible anodes such as described in U.S. application Ser. No. 430,696, filed Sept. 30, 1982. Finally, if one wishes to eventually obtain spheres, fibers or flakes of the alloy, it is merely sufficient to use spheres, fibers or flakes of the host metal which is brought together with the organic solution, the latter being kept in contact with a source of alkali or alkali-earth metal. These particles of alloy should not generally exceed 50μ on at least one their dimensions so as to enable the preparation of the electrodes in the form of thin films starting from these particles. For example, the host structure can be made of particles of Al, Mg, Si, Zn, in the form of spheres, flakes or fibers of preselected granulometry so as to form alloys of lithium whose stoechiometries approximate LiAl, Li 0 .9 Mg, Li 3 .5 Si, LiZn from a solution containing this metal in free radical form. According to another preferred embodiment of the invention, the organic solution is based on benzene and contains naphthalene or biphenyl and N,N,N'-N'-tetramethyl 1,2-ethane diamine or THF saturated with lithium in free radical form and contains an excess of metallic lithium. According to another preferred embodiment of the invention, the organic solution is based on benzene and contains a limited quantity of metallic lithium so as to control the activity and the proportion of alloy formed. According to another preferred embodiment of the invention, the host structure is a sheet made of an aluminum matrix containing fibers or flakes of Al 3 Ni or Al 2 Cu. When the organic solution contains lithium, the latter is obviously in contact with a source of lithium. The solution can be based on naphthalene and N,N,N',N'-tetramethyl 1,2-ethane diamine and the activity of the metallic lithium is then between +200 and +400 mVvsLi°. When the solution is based on biphenyl and THF the activity of the metallic lithium is stable and is about 380 mVvsLi°. If the organic solution of lithium is based on biphenyl and N,N,N',N'-tetramethyl 1,2-ethane diamine, the activity of lithium is between <+50 and +200 mVvsLi°. The method according to the invention is interesting in that it enables a continuous process where the organic solution possesses controlled activity in lithium. Moreover, since the organic solution acts as a transfer agent of the lithium (reversible reaction) there can be an excellent homogeneity of the composition of the final alloy. Moreover, since there is no consumption of the organic solution and because the active components of this solution can be diluted in benzene, for example, the process is economical and mainly dependent on the cost of lithium and of the other components of the alloy. This process moreover removes the usual steps of thermic synthesis, crushing, screening and definite shaping of the alloyed electrodes presently used as described, for example, in U.S. application Ser. No. 430,696, filed Sept. 30, 1982. The invention also concerns a metallic electrode consisting of a structure of the host metal, preferably aluminum, magnesium, zinc, silicon, boron, mercury, and alloys thereof, which have been alloyed with an alkali or alkali-earth metal. The fact that the structure of the alloy prepared by the process according to the invention is continuous, contrary to the composite electrodes, ensures the electronic conduction which is necessary for electrochemical reactions and prevents an extended penetration of the alloy by the electrolyte when the alloy and the electrolyte are contacted together. Formation of films which are electronically non conductive at the interface between the alloy and the polymer electrolyte, inside the alloy, is also prevented because there is no in depth penetration of the electrolyte in the continuous alloy. According to a preferred embodiment of the invention, the host metal structure of the electrode is made of a metallic sheet which is a good electronic conductor, such as Cu, Ni, Al, Zn, Mo, etc., on which there appears a dendritic or planar deposit of a host metal such as Al, Zn, etc. The thickness of the alloyed metal on the metallic sheet is about 5μ to 50μ. The use of dendritic deposit for the host metal after formation of the alloy enables to obtain electrodes with large exchange surfaces with the electrolyte. therefor sustaining high current densities. According to another preferred embodiment of the invention, the structure of the host metal of the electrode is made of a sheet of the host metal alloyed with lithium and whose thickness is between about 5 μ and 500 μ, preferably between about 20 μ and 300 μ. According to another preferred embodiment of the invention, the structure of the host metal of the electrode comprises an aluminum matrix which contains fibers such as intermetallic compounds Al 3 Ni or Al 2 Cu. This host structure is alloyed with lithium and in view of the presence of the intermetallic compounds, it preserves its mechanical properties, even when the activity of lithium in the organic solution is lower than +200 mVvsLi° and the β enriched phase of the lithium-aluminum alloy is formed. According to another preferred embodiment of the invention, the structure of the host metal of the electrode comprises particles of Al, Mg, Si, Zn, B, Ag, alloyed with lithium under stoechiometric values close to LiAl, Li 0 .9 Mg, Li 3 .5 Si, LiZn. According to another preferred embodiment of the invention, the host structure corresponds to particles of Al, Mg, Zn, Si, previously classified according to size or shape (spheres, flakes, fibers) for example at 20±5μ, so as to permit the preparation of composite electrodes after reaction with lithium, according to U.S. Pat. Ser. No. 430,696 of Hydro-Quebec filed on Sept. 30, 1982. The cost of production of said electrodes is then substantially reduced and the performance is improved by means of the precise control of the size and shape of the particles of alloy prepared according to the present invention. For example, the stoechiometries obtained can be in the vicinity of Li 0 .9 Mg, Li 3 .5 Si, LiZn, LiAl starting from a biphenyl solution of excess lithium, and N,N,N',N'-tetramethyl 1,2-ethane diamine; or still Li 1- ε Al+Al starting from a naphthalene solution, an excess of lithium and THF. In the latter case, the reason for allowing a small amount the host metal of the alloy to coexist with the alloy is to promote a thermodynamic control of the activity of lithium during successive recharge cycles. Another important advantage of the present invention concerns the remarkable electrochemical properties observed with the electrodes and the devices produced with polymeric electrolytes according to the present invention. Indeed, it has been realized that the claimed process enables the preparation of alloys of generally continuous structure whose mechanical properties are sufficient after lithium has been introduced therein so that once in the presence of the polymeric electrolyte, all the parts of the alloy remain in electronic contact. The net effect is to dispense with the need of electronic conduction additives in the electrode, such as carbon, and to improve the densities of voluminal and mass energy. On the other hand, the control of the morphology of the alloy before introducing lithium enables to localize in the electrode zones of alloy with varying densities and to specifically determine the surfaces of ionic exchange between the zones of alloy and the polymeric electrolyte. For example, the choice at the start of dendritic structures (Al, Zn or the like) or thin sheets (Al, Mg or the like) will enable to obtain in the first case electrodes which can sustain high current densities and in the second case, thin electrodes with large surfaces and high densities of voluminal and mass energy. It is believed that the remarkable electrochemical properties of cycling of the electrodes obtained by coupling alloys according to the invention with a polymeric electrolyte, which will be described in the examples which follow are due on the one hand to the high viscosities of the polymeric electrolytes which tend to reduce or eliminate the penetration of the electrolyte between the more or less broken up grains of the alloy zones, then prevent the formation of electronically insulating films and consequently the loss of utilization of the electrode during cycling; moreover, since the polymeric electrolyte acts as a binder about the zones of agglomerated alloy there is no desintegration of the alloy during cycling. Another factor which is very important in so far as the cycling properties of the negative electrodes according to the present invention is that the alloys produced can contain, if needed, zones of unreacted host metal, for example aluminum or α-aluminum in the presence of the electrochemically active alloy β-LiAl. This helps to control of the activity of the alloy close to +380 mVvsLi° and as illustrated in the examples which follow, has a favorable effect on the preservation of the structure of the electrode and on the maintenance of the cycling properties. An inherent advantage of the process according to the present invention is to permit that the important voluminal variations which take place in the host structure during the formation of the alloy do indeed take place before the alloy is contacted with the electrolyte and is mounted in a complete generator. This advantage becomes obvious if, by way of example, one prepares a large surface generator starting from a sheet of aluminum and a positive electrode prepared in discharged state. It is then observed that during the first charge, such a device is rapidly short-circuited following important dimensional variations which are higher than 30% of the sheet when the lithium is introduced. These variations of the dimensions of the sheet frequently produce short-circuits in the electrolyte, mainly when the latter is constituted of a thin film of polymer (100-10μ). The existence of solutions of alkali metal, generally in free radical form, which closely resemble those utilized in the present invention, has been known for many years. For example, reference may be made to "Electrons in Fluids" (The Nature of Metal-Amonia Solution), J. Jortner & N. R. Kestner, Springer - Verlag, 1973. According to the present invention, it has been however noted that for certain compositions, such solutions can be obtained with lithium whose activities are controlled and are closed to metallic lithium, for example +200 to +400 mVvsLi° for solutions comprising naphthalene and N,N,N',N'-tetramethyl 1,2-ethane diamine; for solutions comprising biphenyl and THF, the activity is relatively stable at +380 mVvsLi°, finally, for solutions comprising biphenyl and N,N,N',N'-tetramethyl 1,2 ethane diamine the activity of lithium is between the +200 and less than +50 mVvsLi°. Moreover, it has been established that such solutions can be used as transfer agents for lithium in the preparation of charged negative electrodes having high activities of lithium <+400 mVvsLi° and controlled shapes, from an initial structure. Moreover, the preferred but non limiting choice of solutions having a high content of benzene and a low content of aromatic compounds and polar solvents capable of solvating lithium ions, and compatible with lithium, corresponds to a process of manufacture which is not very costly and leads to alloys which are not chemically passivated. The invention is not limited to metals mentioned, to the aromatic compounds and polar solvents mentioned, which may in certain cases combine the functions of solvating Li°, delocalizing electrons of the metal or of diluent, as long as the organic solution of lithium acts as carrier of Li°, that it is reversible so as to enable the homogenization of the alloy and permits the control of the activity of dissolved lithium, preferably at values of +600 mVvsLi°. BRIEF DESCRIPTION OF DRAWINGS The invention is illustrated without being limited by the annexed drawings in which: FIG. 1 is a schematic representation of an electrochemical generator utilizing a negative electrode according to the present invention; FIG. 2 represents a phase diagram of the system Li-Al; FIG. 3 represents a serie of curves illustrating the trend of discharge plateaus obtained at 27° C. and 60 μA; FIG. 4 is a schematic representation of a host structure made of a metallic sheet comprising a plane layer of host metal on the two faces; FIG. 5 is a schematic representation of a host structure made of a metallic sheet comprising two layers of host metal having a dendritic appearance; FIG. 6 is a schematic representation of a host structure essentially constituted of the host metal of which the two surfaces have zones of alloyed host metal; FIG. 7 is a schematic representation of a host structure essentially constituted of the host metal alloy alloyed in depth to preserve the structure of the sheet; FIG. 8 is a schematic representation of particles of alloyed host metal resulting from the desintegration of a sheet as illustrated in FIG. 7; FIG. 9 is a schematic representation of a mixture of spheres, fibers and flakes of host metal alloyed according to the present invention at their surface as in the case of FIG. 6; FIG. 10 is a curve illustrating the cycling properties of a generator according to the present invention at 26°, 48° and 55° C.; FIG. 11 is another curve illustrating the cycling plates of a generator according to the invention obtained at 100° C.; and FIG. 12 is a curve illustrating the behavior of anodes according to the invention. DESCRIPTION OF PREFERRED EMBODIMENT The examples mentioned below and illustrated on the figures illustrate how the process according to the invention is particularly well adapted to the production of thin electrodes intended for generators with large surfaces, generally operating with polymer electrolytes and optimized in order to obtain high densities of current and multiple cycles of discharge charge and high density of mass and voluminal energy. EXAMPLE 1 This example illustrates the dependency of the lithium activity from solutions containing free radicals with respect to the nature and the concentration of its constitutive elements. (a) Given a free radical solution in final state, containing 0.1M naphthalene, 0.06M tetramethyl ethane diamine and benzene, in the presence of a source of metallic lithium in excess. The activity of lithium of the free radical solution is measured precisely according to the following electrochemical chain: ##EQU1## for the free radical solution described the potential observed, after stirring and stabilization (≃1 hr.) is: E=+0.40 V vs Li°. (b) The free radical solution comprises 0.03M naphthalene, 0.06M tetramethyl ethane diamine and benzene in the presence of a source of metallic lithium in excess. The potential observed, after stirring and stabilization is E=+0.31 V vs Li°. (c) The free radical solution comprises 0.005M biphenyl, 0.01M tetramethyl ethane diamine and benzene in the presence of a source of metallic lithium in excess. The potential observed after stirring and stabilization is: E=+0.10 V vs Li°. (d) The free radical solution comprises 0.007M benzophenone, 1.0M tetrahydrofuran and benzene in the presence of a source of metallic lithium in excess. The potential observed after stirring and stabilization is: E=+1.40 V vs Li°. Therefor, it appears possible to control the activity of lithium from the nature, relative ratios and concentrations of the constitutive elements of the free radical solutions. A wide domaine of activity of lithium is accessible (0<a Li s<+1.5 V vs Li°). The control of the activity of lithium at voltages ≦600 mV vs Li° is particularly interesting for the synthesis of alloys with elevated activities of lithium which, when used in electrochemical generators will produce high battery voltages and high energy densities. EXAMPLE 2 A first example of negative electrode and generator prepared according to the invention is illustrated in FIG. 1 and is obtained in the following manner: A host structure of aluminum 1a is prepared by electrochemically depositing in the form of dendrites of nodular shapes aluminum 1b on a sheet of copper 1c to give a total thickness of aluminum of about 25μ. This structure is then immersed in an organic solution of benzene whose composition is 5×10 -3 molar naphthalene, 1.5×10 -2 molar tetramethyl ethane diamine, which is saturated with lithium in free radical form and in the presence of an excess of metallic lithium so as to give a lithium activity of the order of +400 mVvsLi°. After about 8 hours, the reaction of formation of the alloy is completed and the alloy has an activity corresponding to that of the free radical solution. The control of the activity of the free radical solution enables in this case to prevent a desintegration of the aluminum alloy which would take place if the high content phase of the phase diagram of the system Al-Li would be formed (see FIG. 2). This alloy which has preserved the shape of the initial aluminum and whose lithium composition is about 10 C/cm 2 is thereafter contacted by transfer at 80° C. with a film of polymeric electrolyte 1d which comprises a copolymer of ethylene oxide and propylene oxide whose composition is according to the ratio EO/PO=95/5 and having a molecular weight of about 500,000. Such copolymers of ethylene oxide and their method of preparation and of use in electrochemical generators are described in U.S. application Ser. No. 500,193, U.S. Pat. No. 4,505,997, and Ser. No. 500,194, U.S. Pat. No. 4,556,616, filed June 1, 1983. The positive electrode is made of particles of MoO 2 of about 15μ and of acetylene black bonded by the polymer of the electrolyte in the volume ratios of (0.30-0.10-0.60) and has a capacity of about 3.5 C/cm 2 . The ratio 0/Li between the oxygen of the monomer metal of the polymer and the lithium salt LiClO 4 is about 12/1 for the entire generator and the total surface of the generator is about 3.9 cm 2 . FIG. 3 illustrates the trend of the discharge plateaus obtained at 27° C. and at 60 μA and the maintenance of the capacity observed in coulombs at discharged cycles identified D2, D5 and D15. It is observed that the dendritic form of the negative electrode enables to obtain relatively high currents at 27° C. as a result of the important exchange surface between the alloy and the polymeric electrolyte while the good behavior during cycling confirms the good maintenance of the electronic contact between the various parts of the alloy and the absence of the phenomenon of electrical insulation of the alloy as a result of the formation of passivating films. EXAMPLE 3 In this example, the negative electrode is obtained from a sheet of aluminum whose thickness is about 300μ which is immersed during about 6 hours in a benzene solution containing 1.4×10 -1 molar tetramethyl ethane diamine and 6×10 -2 molar naphthalene. In this case, the control of the activity of lithium in the solution and of the time of reaction enable to preserve the initial shape of the sheet since the activity of the solution does not permit the formation of the high content β-rich phase and because unreacted pure or α-aluminum remain present in the center of the structure (FIG. 6). The capacity of the alloy formed superficially under these conditions is about 7 C/cm 2 . The electrode is completed by applying on the alloy some polymeric electrolyte dissolved in a solvent such as benzene and allowing the latter to evaporate. The battery is completed by means of an electrolyte comprising a copolymer of ethylene oxide and methyl glycidyl ethers EO/MGE=95/5 of molecular weight of about 500,000 and having a ratio O/Li:≃16/1, the salt of lithium being LiClO 4 . The battery also comprises a positive electrode and its stainless steel collector including MoO 2 , acetylene black, a polymeric electrolyte in a volume ratio (0.40-0.10-0.50) whose capacity is about 5 C/cm 2 . The thickness of the electrolyte is ≃110μ and the surface is 5.6 cm 2 . The cycling properties at 26°, 45° and 55° C. of the generator are indicated in FIG. 10 and appear excellent on more than 60 consecutive cycles at rates varying from C/70 to ≃C/20. Even though in this example the alloy formed is electrochemically utilized only on one of its face, the man of the art will understand that this technology is easily accessible to fabrication of two face electrodes and enabling to optimize the densities of energy of generators. On the other hand, unreacted aluminum, or aluminum present at the center of the structure can facilitate the collection of current in the assembly of such electrodes. Moreover, this example shows how the electrode prepared so as to permit the coexistence of the alloy formed with a second phase, in the present case unreacted aluminum, promotes the cycling properties by thermodynamically promoting the control of the activity of the lithium of the electrode close to +300 mVvsLi° which prevents the formation of the high content β-rich phase during the recharge and ensures the physical integrity of the electrode. EXAMPLE 4 In this example the initial structure is a thin sheet of aluminum 25μ and the organic solution is based on benzene and contains 9.0×10 -2 molar biphenyl and about 1 molar THF. The reaction is continued during about 100 hours and it is noted that the initial sheet is transformed into an alloy whose final thickness is about 40μ after complete conversion. The lithium activity of the alloy measured according to example 1 is about 380 mVvsLi° which is substantially the same value as one observed for the solution. This example therefor shows how the control of the activity of the organic solution enables to preserve the original shape of the sheet as long as the activity does not permit the formation of μ-rich aluminum. A generator prepared from this alloy in the same manner as example 2 leads substantially to the same performances as those of FIG. 3. EXAMPLE 5 In this example, the initial structure is a sheet of aluminum about 300μ which is contacted with a solution 1.5×10 2 molar of tetramethyl ethane diamine and 6.5×10 -3 molar naphthalene during 12 hours after which lithium is removed, then one hour later, the alloy is also removed and washed. This treatment permits to control the quantity of alloy formed (≃20 C/cm 2 ) superficially and its homogeneity. The generator is thereafter mounted by utilizing an electrolyte based on polyethylene of molecular weight 5M which is first fused on the alloy at about 90° C. then contacted on the other face with a positive composite electrode formed of V 6 O 13 (<38μ≃2 C/cm 2 ), acetylene black and a polymeric electrolyte under volume ratios of (0.40-0.15-0.45) and its stainless steel collector. The surface of the generator is about 3.9 cm 2 , the ratio 0/Li is -9/1 for LIClO 4 and the discharged and charged currents are about 100 μA/cm 2 . The discharge plates of this generator obtained at 100° C. are illustrated in FIG. 11 for tests D1, D2, D15, D105. Except for the first discharge whose shape is typical of the behaviors of V 6 O 13 and whose capacity is lower than planned, following a partial discharged when assembling the parts, the following plates are remarkably stable on more than 100 cycles of deep discharge (≧60%) and appear controlled by the positive electrode. This example is a good illustration of the advantages of the electrodes prepared according to the invention under relatively high conditions of temperature. EXAMPLE 6 Given a free radical solution comprising an excess of metallic lithium, an excess of benzene and limited quantities of biphenyl and tetramethyl ethylene diamine. The last two components are present in molar ratios of 3.5 and at concentrations such that the lithium activity of the solution is comprised between +100 and +200 mVvsLi°. A known weight of aluminum, in the form of a sheet 25μ thick by ≃1 cm 2 of surface is immersed in the solution. The reaction takes place at room temperature and lasts about 20 hours. The product obtained, when the reaction is completed, is a powder of an alloy of lithium and aluminum consisting or granular particles of cubic shape whose average dimensions are approximately 20μ×10μ×10μ. This powder is filtrated from the solution dried then weighted. The weight gain resulting from the formation of the alloy with respect to the initial weight of aluminum enables to evaluate the stoechimetry of the alloy at about Li 0 .5 Al 0 .5. The chemical activity of lithium in the alloy, measured according to the method described in example 1 is: 188 mVvsLi°, which corresponds to the activity of lithium in the β-rich phase (FIG. 2) at a stoechiometry of Li 0 .56 Al 0 .44 according to the diagram activity/composition published by T. R. Jow and C. C. Liang (Journal of the Electrochemical Society 129, 7, (1982) 1429-1434). The production of an alloy having high lithium activities, a high content of β-rich phase, is accompanied by an increase of volume which results for the case described here in a desintegration of the initial sheet. The determination of the stoechiometry of the alloy by measuring the chemical activity of lithium is an agreement with gravimetric determination of the stoechiometry of the same synthetic alloy. Powders of predetermined granulometries obtained by screening, in which the diameters of the particles are <38μ, containing Zn, Si and Ag are consecutively immersed in the free radical solution. After about 24 hours of reaction time, the powders produced are filtrated from the solution, dried and weighted. The stoechiometries of the synthetized alloys are determined and the results are as follows: Li 0 .55 Ag 0 .45, Li 0 .51 Zn 0 .49 and Li 0 .76 Si 0 .24. By the same technical method as previously, the chemical activity of these alloys is measured and the following results are obtained: +114 mV, 180 mV and +144 mV respectively. EXAMPLE 7 The alloy powders Li 0 .56 Al 0 .44, Li 0 .55 Ag 0 .45 and Li 0 .51 Zn 0 .49 described in example 6 are used to prepare composite negative electrodes according to the procedure described in U.S. Ser. No. 430,696. After having prepared these electrodes, they are mounted with a polymeric electrolyte and a positive electrode so as to give complete electrochemical generators. In the present case, the polymeric electrolyte comprises an elastomeric membrane whose thickness varies between 75μ and 150μ and which is formed of a polyether and lithium perchlorate (POE-LiClO 4 ) complex in a ratio O/Li=8. The positive electrode is made of a sheet of about 25 μm thick, of metallic aluminum supporting a composite material based on MoO 2 (≃40% V), Shawinigan black (≃10% V) and complex: polyether-LiClO 4 having a ratio O/Li of 8. (a) 3 g of the alloy powder Li 0 .51 Al 0 .49 described in example 6, that is 67% by by weight, and 1.5 g of Shawinigan black, that is 33% by weight have been intimately mixed. From this mixture, 1.46 g has been sampled and the latter was added to 0.6 g of ethylene polyoxide in solution in an organic organic solvent, then the suspension was homogenized before being spread in thin film on a stainless steel support. From this anode, there is taken a sample of 4 cm 2 ; (b) the operation as in (a) is repeated with commercial pyrometallurgical Li 0 .5 Al 0 .5 (KBI). Two generators have been mounted according to the procedure described, and the anodes were discharged at 100° C. and 125 μA cm -2 . In both cases, the initial use of the lithium of the alloys is close to 58% to 60% of theoretical capacities. The behavior of these two anodes is illustrated and compared in FIG. 12, where curve 1 is obtained for the lithium aluminum allow described in example 6 and curve 2 is obtained for a commercial lithium aluminum alloy. The voltages of the anodes are measured with respect to a lithium electrode of reference. (c) A composite anode containing the following components has been prepared in the following proportions: 64% by weight of Li 0 . 51 Zn 0 .45, 9% by weight of Shawinigan black and 27% by weight of polyethylene oxide in the form of a benzene solution containing 6% of material. After homogenization, there is obtained a suspension which is spread on a thin sheet of stainless steel and which after evaporation of benzene leaves a film of about 25 μm. A sample of 4 cm 2 is taken. An electrochemical generator is mounted, wherein the positive electrode is based on MoO 2 , as previously described. The anode is discharged at 50° C. and at 60 μA. Under these conditions, 35% of the lithium present in the alloy is used to give a battery voltage close to +1.3 to +1.4 volt. (d) A composite anode containing 74% by weight of Li 0 .55 Ag 0 .45 and 26% by weight of polyethylene oxide has been prepared in the manner described in (c). An electrochemical generator is mounted wherein the positive electrode is also based on MoO 2 . The anode is discharged at 50° C. and at 60 μA. Under these conditions, 42% of the lithium present in the alloy is used to give a battery voltage of close to 1.5 volt. EXAMPLE 8 The organic solution of example 6 having an activity lower than +200 mV is used in the presence of a structure of aluminum containing a small amount of intermetallic compounds of Al 3 Ni in the form of fibers present in the aluminum. In this case, in spite of a high activity of lithium, the formation of LiAl having a high content of β-rich phase does not result in the desintegration of the structure in view of the presence of the fibers. A test made with a generator similar to the one of example 2 leads to equivalent performances except for the voltage of the first discharge which is higher by about +175 mV. It is understood that these examples are intended to illustrate the advantages of the present invention but are not limiting in so far as the choice of the initial structures, the composition of the organic solution, of the elements forming the alloy and of the electrolytes used which may, by way of examples, under certain conditions, be organic, liquid or molten salts operating at low temperatures.
The disclosure describes a method for the preparation of metallic alloys containing an alkali or alkali-earth metal, such as lithium, and a host metal, such as aluminum. Initially, an active organic solution of the alkali or the alkali-earth metal is prepared, and a source of the alkali or alkali-earth metal which are both brought together with one another. On the other hand, a metallic structure containing the host metal is prepared, the metallic structure is brought together with the organic solution which is kept in touch with the source of metal until there is formed an alloy of the host metal and of the alkali or alkali-earth metal with the metallic structure, and the alloy possesses an activity which is determined by that of the organic solution. The organic solution then acts as transfer agent of the alkali or alkali-earth metal towards the host metallic structure. To prepare a negative electrode, the alloy is brought together with an electrolyte, such as a thin polymeric film. The disclosure also describes the electrodes as well as the electrochemical generators produced by using these electrodes. Considerably improved properties of cycling are obtained.
7
BACKGROUND OF THE INVENTION The invention relates generally to the field of gas lasers which have loss mechanisms and, more particularly, to the field of gas resupply valves for such gas lasers to supply new gas to maintain gas pressure within the laser tube within acceptable limits. In almost all gas lasers there is a loss mechanism whereby gas molecules trapped in the laser tube are lost either through leaks or through chemical combination with or sputtering into the materials on the inside of the laser tube. In the field of ion lasers, and especially in the field of argon ion lasers, the argon atoms are ionized by electrical discharges passing through the gas-filled laser tube. These ions are then excited to higher energy states by pumping energy supplied from an outside source. Although argon is a noble gas, argon ions can "sputter" into the walls of the laser tube and be lost for further laser action. Because there is a very narrow band of acceptable pressures for gas in the laser tube which will cause lasing action, it is important that the pressure of argon gas in the laser tube remain relatively constant. Thus, when argon ions are lost, pressure in the laser tube will drop. This loss of pressure can be detected by monitoring the voltage appearing across the electrodes which ionize the argon gas since the voltage drops as the pressure drops. If the lost argon ions are not replaced with new gas molecules, the laser will become unstable. If the pressure in the gas tube drops low enough, the laser will stop lasing. In the prior art, the lost gas has been replaced by the use of gas resupply valves. These valves have small reservoirs for storing argon gas at atmospheric pressure (or any other pressure) and have metering volumes. When the pressure in the laser gets too low, the metering volume is filled with gas through a valve and this gas is then allowed to enter the highly evacuated laser tube to replenish the gas supply. The use of the metering volume allows a known quantity of gas to be injected into the laser tube on each "charging" cycle. Very tiny amounts of gas are involved in this process. This is because if too much gas is allowed to enter the laser tube, the laser can be essentially ruined since higher pressures mean higher voltages between the ionization electrodes which the power supplies are not designed to handle. When too much gas enters the tube, the tube must be sent back to a refurbishing facility for reprocessing to get the pressure back down to an acceptable level. The requirements for a gas resupply valve for gas lasers are three. First, the valve must have a negligible leak rate when the valve is closed. This is required so that gas laser tubes which sit in inventory unused for many weeks or months do not leak gas to the extent that the laser becomes unusable or inoperative before it is ever used. A second requirement is that the valve have a lifetime of at least 1,000 cycles between open and closed positions without failure or degradation in the residual leak rate when the valve is closed. Finally, such gas resupply valves must have extremely short cycle times between opening and closing in embodiments where only one valve member and a controlled leak aperture is used. There are prior art embodiments to be discussed below which use two valve members. For these valves, it is not necessary that the cycle time be as small as noted above. But all gas resupply valves must meet the first two requirements. An early gas resupply valve design known to workers in the art used two valve seats and two valve members. The metering volume was the volume trapped between the valve seats when the two valve members were seated on their respective valve seats. A chamber around one valve was coupled to the gas reservoir, and the other valve opened into the gas laser tube or another tube coupled thereto. In operation, the "reservoir" valve was opened for a time sufficient to cause the metering volume to fill up with replacement gas at the pressure of the reservoir. After the metering volume was full, the "reservoir" valve was closed and the second or "laser tube" valve was opened thereby allowing the gas in the metering volume to be drawn into the laser tube, which has an internal pressure much lower than atmospheric pressure, to replenish the supply of gas therein. The difficulty with this design was that two valves and corresponding driving mechanisms were necessary. This made the valve relatively expensive, and more parts were present to fail. In an effort to simplify this design, workers in the art eliminated one of the valves and replaced it with a capillary tube having an inside diameter of five thousandths of an inch. This capillary tube had a diffusion constant which was longer than the interval during which the first valve coupled to the reservoir was opened. The capillary tube was connected to the interior of the laser gas tube. In operation, the first valve coupled to the reservoir was opened for a very short time which was shorter than the diffusion constant of the capillary tube. During this time the replacement gas from the reservoir filled the metering volume. The diffusion constant of the capillary tube had to be long compared to the time of opening of the first valve so that the capillary tube not appear as a leak. When this was true, the metering volume appeared to have no leak therein during the time that the valve was open, and the amount of gas that entered the metering volume could be accurately predicted. After the valve was closed and the diffusion time constant had passed, the gas trapped in the metering volume leaked into the laser tube through the capillary tube to replenish the laser tube gas supply. One difficulty with this approach was that the capillary tube was difficult to keep clean. In order to have a diffusion constant which was smaller than the open time of the valve, it was necessary to use a capillary tube with a very small inside diameter. This made it extremely difficult to keep the bore of the capillary tube clean and resulted in contaminants in the capillary tube being sucked into the laser tube. The resultant contamination caused failure of laser tubes. Another difficulty with the capillary tube design was that the capillary tube acted as a virtual leak in the laser tube during the evacuation step of the process of manufacturing the laser tube. During manufacture of a gas laser, the tube is pumped down to the desired vacuum level prior to filling it with the desired gas. The virtual leak represented by the capillary caused the time to pump the laser tube down to the necessary level to be longer than would otherwise be necessary. Those skilled in the art will appreciate that the capillary tube coupled to the metering volume appears to be a crevice in the wall of the tube which couples into a cavern. In order for the laser to be effectively evacuated, all the gas molecules in the metering volume and the capillary tube had to be pumped out through the restrictive passageway presented by the capillary tube. Thus a need exists for a simple, reliable, relatively inexpensive gas resupply valve for gas lasers. SUMMARY OF THE INVENTION According to the teachings of the invention, a gas resupply valve is taught using a metering volume which uses one valve at an inlet and which has an outlet comprised of one wall which has a microscopically small aperture therein. Typically, this aperture is laser drilled and has a diameter of from 10-15 microns. The valve opens for a predetermined interval to gate gas from the gas reservoir into the metering volume. Input gas comes from a resupply gas reservoir coupled to a chamber surrounding the valve. The small aperture in the wall of the metering volume is in fluid communication with the interior of a gas laser tube such that the vacuum level in the gas laser tube is present in the metering volume at all times except when the valve is open. The gas resupply reservoir is at atmospheric pressure typically however any pressure could be used. When the valve opens, the lower pressure in the metering volume causes gas from the reservoir and the chamber surrounding the valve to enter the metering volume. However, the aperture size and length is such that the diffusion constant for gas molecules moving through this aperture into the laser tube is longer than the time during which the valve is open. Thus, the metering volume is a virtual closed cavity as long as the valve is not open for a time which is longer than the diffusion constant for the aperture. The wall of the metering volume having the aperture therein is thin so that the length of the aperture is short. Thus the aperture has a length which is short compared to the 1 to 2 inches of capillary tube used in prior art valves. This makes the aperture far easier to clean than the prior art capillary tubes. Conventional laser drilling techniques may be used to form the aperture. Any conventional technique such as chemical machining may be used to make the aperture. The critical element is that the size and length of the aperture cause it to have a diffusion constant which is longer than the time during which the valve will be open on each "charging cycle". After the valve is closed, the gas in the metering volume leaks into the interior of the laser tube through the aperture. The voltage across the laser tube is then monitored during operation to determine if the amount of gas metered into the laser tube is sufficient to bring the pressure back to within the desired pressure range. If the gas charge is insufficient, one or more additional gas charges is provided by cycling the valve open and closed one or more times. This process is repeated until the pressure rises to the desired pressure range and the voltage across the tube rises to the desired level. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross sectional view of a gas resupply valve according to the teachings of the invention. FIG. 2 is a cross sectional view of a gas resupply valve according to another embodiment of the invention. FIG. 3 is a cross sectional view of a gas resupply valve according to the preferred embodiment of the invention. FIG. 4 is a cross sectional view of a gas resupply valve having a flat metal diaphragm according to another embodiment of the invention. FIG. 5 is a cross sectional view of a valve having a flat metal diaphragm according to another embodiment of the invention useful outside the field of gas lasers. FIG. 6 is a cross sectional view of a valve having a flat metal diaphragm which attached to the valve body at welds and which has folds in the diaphragm to relieve stresses of any origin which might cause the diaphragm to bow. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT Referring to FIG. 1, there is shown a cross-section of a gas laser resupply valve having one valve and a small aperture in a wall of the metering volume. The valve is comprised of a resupply reservoir 10 which is filled with, for example, argon gas at atmospheric pressure. In the preferred embodiment, this resupply reservoir 10 can be a chamber machined in the body 12 of the valve. In other embodiments, the reservoir 10 may be coupled to the body of the valve through an external port (not shown). The resupply reservoir 10 is coupled via a fluid passageway 14 to a chamber 16 containing a valve 18. This valve is comprised of a solenoid slug 20 and a softer material 22 on the end of the solenoid slug. The softer material must be capable of cold flow so that a seal may be formed but must be tough enough to withstand at least 1000 cycles of the valve. In the preferred embodiment, this softer material 22, which will hereafter be called the sealing member, is a polymer marketed by DuPont under the trademark CALRES. The solenoid slug 20 is driven linearly along the y axis to open and close the valve to allow gas from chamber 16 to enter a metering volume 24. One wall of the metering volume 24 is comprised of a diaphragm 25. This diaphragm has formed therein by any known process a very small aperture 28. In the preferred embodiment, this aperture has a diameter of from 10-15 microns and is laser drilled. The thickness of the diaphragm 25 is not critical other than it must be such as to establish the diffusion time of gas moving through the length of the aperture 28 along the negative y axis. Also, the diaphragm 25 must have sufficient thickness to withstand pressures exerted on it during the short time when the metering volume has been filled with gas at atmospheric pressure and gas is leaking through the aperture 28 into the laser tube. The valve opens when the CALRES™ sealing member 22 leaves contact with a valve seat 26. The valve closes when the sealing member 22 again is reestablished in contact with the valve seat 26 under the influence of the solenoid slug 20. In the preferred embodiment, the solenoid slug 20 moves in the direction of the positive y axis to open the valve. Typical open times are on the order of 5 milliseconds. The valve 18 may have a different construction in other embodiments. Further, other open times may be used for the valve 18. It is critical, however, that the open time selected be less than the diffusion time for gas moving through the aperture 28. The gas in chamber 16 is sealed therein by a sealing member 32 which is sealed to the body 12 by a copper washer 34 and sealing ribs 36 and 38. In operation, the valve 18 opens thereby creating a path between the sealing member 22 and the valve seat 26 through which gas from chamber 16 flows into the metering volume. The solenoid slug 20 then moves in the negative y direction thereby forcing the sealing member 22 to make sealing contact with the valve seat 26. Because the laser tube coupled to fluid communication path 30 is at low pressure, and because the gas in chamber 16 is at atmospheric pressure, gas from chamber 16 naturally flows into metering volume 24. However, the diffusion time constant of gas moving through the aperture 28 is long compared to the time during which sealing member 22 is not in contact with valve seat 26. Thus, virtually no gas escapes from the metering volume 24 into the fluid communication path 30 and the corresponding laser tube during the time the valve is open. This is important so that precise control over the amount of gas which is injected into the laser tube is maintained. If too much gas is injected, the laser tube will reach too high a pressure and be out of the optimum range for lasing action. In such a situation, there is no way to get gas out of the tube in the field, and the laser may be out of service. After the sealing member 22 has sealed the metering volume 24, the diffusion time passes and the gas trapped in the metering volume 24 escapes through the aperture 28 into the lower pressure laser tube via fluid communication path 30. This process may be repeated as many times as necessary to raise the pressure in the laser tube to within the desired pressure range and to raise the voltage across the laser tube to the desired voltage. Referring to FIG. 2, there is shown a cross-sectional view of another gas resupply valve according to the teachings of the invention. The valve is comprised of a valve body 40 which has a valve seat 42 and a metering volume 42 formed therein. The metering volume has one wall which is a diaphragm 46. This diaphragm has an aperture 48 formed therein generally by laser drilling or any other convention process that can make an aperture from 10 to 15 microns in diameter. The size of the aperture 48 is determined by the same considerations used to determine the size of the aperture 28 in FIG. 1. The aperture 48 couples the metering volume 44 to a fluid communication pathway 50. This fluid path couples the metering volume 44 to the internal volume of the laser tube. A valve is formed by the interaction between a sealing member 52 and the valve seat 42 under the influence of forces generated by a solenoid slug 54 and a spring 56. The sealing member 52 is a flexible material capable of cold flow such as CALRES™ by DuPont. The spring 56 engages an annular shoulder 58 formed on the solenoid slug 54 and forces the slug 54 in the negative y direction. This causes the sealing member 52 to deform to the position shown in dashed lines at 60. In this position, the underside of the sealing member 52 engages the valve seat 42 with sufficient force to cause the valve seat to cause slight indentations in the sealing member 52 by cold flow. This establishes a seal. When the valve is to be opened, a solenoid coil (not shown) driven by a pulse of approximately 5 milliseconds duration causes the solenoid slug 54 to move in the positive y direction sufficiently to allow the sealing member 52 to disengage the valve seat 42. This movement to disengage the valve seat happens without any external force being applied to the sealing member 52 by virtue of the elastic properties of the sealing member. That is, the sealing member 52 must have sufficient elasticity and memory to spring back to its undeformed position from the position 60 when force by the solenoid slug is released. Note that in FIG. 2 the sealing member 52 is not physically attached to the solenoid slug 54 whereas in the valve shown in FIG. 1, the sealing member 22 is physically attached to the solenoid slug 20. Thus, if the solenoid slug 20 wobbles or rotates during its movement in the valve of FIG. 1, the sealing member 22 will not always engage the valve seat 26 in the same relative positions on the surface of the sealing member. If this happens, the resealing of the sealing member 22 to the valve seat 26 takes somewhat longer than if the sealing member 22 always strikes the valve seat 26 at the same place. In the valve shown in FIG. 2, the sealing member 52 is supported by a spacer ring 62 and the valve body as opposed to being supported by the solenoid slug. This means that the sealing member remains stationary even if the solenoid slug 54 wobbles, rotates or otherwise moves during its travel along the y axis. The instability of the solenoid slug results quite frequently since a very loose fit between the solenoid slug and its support is necessary to keep friction acting on the slug down. This is necessary because of the very small opening time of the slug, i.e., on the order of 5 milliseconds. If too much friction is present, the cycle time to open and close the valve will be longer than the diffusion time constant. This means that the sealing member 52, when deformed to the position 60, always has the valve seat 42 strike the undersurface of the sealing member at the same location. This results in the cold flow indentations in the sealing member 52 being engaged with the tips of the valve seat 42 as a perfect match. That is, the cold flow indentations in the undersurface of the sealing member 52 will be perfectly matched in shape to the tips of the valve seat 42. The perfect match results because the tips of the valve seat cause the cold flow indentations in the first place. Because the sealing member 52 always maintains its position relative to the tips of the valve seat 42, the valve seat never has to form new indentations in the undersurface of the sealing member 52. This improves the resealing time from approximately 20 milliseconds for the valve shown in FIG. 1 to approximately 1 millisecond for the valve shown in FIG. 2. The resealing time is the interval between the time when the sealing member 52 first contacts the valve seat 42 to the time when gas flow into the metering volume 44 ceases. The spacer ring 62 is engaged in a well 64 formed in the valve body 40 and serves to hold the sealing member 52 above the valve seat 42 in the positive y direction by a small distance. This distance is shown as dimension A in FIG. 2. It should be not so great that the sealing member 52 is incapable of deforming far enough to engage the valve seat 42. But the distance should be large enough to allow the metering volume 44 to fill rapidly during the 5 milliseconds or so that the sealing member 52 is not engaged with the valve seat 42 during a charging cycle. The valve body 40 also has formed therein a gas reservoir 66 which is coupled to the well 64 by a gas passageway 68. The gas reservoir 66 stores a volume of gas which is identical to the gas in the laser tube. This gas is stored at atmospheric pressure generally. The valve body 40 has sealing teeth 70 and 72 (actually this is one annular tooth) which engage a copper sealing washer 74. The surface of the sealing washer 74 having the most positive y coordinate is engaged by sealing teeth of 76 and 78 of a cap member (not shown) which forms a gas tight chamber surrounding the metering volume 44, the sealing member 52 and the solenoid slug 54. Thus, if any gas in well 64 gets past the sealing member 52 to the vicinity around the solenoid 54, that gas is trapped in the structure. In operation, when a recharge cycle is to be performed, a short pulse, generally 5 milliseconds in duration, is applied to the solenoid coil which drives the solenoid slug 54 in the positive y direction. This disengages the sealing member 52 from the valve seat 42 thereby allowing gas at atmospheric pressure in well 64 to fill the metering volume 44. No gas escapes through the aperture 48 into the fluid passageway 50 since the diffusion time constant for gas moving through the aperture 48 is longer than the time which the valve is open. After the pulse to the solenoid coil returns to zero voltage, the spring 56 exerts a force on the annular shoulder 58 sufficient to cause the solenoid slug 54 to move in the negative y direction. This causes a force on the sealing member 52 which causes it to deform to the position 60. This closes the valve and cuts off fluid communication with the well 64. A known amount of gas is then trapped in the metering volume since the volume of this chamber is known and it is known that no gas could have escaped through the aperture during the 5 millisecond fill time. Gas trapped in the metering volume 44 then leaks through the aperture 48 into the lower pressure laser tube via passageway 50. This process is repeated as many times as necessary to raise the pressure in the laser tube to within the desired pressure range. Referring to FIG. 3, there is shown another embodiment of the valve of FIG. 2. The main difference between the embodiment shown in FIG. 3 and the embodiment shown in FIG. 2 is that the sealing member 82 is not supported by a spacer ring such as the spacer ring 62 in FIG. 2. Instead, the sealing member 82 is engaged with the sealing teeth 84 and 86 of the valve body 88 on the undersurface and engaged with sealing teeth 90 and 92 on the upper surface. Sealing teeth 90 and 92 are part of a cap (not shown) which encloses the entire valve to form a gas tight seal. Also, the solenoid slug 94 does not have an annular shoulder thereon such as the shoulder 58 in the valve of FIG. 2. However, the solenoid slug 94 could be formed with the same configuration as the solenoid slug 54 in FIG. 2. Other means of applying pressure in the negative y direction to the sealing member 82 may also be used. Note also that the valve body has a gas passageway 96 formed therein to conduct gas from an external port 98 coupled to an external gas reservoir (not shown) to the internal chamber 100. Note that the sealing member 82 is physically engaged by the sealing teeth 84, 86, 90 and 92 and therefore is fixed in position relative to the valve seat 96. Therefore, if the solenoid slug 94 wobbles, rotates or otherwise moves during its movements along the y axis, the sealing member 82 does not move relative to the x axis during the process of engaging the valve seat 96. Thus, the advantages of the embodiment of FIG. 2 over that of FIG. 1 are also achieved in the embodiment shown in FIG. 3. The resealing time of the embodiment of FIG. 3 is comparable to the embodiment of FIG. 2. In both the embodiments of FIGS. 2 and 3, the distance A between the underside of the sealing members and the valve seat is approximately 10 to 15 thousandths of an inch. Referring to FIG. 4 there is shown in cross-section another valve construction for a gas resupply valve according to the teachings of the invention. In this embodiment a valve body 110 has a flat upper surface 112 which has two ports 114 and 116 formed therein. The surface 112 may be ground flat and does not have to be optically flat. The port 114 serves as an input port for gas while the port 116 serves as an output port. A 5 mil thick foil diaphragm 118 rests on the surface 112 and is supported at sealing rings 120 and 122 which are in fact a single rubber sealing ring in the preferred embodiment. Movement of the diaphragm 118 in the x direction is restrained by retaining walls 124 and 126 in the preferred embodiment. With a circular valve construction, the retaining walls 124 and 126 are in fact a single annular retaining wall. The port 116 serves as an inlet port to a metering volume 128. The metering volume 128 has one wall which is a diaphragm 130 in which is formed an aperture 132. This diaphragm 130 and the aperture 132 serve the same purpose as the diaphragms and apertures in the valves of FIGS. 1-3. The metering volume is in fluid communication with the laser tube through the aperture 132 and a fluid communication path 134. A solenoid core 136 having a soft material 138 formed on the end thereof serves to open and close the valve in a manner to be described below. The soft material 138 can be CALRES™ by DuPont or any other soft material such as rubber, or soft metals such as brass or aluminum. Preferably, the materials for all elements in the valve of FIG. 4 should have a high melting point. For this reason, an all metal structure is preferred. Thus brass is the preferred material for the element 138. The reason for this preference is that during the construction of a gas laser, during the pump down stage where the laser tube is evacuated, it is desirable to heat the tube to as high a temperature as possible to speed up the process. This aids in removal of gas molecules trapped in crevasses in the surface of the metal inside the tube and in removing the monolayer of gas atoms which adhere to the walls of the metal inside the tube. The increased thermal activity of the atoms decreases the diffusion time for gas molecules coming out of crevasses and decreases the time it takes to liberate the monolayer gas atoms from the walls of the internal structure of the laser tube. Since the gas resupply valve is already attached to the laser tube during this process, it too is subjected to high temperatures. Therefore the presence of any polymers or other materials which cannot withstand the high temperatures of the bake process are undesirable. In operation, the valve of FIG. 4 is initially sealed, thereby preventing gas flow from port 114 into the metering volume 128. This sealing occurs when the solenoid slug 136 is moved in the negative y direction thereby forcing the soft material 138 against the diaphragm 118. The force exerted upon the diaphragm causes it to comes down upon and conforms to the contour of the surface 112 thereby forming a seal. This is the reason that the surface 112 should be as flat as possible although perfect flatness is not necessary. This is also the reason that the diaphragm 118 should be relatively thin. The only criterion is that the flatness of the surface 112 and the thinness of the diaphragm 118 combine to make a seal which is adequate to meet the requirement that there be a negligible leak rate when the valve is closed. In the preferred embodiment, this seal was experimentally found to be better that 1×10 -10 liters per minute leak rate. To recharge the laser tube when the pressure therein drops too low, the solenoid core 136 moves in the positive y direction for a short time such as 5 milliseconds. This allows the elastic diaphragm 118 to spring back to its original shape thereby creating a passageway for gas flow between the port 114 and the port 116 between the diaphragm 118 and the surface 112. This fills the metering volume 128. Since the diffusion time constant of the aperture 132 is short relative to the time that this passageway is open, no gas leaks into the laser tube during the time that the gas flow pathway between port 114 and port 116 is open. After the metering volume is filled, the solenoid core 136 again moves in the negative y direction thereby sealing the metering volume 128 from further gas input. Thereafter, the gas trapped in the metering volume 128 is drawn into the laser tube through the aperture 132 and the fluid communication path 134. Referring to FIG. 5, there is shown a cross-section of another valve built according to the principles of the valve of FIG. 4 except the metering volume 128 and the diaphragm 130 and aperture 132 are replaced by a single output port 140. All other structures are the same and serve the same purpose. Thus the structure of FIG. 5 is a simple valve having a gas input port 142 and a gas output port 140. Of course, other materials than gas can be controlled using the valve of FIG. 5 such as liquids. If corrosive liquids are to be handled, materials must be selected for the valve structures which come into contact with the liquid which cannot be damaged by the liquid. Those skilled in the art will appreciate the selection of materials necessary to such applications. Referring to FIG. 6, there is shown another embodiment of a valve according to the principles shown in FIGS. 4 and 5. In this valve, the principle difference is that the diaphragm 144 is permanently attached to the valve body 146 by welds 148 and 149. These welds can also be braised connections or other forms of connection suitable for connecting the material of the diaphragm 144 to the material of the valve body. In FIG. 6, the diaphragm 144 is shown as a single line. The diaphragm 144 has bellows 150 and 152 formed therein. The purpose of these bellows is to allow for differences in the rates of thermal expansion and contraction between the diaphragm 144 and the valve body 146. Such differences could cause the diaphragm 144 to bow away from the flat surface 154 of the valve body 146 under certain conditions. In other words, the diaphragm 144 could bow up and away from the surface 154 in the positive y direction under certain circumstances. This bowing action could make it impossible to properly seal the valve between input port 156 and output port 158. The bellows 150 and 152 can expand or contract to account for these differences thereby maintaining the relative relationship in the y direction between the diaphragm 144 and the surface 154. In the embodiment of FIG. 6, a single simple output port 158 is shown. However, those skilled in the art will appreciate that the single output port 158 may be configured as a metering volume/diaphragm/aperture/fluid communication path as shown in FIG. 4 at 128, 130, 132 and 134 respectively. Such a configuration would make the valve of FIG. 6 suitable for use in gas resupply to gas lasers having loss mechanisms. In operation, the valve works the same way as the valves shown in FIGS. 4 and 5 in that solenoid core 160 moves in the negative y direction to force soft material 162 against the diaphragm 144 thereby causing it to contact the flat surface 154 and seal the valve. This prevents any fluid flow between the input port 156 and the output port 158. When the valve is to be opened, the solenoid core 160 is moved in the positive y direction thereby allowing the diaphragm 144 to move in the positive y direction and opening a fluid communication path between the port 156 and the port 158. Although the invention has been described in terms of the multiple embodiments disclosed herein, those skilled in the art will appreciate many modifications which may be made to these structures to utilize the concepts disclosed herein without departing from the true spirit and scope of the invention. All such modifications, substitutions and other equivalents to structures are intended to be included within the scope of the claims appended hereto.
There is disclosed herein several gas resupply valves for replenishment of lost gas in gas lasers in general and argon ion lasers in particular. The first embodiment uses a valve which controls flow of gas into a metering volume. The metering volume has an aperture therein which is microscopically small and which has a diffusion constant for gas moving through the aperture which is less than the time the valve is held open. The second embodiment uses the same general structure, but separates the soft sealing member of the valve from the solenoid core which moves to open and close the valve. The soft sealing member is attached to the valve body and supported above a valve seat surrounding the opening of the metering volume. The third embodiment uses a thin diaphragm which overlies a flat surface of the valve body in which are formed an input port and an output port. A solenoid applies pressure against the diaphragm to cause it to flatten against the flat surface thereby sealing the valve.
5
BACKGROUND OF THE INVENTION Electronic circuit interruption devices are supplementing thermal and magnetic circuit breakers in many industrial applications. The electronic circuit interrupter includes a signal processing circuit in the form of a printed wire board contained within the circuit interrupter enclosure. The arrangement of the circuit interrupter enclosure provides for selection of various electrical accessories that are field-installed. U.S. Pat. Nos. 4,754,247; 4,757,294 and 4,788,621 describe such electronic circuit interrupters along with the trip actuator module that responds to the electronic trip circuit to separate the circuit interrupter contacts. U.S. Pat. Nos. 4,589,052 and 4,741,002 describe electronic trip circuits used to provide the trip signal to the trip actuator module. U.S. Pat. No. 4,679,019 describes a trip actuator module in the form of an electromagnetic trip actuator which includes mechanical linkage for interfacing with the circuit interrupter operating mechanism to separate the circuit interrupter contacts. All of the aforementioned U.S. patents are incorporated herein for reference purposes. The electromagnetic trip actuator described within the aforementioned U.S. Pat. No. 4,679,019 is designed for operation within electronic circuit interrupters rated at 600 amperes or less. With industrial circuit interrupters rupters rated at more than 600 amperes, the circuit interruption mechanism and corresponding circuit interrupter contacts are sized to provide continuous current transfer at the higher ampere rating without becoming overheated. The compact size of the electromagnetic trip actuator limits the amount of motive-force applied to the circuit interrupter operating mechanism such that the electromagnetic trip actuator, per se, is incapable of articulating the larger size operating mechanisms. One purpose of the instant invention, is to provide dual trip actuators and electronic control circuits that are capable of operation over a wide range of circuit interrupter ampere ratings. SUMMARY OF THE INVENTION A molded case electronic circuit interrupter includes an electronic trip unit for operating a first electromagnetic trip actuator to separate the circuit interrupter contacts over a predetermined range of overcurrent conditions. A supplemental electromagnetic trip actuator and a separate electronic control circuit separates the circuit interrupter contacts at higher overcurrent conditions. The supplemental electromagnetic trip actuator is supplied with operating power from the electrical distribution circuit through current transformers. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a top view of an electronic circuit interrupter containing the dual electromagnetic trip actuator units in accordance with the invention; FIG. 2 is a top perspective view of the electronic circuit interrupter of FIG. 1 with one of the electromagnetic trip actuators of the invention shown in isometric projection; FIG. 3 is a top perspective view of the electronic circuit interrupter of FIGS. 1 and 2 with the cover removed and with the supplemental electromagnetic trip actuator and supplemental control circuit according to the invention depicted in isometric projection; FIG. 4 is a schematic representation of the electronic circuits employed within the electronic circuit interrupter depicted in FIGS. 1-3; FIG. 5 is an alternative embodiment of the circuit shown in FIG. 4; FIG. 6 is a further embodiment of the circuit depicted in FIG. 4; and FIG. 7 is an additional embodiment of the circuits depicted in FIG. 4. DESCRIPTION OF THE PREFERRED EMBODIMENT An electronic trip circuit breaker 10 is depicted in FIG. 1 wherein the circuit breaker case 11 containing the circuit breaker components is sealed by means of a circuit breaker cover 12 and an accessory cover 13. The circuit breaker is switched ON and OFF by means of a handle operator 14 which projects through the handle slot 15 formed within the circuit breaker cover 12. An externally-accessible rating plug 16 fits within the accessory cover for setting the circuit breaker ampere rating. A wiring access slot 11A formed in the side of the case provides for the egress of electrical wire conductors for internally accessing the circuit breaker accessories contained therein. The electronic circuit breaker 10 is depicted in FIG. 2 with the current transformers 37 already assembled within the circuit breaker case 11 such that the Three such transformers are employed, one for each separate phase of the electrical distribution circuit to which the electronic circuit interrupter is connected. The auxiliary switch 32 is depicted within the auxiliary switch recess 32A prior to insertion of the actuator-accessory unit 17 within the actuator access 17A and the insertion of the printed wire board 27 within the printed wire board recess 27A. When these components are inserted within the respective recesses within the cover 12, the accessory cover 13 is attached by means of screws 34, thru-holes 35 and threaded openings 36 at which time the rating plug 16 is next inserted within the rating plug recess 16A to complete the electronic circuit interrupter assembly. The printed wire board 27 contains an electronic trip circuit such as that described within aforementioned U.S. Pat. No. 4,741,002. The printed wire board electrically connects with the current transformers 37 by attachment between the pins 38, 76 upstanding on the printed wire board and the transformer pin connectors 33, 66. When the printed wire board is electrically connected with the current transformers, the actuator-accessory unit 17 is positioned over a part of the printed wire board such that the printed wire board pins 28 are received within the connector sockets 26 that are formed within the undervoltage release and shunt trip printed wire board 24 situated within the housing 18. The actuator-accessory unit is described within aforementioned U.S. Pat. No. 4,788,621. A good description of the undervoltage and shunt trip circuit is found within U.S. patent application Ser. No. 176,589 filed Apr. 1, 1988, which Application is incorporated herein for reference purposes. The rating plug 16 connects with the printed wire board 27 by positioning the connectors 29 formed on the bottom of the rating plug over the pins 30 upstanding from the printed wire board. The rating plug is described within U.S. Pat. No. 4,728,914, which Patent is incorporated herein for purposes of reference. As further described in aforementioned U.S. Pat. No. 4,788,621, the actuator-accessory unit includes an actuator-accessory electromagnetic coil 19 hereafter "actuator-accessory coil" that interacts with a plunger 20 to control the operation of the actuator lever 21 to electrically disconnect the circuit breaker upon internal signals generated by the printed wire board 27 as well as by external signals supplied to the undervoltage and shunt trip printed wire board 24. The actuator-accessory unit connects with a remote voltage source by means of conductors 22 to provide undervoltage release facility and with a remote switch by means of conductors 23 to provide shunt trip facility to the actuator-accessory unit. The actuator-accessory coil 19 electrically connects with the undervoltage and shunt trip printed wire board 24 over conductors 25. The printed wire board 27 connects with an additional trip actuator printed wire board 54 by means of conductors 55, 79 best seen by referring now to FIG. 3 wherein the circuit breaker case 11 is depicted with the cover removed to show the positioning of the current transformers 37 within the three respective compartments 44-46. The additional trip actuator printed wire board is supported within compartment 46 by means of ledges 75. Also included within the case is a crossbar assembly 40 which carries the movable contact arms 41 and movable contacts 42 The position of the movable contacts with respect to corresponding fixed contacts 43 is controlled by the operating mechanism 39 by means of a trip bar 53. The trip bar is acted upon by operation of the accessory actuator unit 17 shown earlier in FIG. 2 along with an auxiliary trip actuator 47 within a U-shaped housing 48 which is positioned within the compartment 44. The auxiliary trip actuator is similar to that described within U.S. Pat. No. 3,693,122, which Patent is incorporated herein for reference purposes and should be reviewed for its description of a flux "diverter" which allows the plunger 50 to be rapidly propelled by the trip spring 51 when the auxiliary trip coil 49 is actuated by signals transmitted over the two-conductor cable 52. The three-conductor cables 71, 77 connect the trip actuator printed wire board 54 with the transformer pin connectors 33, 66. The interaction between the trip unit printed wire board 27 of FIG. 2 and the trip actuator printed wire board 54 of FIG. 3 can be seen by referring now to FIGS. 4-7. The electronic circuit arrangement 80 in FIG. 4 denotes the connection between the external three-phase power conductors 56A-56C, the electronic trip unit circuit 27 and the trip actuator control circuit 54'. Three corresponding current transformers 37A-37C each interconnect with the trip unit circuit and the trip actuator control circuit by means of a primary winding 57, core 58 and secondary winding 59 for transformer 37A associated with power conductor 56A, for example. The secondary windings connect with the first inputs to three bridge rectifiers 60-62 consisting of diodes D 1 -D 12 over the three-conductor cable 77 as indicated. The other inputs to the bridge rectifier are connected with the secondary windings by means of a separate three-conductor cable 71. The secondary windings also connect with the trip unit circuit by means of a separate three-conductor cable 79. The bridge rectifiler first outputs connect with the trip unit circuit over a separate three-conductor cable 55 through current limiting resistors R 1 -R 3 . One output from the bridge rectifiers connects with the positive rail 65 of the trip actuator circuit 54' while the other output connects with the negative rail 78. Varistor 64 is connected across the positive and negative rails to clamp the voltage that occurs during a short circuit condition on the power conductors. The auxiliary trip coil 49 within the auxiliary trip actuator 47 is connected to the trip actuator printed wire board circuit 54' by means of the two-conductor cable 52. Electrical connection between the trip unit circuit 27 and the trip actuator circuit is made by means of the two-conductor cable 79 and the pulse transformer 63. Upon the occurrence of an overcurrent condition sensed within the trip unit circuit, the actuator-accessory coil 19 within the actuator-accessory unit 17 (FIG. 2) becomes energized which, in turn, generates a signal at the gate of a first thyristor Q 1 through pulse transformer 63, RF by-pass capacitor C 1 and resistor R 4 . With Q 1 conductive, a gate signal is applied through R 16 to the gate of a second thyristor Q 2 thereby rendering Q 2 conductive and causing current to flow through the auxiliary trip coil 49. R 6 supplies latching current to insure that the second thyristor remains on while the current through the auxiliary trip coil continues to rise. The gate sensitivity of Q 2 is set by resistor R 5 connected between the gate of Q 2 and the negative rail 78. Capacitor C 3 limits the rate of rise of voltage across the second thyristor to prevent false triggering from transient voltages while capacitor C 2 limits the rate of rise of voltage occurring across the Q 1 to prevent false conduction by means of rapidly rising transient voltages. With Q 2 conductive, some of the current provided by the current transformers 37 becomes diverted from the trip unit circuit 27 and transferred to the trip actuator circuit 54' via cable conductors 71, 77 through the bridge rectifiers 60-62 over to the auxiliary trip coil 49. The proportion of current from the current transformers that flows through the auxiliary trip coil is determined by the ratio between the auxiliary trip coil impedance and the impedance of the trip unit circuit. The impedance for the trip unit circuit is mainly determined by the values of current limiting resistors R 1 -R 3 which can vary from approximately 0 to 30 ohms. In operation, Q 2 becomes triggered at low levels of overcurrent conditions sensed within the trip unit circuit 27. At the low level overcurrent conditions however, the current that flows from the current transformers 37 is insufficient to cause the auxiliary trip coil 49 to release its associated plunger 50 to articulate the circuit breaker operating mechanism 39 (FIG. 3). At higher overcurrent conditions, above a predetermined value, the overcurrent levels are sufficient to release the plunger and thereby articulate the operating mechanism. In the electronics circuit arrangement 80 of FIG. 4, the thyristors Q 1 , Q 2 are associated with the pulse transformer 63 in a "master"-"slave" arrangement whereby slave thyristor Q 1 , for example, is smaller in size and rating than master thyristor Q 2 to minimize the energy required to trigger the thyristors from the pulse transformer 63. This in turn allows the pulse transformer to be of a smaller size and rating and hence require less energy for operation. It is to be clearly understood that a larger-rated pulse transformer can be directly connected with thyristor Q 2 and thyristor Q 1 could be eliminated, if so desired. In operation therefore, the current within the current transformers 37 is processed within the trip unit circuit 27 and an output signal is provided to the actuator-accessory coil 19 which is reflected via the trip actuator circuit 54' within the auxiliary trip coil 49. Until a predetermined overcurrent conditions occurs, there is insufficient current from the current trans-formers through the trip actuator coil to articulate the circuit breaker operating mechanism. Upon reaching the predetermined overcurrent condition, sufficient current flows from the current transformers through the auxiliary trip coil to thereby articulate the circuit breaker operating mechanism and separate the circuit breaker contacts (FIG. 3) to interrupt the circuit current. The use of the current transformers 37 to energize the auxiliary trip coil 49 is advantageous over the prior art use of storage capacitors as a source of energy. The use of such a storage capacitor is described, for example, in U.S. Pat. No. 4,672,501, which Patent is incorporated herein for reference purposes. Since the storage capacitors are generally rated at several hundred microfarads there is a substantial savings in space requirements when such capacitors are eliminated from the trip unit circuit. An alternate arrangement of the circuit electronics within the circuit breaker 10 of FIG. 1 is depicted at 81 in FIG. 5 wherein the current transformers 37A-37C are coupled with the respective power conductors 56A-56C by means of a primary winding as indicated at 57 for transformer 37 for example are connected with the trip actuator circuit 54' by means of conductors 71A-71C and 77A-77C as illustrated. The transformer pins 33, 66 (FIG. 2) connect both with the trip unit circuit 27 by transformer pins 33A-33C, trip unit pins 38A-38C and conductors 55A-55C as well as with the trip actuator circuit 54' by means of transformer pins 66A-66C and conductors 79A-79C respectively. The trip actuator circuit 54' contains elements common to those described earlier with respect to FIG. 4 and common reference elements will be employed, where possible. The bridge rectifiers 60-62 serve to rectify the current received from the current transformers and supply power to the positive and negative rails 65, 78. The auxiliary trip coil 49 is located within the auxiliary trip actuator 47 separate from the trip actuator circuit 54' and is connected therewith by means of the two-conductor cable 52. The varistor 64 is connected between the positive and negative rails in a manner, described earlier and the thyristor Q 2 , resistors R 4 , R 6 and capacitor C 3 function in the manner described earlier with respect to FIG. 4. The circuit differs from that of FIG. 4 in that the trip actuator coil 19 directly connects with the trip unit circuit 27 by means of the connectors 26 and serve to interrupt lower overcurrent conditions upon command signals originating within the trip unit circuit. The auxiliary trip coil 49 is again supplied directly from the current transformers upon triggering of the thyristor Q 2 . Q 2 in turn is provided with gate current by means of a pulse transformer 70 which is coupled with three primary windings 85A-85C through a common core 84. The bridge rectifiers 60-62 connect with the transformer primary windings 85A-85C through second bridge rectifiers 67-69 and silicon switches S 1 -S 3 . The second bridge rectifiers comprise diodes D 13 -D 24 . The output of each of the second bridge rectifiers is connected to the silicon switches by means of respective burden resistors R 7 -R 9 . The burden resistors generate corresponding voltage signals in proportion to the current transferring through the current transformers. The value of the burden resistors R 7 -R 9 is selected so that the respective capacitors C 7 -C 9 will charge to a value in excess of the break-over threshold of the silicon switches S 1 -S 3 causing the capacitors to discharge into the primary windings 85A-85C of the pulse transformer 70. Resistors R 10 -R 12 provide an RC-timing network with capacitors C 7 -C 9 to prevent break-over of the silicon switches upon the occurrence of spurious overcurrent conditions. The output of the pulse transformer is reflected at the gate of thyristor Q 2 causing the current from the current transformers 37 to flow through the auxiliary trip coil 49 and thereby articulate the circuit breaker operating mechanism 39, of FIG. 3. Resistors R 13 -R 15 serve to limit the current through the respective silicon switches S 1 -S 3 while capacitors C 4 -C 6 provide RF by-pass in order to prevent the silicon switches from inadvertent break-over upon occurrence of voltage transients. This circuit differs from that described in FIG. 4 in that the trip unit circuit 27 governs the operation of the actuator-accessory coil 19 to articulate the operating mechanism for overcurrent conditions up to a predetermined value. When the overcurrent conditions exceed the predetermined value, the operating mechanism becomes articulated by operation of the auxiliary trip coil 49. The actuating current for the auxiliary trip coil is directly provided by the current transformers and allows the auxiliary trip coil to articulate the circuit breaker operating mechanism without the intervention of the trip unit circuit 27 and without requiring energy supplied by large storage capacitors. The pulse transformer 70 provides electrical isolation between the individual phases within the separate phase conductors 56A-56C by means of the separate primary windings 85A-85C. An alternate arrangement of the electronics within the circuit breaker of FIG. 1 is depicted at 82 in FIG. 6 and is similar to that described earlier with respect to FIG. 5 and similar reference numerals will be used for similar components where possible. The trip actuator circuit 54' is connected with the current transformers 37A-37C by means of conductors 71A-71C and conductors 77A-77C respectively. The bridge rectifiers 60-62 connect with the trip unit circuit 27 through transformer pins 33A-33C, trip unit pins 38A-38C, 66A-66C and conductors 55A-55C, 79A-79C. The silicon switches S 1 -S 3 , burden resistors R 7 -R 9 , resistors R 10 -R 12 and capacitors C 4 -C 9 perform in the manner similar to that described earlier with reference to FIG. 5. The auxiliary trip coil 49 within the auxiliary trip actuator 47 connects with the trip actuator circuit 54' by means of the two-conductor cable 52 and the varistor 64 connects across the positive and negative rails 65, 78 as earlier described. The trip actuator circuit differs from that described within FIG. 5 by the inclusion of three opto-isolators 72-74 which connect with the thyristor Q 2 over conductor 86 as indicated. The silicon switches S 1 -S 3 connect with the photo-diodes D 25 -D 27 within the opto-isolators through current limiting resistors R 13 -R 15 . The respective emitters of the photo-transistors Q 3 -Q 5 are connected together and to the gate of the thyristor Q 2 to trigger the thyristor to its "ON" state when the current through the power conductors 56A-56C exceed a predetermined value. The collectors of the photo-transistors are connected together and to the positive rail 65 by means of current limiting resistor R 17 and conductor 87. The bases of the phototransistors are connected together and to their emitters by means of capacitor C 10 and resistor R 18 as indicated. The trip actuator coil 19 functions in the manner described earlier to articulate circuit breaker operating mechanism upon receipt of energizing current supplied by the trip unit circuit 27. The auxiliary trip coil 49 articulates the circuit breaker operating mechanism upon the occurrence of overcurrent conditions in excess of a predetermined value by operation of the silicon switches S 1 -S 3 and thyristor Q 2 to supply operating current directly from the current transformers 37A-37C. The optoisolators 72-74 serve to electrically isolate the current transformers 37A-37C within the individual phases of the three-phase conductors 56A-56C. The circuit electronics arrangement depicted at 83 in FIG. 7 operates in a manner similar to that described earlier with reference to FIG. 4 and similar reference numerals will be used to indicate similar circuit components where possible. The trip actuator circuit 54' connects with the phase conductors 56A-56C through current transformers 37A-37C and the three-conductor cables 71, 77 as indicated. The cable conductors provide input to the bridge rectifiers 60-62 comprising diodes D 1 -D 12 , the outputs of which are connected to the positive and negative rails 65, 78 respectively. The trip actuator circuit connects with the trip unit circuit 27 by means of the three-conductor cables 55, 79 and pin connectors 38 and 76. The actuator-accessory coil 19 connects with the trip unit circuit 27 by means of pins 28 and connectors 26. The auxiliary trip coil 49 within the auxiliary trip actuator 47 connects with the trip actuator circuit 54' by means of the two-conductor cable 52. Current limiting resistors R 1 -R 3 and R 18 -R 20 serve to provide input voltage to the trip actuator circuit for overcurrent determination. The varistor 64 serves to clamp the positive and negative rails 65, 78 against voltage conditions that occur upon short circuit overcurent conditions. The circuit differs from that described with reference to FIG. 4 in that the actuator-accessory coil 19 articulates the circuit breaker operating mechanism upon receipt of signals generated by the trip unit circuit 27 upon the occurrence of overcurrent conditions up to a predetermined level. The trip actuator circuit 54' operates independently of the actuator-accessory coil to articulate the circuit breaker operating mechanism by energizing the auxiliary trip coil 49 upon occurrence of an overcurrent condition in excess of the predetermined amount. The operation of the trip actuator circuit 54' is set by means of the voltage divider consisting of resistors R 21 and R 22 connected across the positive and negative rails 65, 78. When a fault occurs within any of the power conductors 56A-56C a voltage is generated across the voltage divider causing the voltage across C 12 to exceed the threshold voltage of the silicon switch S 4 which in turn becomes conductive causing the capacitor C 12 to discharge into resistor R 4 and triggering thyristor Q 2 into conduction. Current thereby transfers from the current transformers through the trip actuator coil 49, which in turn, articulates the circuit breaker operating mechanism to interrupt the circuit current. As described earlier, resistors R 1 -R 3 and R 18 -R 20 function to increase the current transformer voltage, while dividing the current transformer current between the trip unit circuit 27 and the auxiliary trip coil 49 once the trip coil becomes energized. Capacitor C 11 serves to prevent the silicon switch from becoming conductive due to spurious voltage signals while resistor R 6 serves to provide latching current to Q 2 as earlier described with respect to the circuit configuration depicted in FIG. 4. There has herein been described several circuits for controlling the operation of dual trip coils in the form of a low overcurrent actuator-accessory coil and a larger overcurrent auxiliary trip coil. One of the circuits described herein utilizes the actuator-accessory coil in combination with the auxiliary trip coil to provide overcurrent circuit protection over a wide range of overcurrent values. A separate pair of circuits provide low overcurrent protection by operation of the trip unit circuit with the actuator-accessory coil while simultaneously providing higher overcurrent protection by means of the auxiliary trip coil and the trip actuator circuit, independent of the actuator-accessory coil.
An electronic trip unit within a self-contained circuit interrupter utilizes dual electromagnetic trip actuators. One such actuator responds to overcurrent conditions to interrupt the protected circuit up to a predetermined value. The other such actuator interrupts the protected circuit at all overcurrent conditions in excess of the predetermined value.
7
BACKGROUND OF THE INVENTION The present invention relates to an apparatus for elevational adjustment of a traveling service unit vertically with respect to an associated textile machine in a textile spinning mill and, more particularly, to an apparatus of the aforementioned type for vertically adjusting a traveling service unit with respect to a longitudinal guide rail along the spinning mill machine on which the service unit is guided by at least one guide element. Traveling service units of the aforementioned type are commonly operated in association with various machines in textile spinning mills for performing automatic servicing functions thereon, such as the doffing and donning of bobbins and the piecing of broken yarn ends. In order for such service units to function reliably, the units must be precisely adjusted in elevation with respect to the associated spinning mill machine. In this regard, it has been suggested in the prior art that elevational adjustment of traveling service units with respect to the associated textile machine may be achieved by guiding the service unit along a supporting rail which is mounted to the associated machine in precise relative adjustment thereto. However, in this arrangement, the entire weight of the traveling service unit, which often is considerable, must be supported by the machine. For this reason, the framework of such textile machines must be suitably reinforced, but nevertheless the machine framework undergoes detrimental deformation during traveling movement of the service unit. It has also been suggested in the prior art to provide the traveling service unit with floor-supporting rollers to transfer at least a portion of the weight of the service unit to the supporting floor with only the remaining portion of the weight of the service unit being required to be supported by the guide rail of the spinning mill machine. Hereagain, however, the frame of the spinning mill machine is still required to support a considerable portion of the weight of the traveling service unit. SUMMARY OF THE INVENTION It is accordingly an object of the present invention to provide an apparatus for precise elevational adjustment of a traveling service unit in relation to an associated textile spinning mill machine without placing any significant load on the machine framework. The aforestated objective is satisfied by the present invention by utilizing a guide rail arranged as an elevational reference longitudinally along the associated textile spinning machine and a guide element arranged as a feeler for engagement with the reference guide rail for guiding the traveling service unit therealong. Suitable means are provided in association with the feeler guide element for controlling elevational adjustment of the traveling service unit in relation to the reference guide rail. Preferably, the feeler guide element comprises a lever arm pivotably mounted at one end of the traveling service unit about a horizontal pivot axis and being guided at the opposite end along the reference guide rail. The controlling means includes an inclination detector, e.g., an electronic level detector, operatively connected to the lever arm for detecting the angular relationship thereof to horizontal and for producing a corresponding control signal for vertical adjustment of the traveling service unit. The feeler guide element is preferably disposed in an operating area of the traveling service unit whereat the operational service components thereof are positioned. A control element is operatively associated with the feeler guide element for detecting the elevation of the traveling service unit and for de-actuating it when a predetermined elevation tolerance range is exceeded. The traveling service unit is supported on a floor surface by a suitable supporting means which is selectively adjustable for varying the elevation of the traveling service unit with respect to the floor surface. The supporting means includes a plurality of roller assemblies mounted to the traveling service unit for rolling floor engagement, each roller assembly being adjustable vertically relative to the traveling service unit. The roller assemblies may be independently mounted to the service unit or may be mounted in tandem to an undercarriage associated with the service unit. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic plan view of a traveling service unit embodying one preferred embodiment of the elevational adjustment apparatus according to the present invention; FIG. 2 is a schematic end elevational view, partially broken-away, of the traveling service unit of FIG. 1; FIG. 3 is a schematic broken-away side elevational view of a traveling service unit according to another embodiment of the present invention; and FIG. 4 is a schematic view of an alternative embodiment of feeler guide element according to the present invention. DESCRIPTION OF THE PREFERRED EMBODIMENT Referring now to the accompanying drawings and initially to FIGS. 1 and 2, a traveling service unit of the basic aforedescribed type to which the present invention relates is representatively illustrated schematically at 1. As described, the service unit 1 is adapted for traveling movement longitudinally along an associated textile machine (not shown) such as in a textile spinning mill for performing servicing operations thereon. While the associated textile machine is not depicted, a guide rail is shown at 2 as would be mounted in accordance with the present invention longitudinally along the associated textile machine as an elevational reference. As seen in FIG. 1, the traveling service unit 1 is mounted on four supporting roller wheel assemblies 7,8,9,10 for rolling floor engagement to support the unit 1 for its traveling movement. Each of the supporting roller assemblies 7,8 includes an upstanding screw spindle 18,20 with a supporting wheel rotatably mounted to the lower end thereof and with the upstanding extent of the spindle 18,20 threadedly engaged with an annular nut mounted within the housing of the traveling service unit 1. Each nut associated with the screw spindles 18,20 is drivenly associated with a respective control motor 15,16 for rotational operation of the nuts relative to the screw spindles 18,20, thereby facilitating vertical adjustment of the roller supporting assemblies 7,8 relative to the traveling service unit 1. In similar manner, the supporting roller assemblies 9,10 are mounted in tandem to an undercarriage 11 to which an upstanding screw spindle 19 is affixed in threaded engagement with an associated nut mounted within the traveling service unit 1 in driven association with a control motor 17 for similar vertical adjustment of the roller assemblies 9,10 relative to the service unit 1. Of course, as those persons skilled in the art will readily recognize, many other alternative constructions may be utilized to facilitate selective raising and lowering of the elevation of the traveling service unit 1 with respect to the reference rail 2. For example, each of the four supporting roller assemblies 7,8,9,10 may be individually mounted to the service unit 1, or the roller assemblies 7,8 may be mounted in tandem to an undercarriage similar to the roller assemblies 9,10. Further, hydraulic or pneumatic operating elements, articulated mechanical systems, and other mechanical components and arrangements may likewise be utilized in substitution for the spindle and nut-type assemblies shown. A feeler guide element 3 includes a lever arm pivotably mounted at one end thereof to the traveling service unit 1 about a horizontal pivot axis 5 with the opposite extending end of the lever arm carrying a feeler roller for engagement with the guide rail 2 for guiding the traveling service unit 1 therealong. An electronic level 6 is rigidly mounted to the feeler element 3 for sensing the angular relationship of the feeler element 3 with respect to horizontal. The electronic level detector 6 is operatively connected with each of the control motors 15,16,17 through a common controller 14 for actuating operation of the motors 15,16,17 in relation to the angular disposition of the feeler element 3 relative to horizontal as sensed by the level detector 6. Preferably, the electronic level 6 is disposed in the area of the traveling service unit 1 wherein the operating service components (not shown) of the service unit 1 are located, as represented by the area A in FIG. 1, whereat the elevation of the service unit 1 is desired to be maintained most precisely. In operation, the electronic level detector 6 monitors the angular relationship of the feeler guide element 3 to horizontal, as a reflection of the elevation of the traveling service unit 1 with respect to the elevation reference rail. In turn, the level detector 6 produces a measurement signal indicating the angular disposition of the feeler guide element 3 and transmits the measurement signal to the controller 14 which is programmed, in turn, to control operation of the control motors 15,16,17 in relation to the measurement signal to correspondingly adjust the elevation of the traveling service unit upwardly and downwardly with respect to the reference rail 2 to compensate for deviations in the relative horizontal disposition of the feeler guide element 3 to maintain its measurement signal output at a predetermined zero value. Preferably, a control switch 12 is provided in operative association with the feeler guide element 3 in close is disposition thereto to monitor the elevation of the traveling service unit 1 and to de-actuate operation of the service unit 1 if and when the elevation exceeds a predetermined tolerance range. With reference now to FIG. 3, an alternative embodiment of the present invention is shown wherein the feeler guide element 3' and its associated electronic level detector 6' are pivotably mounted about an axis 5' which is arranged diagonally with respect to the elevation reference rail 2. As in the embodiment of FIGS. 1 and 2, operational control of the motors associated with the supporting roller assemblies, 7,8,9,10 is provided by a common controller 14 operatively associated with the level detector 6' and each motor, only the motor 16 and the supporting roller assembly 7 and its screw spindle 8 being shown in FIG. 3. This arrangement provides an equally simple means for achieving precise elevational adjustment of the traveling service unit 1 with respect to the textile spinning mill machine. While electronic level detectors 6,6' are utilized in the embodiments shown in FIGS. 1-3, a slide-type detector as shown in FIG. 4 may alternatively be utilized. With this type of detector, the feeler guide element 3 is mounted to a slide member 27 slidably disposed on a guide rod 26, with the slide member 27 acting as a ground pick-up in association with a potentiometer 28. The potentiometer 28 generates and transmits an electrical signal to the controller 14 for operating as necessary the drive motors to the supporting roller assemblies 7,8,9,10, thereby for controlling the elevational adjustment of the traveling service unit 1. It will therefore be readily understood by those persons skilled in the art that the present invention is susceptible of a broad utility and application. Many embodiments and adaptations of the present invention other than those herein described, as well as many variations, modifications and equivalent arrangements will be apparent from or reasonably suggested by the present invention and the foregoing description thereof, without departing from the substance or scope of the present invention. Accordingly, while the present invention has been described herein in detail in relation to its preferred embodiment, it is to be understood that this disclosure is only illustrative and exemplary of the present invention and is made merely for purposes of providing a full and enabling disclosure of the invention. The foregoing disclosure is not intended or to be construed to limit the present invention or otherwise to exclude any such other embodiment, adaptations, variations, modifications and equivalent arrangements, the present invention being limited only by the claims appended hereto and the equivalents thereof.
A traveling service unit for an associated textile spinning mill machine may be elevationally adjusted with respect to a reference rail mounted longitudinally along the machine by a feeler guide element pivotably mounted to the service unit in following engagement to the reference guide rail in conjunction with an operatively associated controller connected with vertically adjustable roller support assemblies of the service unit 1 for varying the elevation of the service unit 1 as necessary to compensate for deviations in the pivotal disposition of the feeler guide element with respect to horizontal.
3
RELATED APPLICATION This application hereby claims priority under 35 U.S.C. §119 to U.S. Provisional Patent Application No. 60/283,252, filed on Apr. 11, 2001, entitled “Method and Apparatus for Supporting Multiple Cache Line Invalidations Per Cycle”, by inventors Shailender Chaudhry and Marc Tremblay. BACKGROUND 1. Field of the Invention The present invention relates the design of multiprocessor computer More specifically, the present invention relates to a method and an apparatus for performing multiple cache line invalidations at the same time. 2. Related Art In order to achieve high rates of computational performance, computer system designers are beginning to employ multiple processors that operate in parallel to perform a single computational task. One common multiprocessor design includes a number of processors 151 - 154 with a number of level one (L1) caches 161 - 164 that share a single level two (L2) cache 180 and a memory 183 (see FIG. 1 A). During operation, if a processor 151 accesses a data item that is not present in its local L1 cache 161 , the system attempts to retrieve the data item from L2 cache 180 . If the data item is not present in L2 cache 180 , the system first retrieves the data item from memory 183 into L2 cache 180 , and then from L2 cache 180 into L1 cache 161 . Note that coherence problems can arise if a copy of the same data item exists in more than one L1 cache. In this case, modifications to a first version of a data item in L1 cache 161 may cause the first version to be different than a second version of the data item in L1 cache 162 . In order to prevent coherency problems, computer systems often provide a coherency protocol that operates across bus 170 . A coherency protocol typically ensures that if one copy of a data item is modified in L1 cache 161 , other copies of the same data item in L1 caches 162 - 164 , in L2 cache 180 and in memory 183 are updated or invalidated to reflect the modification. Coherence protocols typically perform invalidations by broadcasting invalidation messages across bus 170 . If such invalidations occur frequently, these invalidation messages can potentially tie up bus 170 , and can thereby degrade overall system performance. In order to remedy this problem, some designers have begun to explore the possibility of maintaining directory information within L2 cache 180 . This directory information specifies which L1 caches contain copies of specific data items. This allows the system to send invalidation information to only the L1 caches that contain the data item, instead of sending a broadcast message to all L1 caches. (This type of system presumes that there exist separate communication pathways for invalidation messages to each of the L1 caches 161 - 164 . These communication pathways are not present in the system illustrated in FIG. 1A.) Note that if more communication pathways are provided between LI caches 161 - 164 and L2 cache 180 , it becomes possible for multiple processors to perform accesses that cause invalidations at the same time. Hence, L1 caches 161 - 164 may receive multiple invalidation requests at the same time. What is needed is a method and an apparatus that facilitates performing multiple invalidations at an L1 cache at the same time. Furthermore, note that L1 caches 161 - 164 are typically set-associative. Hence, when an invalidation message is received by L1 cache 161 , a lookup and comparison must be performed in L1 cache 161 to determine the way location of the data item. For example, in a four-way set-associative L1 cache, a data item that belongs to a specific set can be stored in one of four possible “ways”. Consequently, tags from each of the four possible ways must be retrieved and compared to determine the way location of the data item. This lookup is time-consuming and can degrade system performance. Hence, what is needed is a method and an apparatus for invalidating an entry in an L1 cache without performing a lookup to determine the way location of the entry. SUMMARY One embodiment of the present invention provides a multiprocessor system that supports multiple cache line invalidations within the same cycle. This multiprocessor system includes a plurality of processors and a lower-level cache that is configured to support multiple concurrent operations. It also includes a plurality of higher-level caches coupled to the plurality of processors, wherein a given higher-level cache is configured to support multiple concurrent invalidations of lines within the given higher-level cache. In one embodiment of the present invention, the lower-level cache includes a plurality of banks that can be accessed in parallel to support multiple concurrent operations. In a variation on the above embodiment, the multiprocessor system includes a switch that is configured to couple the plurality of banks of the lower-level cache with the plurality of higher-level caches. In a variation on the above embodiment, each line in a given higher-level cache includes a valid bit that can be used to invalidate the line. These valid bits are contained in a memory that is organized into a plurality of banks that are associated with the plurality of banks of the lower-level cache. Moreover, each bank containing valid bits is hardwired to an associated bank of the lower-level cache, so that the given higher-level cache can receive multiple concurrent invalidation signals from the lower-level cache. In a variation on this embodiment, each bank containing valid bits includes a first port and a second port, wherein the first port can be used to read or write a first location in the bank while the second port is used to invalidate a second location in the bank. This can be accomplished by providing each bank containing valid bits with its own decoder that selects a wordline for the bank's second port, and by sharing a single decoder that selects a single wordline across all the banks. In a further variation, a wordline of the second port causes a memory element to be reset without coupling the memory element to a corresponding bitline. In one embodiment of the present invention, a given invalidation signal received by a given higher-level cache includes, a set location of a line to be invalidated in the given higher-level cache, and a way location of the line to be invalidated in the given higher-level cache. In one embodiment of the present invention, the multiprocessor system is located on a single semiconductor chip. In one embodiment of the present invention, the lower-level cache is an L2 cache, and each of the plurality of higher-level caches is an L1 cache. In one embodiment of the present invention, the plurality of higher-level caches are organized as write-through caches, so that updates to the plurality of higher-level caches are immediately written through to the lower-level cache. BRIEF DESCRIPTION OF THE FIGURES FIG. 1A illustrates a multiprocessor system. FIG. 1B illustrates a multiprocessor system including an L2 cache with a reverse directory in accordance with an embodiment of the present invention. FIG. 2 illustrates an L2 cache with multiple banks within a multiprocessor system in accordance with an embodiment of the present invention. FIG. 3 illustrates a reverse directory in accordance with an embodiment of the present invention. FIG. 4 illustrates an address and an associated invalidation signal in accordance with an embodiment of the present invention. FIG. 5 illustrates the structure of a memory that includes multiple ports for invalidations in accordance with an embodiment of the present invention. FIG. 6 illustrates the structure of a single memory cell within the memory illustrated in FIG. 5 in accordance with an embodiment of the present invention. FIG. 7 is a flow chart illustrating the process of concurrently invalidating multiple cache lines in accordance with an embodiment of the present invention. DETAILED DESCRIPTION The following description is presented to enable any person skilled in the art to make and use the invention, and is provided in the context of a particular application and its requirements. Various modifications to the disclosed embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be applied to other embodiments and applications without departing from the spirit and scope of the present invention. Thus, the present invention is not intended to be limited to the embodiments shown, but is to be accorded the widest scope consistent with the principles and features disclosed herein. Multiprocessor System FIG. 1B illustrates a multiprocessor system 100 with a reverse directory in accordance with an embodiment of the present invention. Note that most of multiprocessor system 100 is located within a single semiconductor chip 101 . More specifically, semiconductor chip 101 includes a number of processors 110 , 120 , 130 and 140 , which contain level one (L1) caches 112 , 122 , 132 and 142 , respectively. Note that the L1 caches 112 , 122 , 132 and 142 may be separate instruction and data caches, or alternatively, unified instruction/data caches. L1 caches 112 , 122 , 132 and 142 are coupled to level two (L2) cache 106 , which includes a reverse directory 302 (described in more detail with reference to FIGS. 3-6 below). L2 cache 106 is coupled to off-chip memory 102 through memory controller 104 . In one embodiment of the present invention, L1 caches 112 , 122 , 132 and 142 are write-through caches, which means that all updates to L1 caches 112 , 122 , 132 and 142 are automatically propagated to L2 cache 106 . This simplifies the coherence protocol, because if processor 110 requires a data item that is present in L1 cache 112 , processor 110 can receive the data from L2 cache 106 without having to wait for L1 cache 112 to source the data. Moreover, no forwarding network is needed to allow L1 cache 112 to source the data. Note that in one embodiment of the present invention, L2 cache 106 is an “inclusive cache”, which means that all items in L1 caches 112 , 122 , 132 and 142 are included in L2 cache 106 . L2 Cache with Multiple Banks FIG. 2 illustrates an L2 cache 106 with multiple banks in accordance with an embodiment of the present invention. In this embodiment, L2 cache 106 is implemented with four banks 202 - 205 , which can be accessed in parallel by processors 110 , 120 , 130 and 140 through switches 215 and 218 . Switch 215 handles communications that feed from processors 110 , 120 , 130 and 140 into L2 banks 202 - 205 , while switch 216 handles communications in the reverse direction from L2 banks 202 - 205 to processors 110 , 120 , 130 and 140 . Note that only two bits of the address are required to determine which of the four banks 202 - 205 a memory request is directed to. Also note that switch 215 additionally includes an I/O port 150 for receiving communications from I/O devices, and switch 216 includes an I/O port 152 for sending communications to I/O devices. Furthermore, in one embodiment of the present invention, each of these banks 202 - 205 includes a reverse directory, which is described in more detail below with reference to FIG. 5 . Note that by using this “banked” architecture, it is possible to concurrently connect each L1 cache to its own bank of L2 cache, thereby increasing the bandwidth of L2 cache 106 . However, concurrent accesses to L2 cache 106 can potentially cause multiple invalidations of lines within L1 caches 112 , 122 , 132 and 142 . In order to support these invalidations, each L1 cache has a separate pathway to receive an invalidation signal from each of the banks 202 - 205 of L2 cache 106 . As illustrated in FIG. 2, L1 cache 112 receives: an invalidation signal 221 from L2 bank 202 , an invalidation signal 222 from L2 bank 203 , an invalidation signal 223 from L2 bank 204 , and an invalidation signal 224 from L2 bank 205 . Each of the other L1 caches 122 , 132 and 142 receive similar invalidation signals from L2 banks 202 - 205 . However, these additional invalidation signals are not illustrated in FIG. 1 for purposes of clarity. Reverse Directory FIG. 3 illustrates L2 bank 202 along with an associated reverse directory 302 in accordance with an embodiment of the present invention. L2 bank 202 contains an eight-way set associative cache 304 for storing instructions and data. A portion of the address is used to determine a set (row) within cache 304 . Within a given set, eight different entries can be stored in each of eight different “way locations,” which are represented by the eight columns in cache 304 . Reverse directory 302 includes a separate block for each L1 cache. More specifically, block 312 is associated with L1 cache 112 , block 322 is associated with L1 cache 122 , block 332 is associated with L1 cache 132 , and block 342 is associated with L1 cache 142 . Note that each of these blocks 312 , 322 , 332 and 342 includes an entry for each line in the associated L1 caches 112 , 122 , 132 and 142 . Moreover, since L1 cache 112 is organized as a four-way set associative cache, the associated block 312 within reverse directory 302 is also organized in the same fashion. However, entries within L1 cache 112 contain data and instructions, whereas entries within the associated block 312 contain indexing information specifying a location of the line within cache 304 . Invalidation Signal FIG. 4 illustrates an address 400 and an associated invalidation signal 430 in accordance with an embodiment of the present invention. The top portion of FIG. 4 illustrates the address 400 , which specifies the location of a data item (or instruction) within memory. L1 cache 112 divides this address into L1 tag 412 , L1 set number 414 , and L1 line offset 418 . L1 set number 414 is used to look up a specific set of the four-way set-associative LI cache 112 . L1 tag 412 is stored in L1 cache 112 , and is used to perform comparisons for purposes of implementing the four-way set-associative memory for each set. L1 line offset 418 determines a location of a specific data item within the line in L1 cache 112 . L2 cache 106 divides address 400 into L2 tag 402 , L2 set number 404 , L2 bank number 406 and L2 line offset 408 . L2 bank number 406 determines a specific bank from the four banks 202 - 205 of L2 cache 106 . L2 set number 404 is used to look up a specific set of the eight-way set-associative bank of L2 cache 106 . L2 tag 402 is stored in a specific bank of L2 cache 106 , and is used to perform comparisons for purposes of implementing the eight-way set-associative memory for each set. L2 line offset 408 determines a location of a specific data item within the line in L2 cache 106 . The corresponding invalidation signal 430 for address 400 contains reduced L1 set number 424 and L1 way number 429 . Reduced L1 set number 424 includes L1 set number 414 without the bits for L2 bank number 406 . The bits for L2 bank number can be removed because, as can be seen in FIG. 5, each invalidation signal is hardwired to a corresponding bank of L2 cache 106 , so the L2 bank number 406 is not needed. L1 way number 429 contains a two-bit index which specifies a way (column) location of the line, out of the four possible way locations for the line, in L1 cache 112 . Memory that Supports Multiple Concurrent Invalidations FIG. 5 illustrates the structure of a memory that stores valid bits for lines within L1 cache 112 in accordance with an embodiment of the present invention. This memory includes multiple banks 501 - 504 , and multiple ports for receiving invalidation signals 221 - 224 , wherein each invalidation signal is coupled to its own bank of memory. More specifically, invalidation signal 221 is coupled to bank 501 , invalidation signal 222 is coupled to bank 502 , invalidation signal 223 is coupled to bank 503 and invalidation signal 224 is coupled to bank 504 Also note that each of these banks is divided into four “ways” to reflect the four-way associative structure of L1 cache 112 . Hence, the way number 429 for each of the invalidation signals 221 - 224 is separated from the set number 424 , and the set number 424 feeds through a decoder to select a wordline. Note that each bank entry has a separate valid bit for each way. Also note that L1 way number 429 enables the specific valid bit associated with an operation. For example, invalidation signal 211 is divided into set number 511 and way number 521 . Way number 521 is used to select a column of bank 501 , while set number 511 feeds through decoder 531 to activate a wordline for bank 501 . Note that the memory also includes at least one additional port in the right-hand side for performing read or write operations at the same time invalidations are taking place from the left-hand side. This port receives an address 541 , which feeds through a decoder 541 that selects a single wordline across all of the banks 501 - 504 of the memory. Memory Cell Structure FIG. 6 illustrates the structure of a single memory cell within the memory illustrated in FIG. 5 in accordance with an embodiment of the present invention. This memory cell receives a wordline 551 from the invalidation port and a wordline 552 from the read/write port. Note that this memory cell may potentially be coupled to other ports and associated wordlines. Activating wordline 551 causes the memory cell to be coupled to ground on the left-hand-side and to VDD on the right-hand-side. Note that no bitlines are required for an invalidation operation because an invalidation operation always sets the memory element to a logical zero value. Also note that enable signal 630 which is determined from L1 way number 429 enables operation of wordline 551 . In contrast, activating wordline 552 causes the memory element to be coupled to differential bitlines D+ 601 and D− 602 , which are used to read from or write to the memory element. Process of Performing Concurrent Invalidations FIG. 7 is a flow chart illustrating the process of concurrently invalidating multiple cache lines in accordance with an embodiment of the present invention. The process starts when multiple invalidation signals 221 - 224 are received at L1 cache 112 (step 702 ). In response to these multiple invalidation signals 221 - 224 , the system performs concurrent invalidations on the multiple banks 501 - 504 of LI cache 112 illustrated in FIG. 5 (step 704 ). Note that read/write accesses can be performed on the memory through the separate read/write port at the same time these concurrent invalidations are taking place (step 706 ). The foregoing descriptions of embodiments of the present invention have been presented for purposes of illustration and description only. They are not intended to be exhaustive or to limit the present invention to the forms disclosed. Accordingly, many modifications and variations will be apparent to practitioners skilled in the art. Additionally, the above disclosure is not intended to limit the present invention. The scope of the present invention is defined by the appended claims.
One embodiment of the present invention provides a multiprocessor system that supports multiple cache line invalidations within the same cycle. This multiprocessor system includes a plurality of processors and a lower-level cache that is configured to support multiple concurrent operations. It also includes a plurality of higher-level caches coupled to the plurality of processors, wherein a given higher-level cache is configured to support multiple concurrent invalidations of lines within the given higher-level cache. In one embodiment of the present invention, the lower-level cache includes a plurality of banks that can be accessed in parallel to support multiple concurrent operations. In a variation on this embodiment, each line in a given higher-level cache includes a valid bit that can be used to invalidate the line. These valid bits are contained in a memory that is organized into a plurality of banks that are associated with the plurality of banks of the lower-level cache.
6
This application claims the benefit of Provisional Application No. 60/345,581, filed Jan. 3, 2002, which is hereby incorporated herein by reference in its entirety. The invention herein described relates generally to a containment shroud for high velocity projectiles and more particularly to an engine fan blade containment shroud including a wall made of a quartz fiber composite. BACKGROUND OF THE INVENTION High-bypass-ratio turbofan engines are used to power modern large commercial aircraft because of their overall efficiency, high thrust at low flight speeds, low jet velocity and low fuel consumption. A fan containment shroud is the largest structural component in these engines. The containment shroud is intended to contain a fan blade in the rare event of a blade loss during engine operation (the centrifugal force acting on a broken blade can cause the blade to puncture the engine nacelle). In addition, the containment shroud should retain its structural integrity after a blade-out incident to limit secondary damage caused by impact debris and to constrain out-of-balance motion of the engine's rotor after a blade or blade fragment is lost. Two approaches are currently used to contain fan blades in modern commercial engines. The first approach (hardwall shroud design) uses an impact resistant metal alloy for a fan case with a wall thickness sufficient to prevent perforation by a fan blade and circumferential ribs for stiffness. In the hardwall shroud design, the wall thickness is much greater than the thickness required for structural loads during normal engine operation. The extra weight, which is needed only in the rare event of a blade-out, is therefore a parasitic weight that reduces overall energy efficiency during normal engine operation. The second approach (softwall shroud design) uses a thin metal alloy case that provides structural capabilities, while containment capability is provided by a fiber or fabric wrap (Kevlar®) around the case. During a blade-out event, the blade passes through the inner metal case and is captured in the outer fabric layers. Case stiffness may be provided by an isogrid rib pattern in the metal case or by using a honeycomb structure on the outside of the case. In the softwall design, the fabric wrap is a parasitic weight. In U.S. Pat. No. 6,003,424, there is described an armor system that is said to be useful as a containment shroud for a fan-blade engine. The armor system comprises a first pliable, cut resistant fibrous layer and a second pliable fibrous layer substantially coextensive with and surrounding the first layer. The first layer is intended to engage any projectile thrown by the engine to slow its velocity, and the second layer is intended to dissipate the incoming energy and thereby resist complete penetration of the second layer by the projectile. The first layer may comprise a plurality of networks selected from the group consisting of an uncoated nonwoven network of randomly oriented fibers and an uncoated knitted, preferably tightly, network of fibers. The second layer may comprise a plurality of networks selected from the group consisting of a loosely woven network of fibers, an open knitted network of fibers, a braided network of fibers, and a nonwoven network of oriented fibers. The '424 patent indicates a wide variety of metallic, semi-metallic, inorganic and/or organic fibers can be used, while stating it is crucial that a sufficient weight percent of cut resistant fibers or combination of fibers with high tensile properties be used to achieve the indicated properties of the layers of the armor systems. Fibers having the high tensile properties desired are those having a tenacity equal to or greater than about 10 g/d, a tensile modulus equal to or greater than about 200 g/d and an energy-to-break equal to or greater than about 8 Joules/gram (J/g), with the fibers of choice having a tenacity equal to or greater than about 35 g/d, the tensile modulus equal to or greater than about 1500 g/d and the energy-to-break equal to or greater than about 50 J/g. According to the '424 patent, these highest values for tenacity, tensile modulus and energy-to-break are generally obtainable only by employing solution grown or gel filament processes, such as are used to produce high strength polyethylene fiber known as Spectra.RTM, a product of Allied-Signal, Inc. While the fibers of the first layer are uncoated, the fibers of the second layer are coated with a matrix material. According to the '424 patent, the proportion of matrix to filament in the network preferably is about 10 to 30%. The network preferably is comprised of a plurality of sheet-like arrays of untwisted fibers with the fibers aligned substantially parallel to one another along a common fiber direction within each array. The arrays are preferably individually impregnated with a matrix binder and stacked. According to the '424 patent, it is important that the arrays not be consolidated between networks with the matrix binder since this will stiffen the layer too much. Heretofore it also has been proposed to use a ceramic layer on the impact surface of a composite wall of a containment shroud. The ceramic layer serves to fragment the projectile and spread the impact load over a larger area of the composite backing. According to U.S. Pat. No. 6,113,347, an annular fan containment shroud may have an interior surface with an abrasive surface texture that is capable of dulling sharp corners and edges of impacting fan blades so as to reduce the ability of the fan blade to pierce the containment shroud. The textured surface may be produced by protuberances in the form of sawtooth steps, sharp spikes or pieces of a hard material impregnated in the textured surface. The present invention was developed to overcome the deficiencies of prior art jet engine fan blade containment shrouds and provide superior stopping power for the same or less areal weight. SUMMARY OF THE INVENTION The present invention provides an aircraft engine fan containment shroud including a containment structure composed of a composite material including a reinforcing fiber in a resin matrix, the reinforcing fiber having an elongation to break of at least about 3.6%, more preferably at least about 4%, still more preferably at least about 4.5%, yet more preferably at least about 5%, and most preferably between about 5% and about 7%, or higher. In a preferred embodiment, the fiber is a quartz fiber having an elongation to break of at least about 3.6%, more preferably at least about 4%, still more preferably at least about 4.5%, yet more preferably at least about 5%, and most preferably about 5.1%. Additionally or alternatively, the reinforcing fiber, in particular quartz fiber, has a hardness of at least about 4 on the Mohs scale, more preferably at least about 5 on the Mohs scale, still more preferably at least about 6 on the Mohs scale, and most preferably between about 6.5 and 7 (or higher) on the Mohs scale, as measured on bulk material. Moreover, the reinforcing fiber preferably has a tensile strength at least about 300 ksi and more preferably at least about 350 ksi. The matrix material may be selected from thermosetting resins, thermoplastic resins, or combinations of such resins. In one embodiment, the matrix material comprises an epoxy resin, whereas in another embodiment the matrix material comprises polyether amide resin. The percent resin content by weight in a fiber prepreg may be from about 10% to about 60%, more preferably about 25% to about 50%, still more preferably between about 31% and about 45%, and most preferably about 38%+/−3%. The percent fiber content by weight in the fiber prepreg is from about 40% to about 90%, more preferably from about 50% to about 75%, still more preferably between about 55% and 69%, and most preferably about 62%+/−3%. The composite material according to the invention may be used as the fan case in hardwall shroud systems to provide improved impact resistance and blade containment, as the fan case and/or outer wrap in softwall shroud systems, or as a containment structure in other containment systems. For high temperature applications, the use of quartz fiber with high temperature polymer matrix resins are contemplated. The composite material provides for weight reduction while providing fan blade containment without loss of structural integrity and with improved impact/puncture resistance. More generally, the invention provides a containment shroud composed of a composite material as above-described and specifically an epoxy/quartz fiber composite. The containment shroud (or other structure composed of a composite material as herein described) may find use in containing blades in a jet engine other than the fan blades, or in various other applications where containment of high velocity cutting or other projectiles is desired. The foregoing and other features of the invention are hereinafter more fully described and particularly pointed out in the claims, the following description and the annexed drawings setting forth in detail certain illustrative embodiments of the invention, these being indicative, however, of but a few of the various ways in which the principles of the invention may be employed. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a longitudinal cross-sectional view illustrating an exemplary high bypass ratio turbofan engine incorporating a softwall-type blade containment system according to the present invention. FIG. 2 is longitudinal cross-sectional view illustrating an exemplary high bypass ratio turbofan engine incorporating a hardwall-type blade containment system according to the present invention. DETAILED DESCRIPTION Referring now in detail to the drawings wherein identical reference numerals denote the same elements throughout the various views, FIG. 1 illustrates a longitudinal cross-sectional view of an exemplary high bypass ratio turbofan engine 10 , such as that shown in U.S. Pat. No. 6,113,347. The engine 10 includes, in serial axial flow communication about a longitudinal centerline axis 12 , conventional structures including a fan rotor 14 and a booster 16 . The other conventional structures of the engine 10 , such as a high pressure compressor, combustor, high pressure turbine, and low pressure turbine are not shown for clarity of illustration. The fan rotor 14 and booster 16 are drivingly connected to the low pressure turbine via a rotor shaft 18 . The fan rotor 14 comprises a plurality of radially extending blades 20 (only one of which is shown in FIG. 1 ) mounted on an annular disk 22 , wherein the disk 22 and the blades 20 are rotatable about the longitudinal centerline axis 12 of engine 10 . The engine 10 also includes a blade containment shroud generally depicted at 24 . The blade containment shroud 24 comprises an annular containment casing (or case) 26 that is positioned radially outward of the blades 20 and in surrounding relationship therewith. An outer shell 28 is spaced radially outward of the casing 26 and is attached to the casing 26 at upstream and downstream locations so as to define a chamber 30 therebetween. Chamber 30 , which is also known as a nesting area, may include a honeycomb structure (not shown) which is used to retain broken blades or blade fragments therein. A composite wrap 32 surrounds the outer surface of the outer shell 28 . Acoustic liners 34 may be affixed to the interior surface of the containment casing 26 at locations fore and aft of the blades 20 . It is noted that although FIG. 1 depicts a blade containment shroud of the type utilizing a nesting area with honeycomb structures therein and a composite material wrap, the present invention can also be used with blade containment systems of other types, including a single containment casing made from a composite material according to the invention. In the illustrated blade containment system 24 , a ballistic barrier 36 may be secured to the interior surface of the containment casing 26 in the section thereof which is axially aligned with the fan blades 20 . The barrier 36 may be composed of a number of elongated ceramic tiles which are abutted side by side so as to form a continuous barrier over the interior circumferential surface of the containment casing 26 . The tile surfaces facing the fan blades 20 may be provided with a roughened or abrasive surface texture. The abrasive surface assists in dulling the sharp edges and corners of a fan blade impacting thereon, thereby reducing the ability of the fan blade to pierce the containment casing 26 . FIG. 2 shows another type of blade containment shroud 60 , such as that shown in U.S. Pat. No. 5,823,739. The shroud 60 circumscribes an array of fan blades 48 and has an impact zone 68 which is the region where a separated blade fragment is anticipated to strike the containment shroud. A containment ring or casing 70 having sufficient thickness and rigidity to absorb the impact of a blade fragment is axially coincident with the impact zone. The containment shroud also may include an airseal 72 comprising an abradable layer 74 bonded to a substrate 76 which, in turn, is bonded to the floor 78 of a circumferentially extending channel 80 in the casing 70 . Stiffening rings 84 and 86 provide additional stiffness to the casing and thus the shroud. In accordance with the invention, the casing 26 ( FIG. 1 ), casing 70 ( FIG. 2 ), outer shell 28 ( FIG. 1 ) and/or composite wrap 32 ( FIG. 1 ) are composed of a composite material including a reinforcing fiber in a resin matrix, the reinforcing fiber having an elongation to break of at least about 3.6%, more preferably at least about 4%, still more preferably at least about 4.5%, yet more preferably at least about 5%, and most preferably between about 5% and about 7%, or higher. In a preferred embodiment, the fiber is a quartz fiber having an elongation to break of at least about 3.6%, more preferably at least about 4%, still more preferably at least about 4.5%, yet more preferably at least about 5%, and most preferably about 5.1%. Additionally or alternatively, the reinforcing fiber has a hardness of at least about 4 on the Mohs scale, more preferably at least about 5 on the Mohs scale, still more preferably at least about 6 on the Mohs scale, and most preferably between about 6.5 and 7 (or higher) on the Mohs scale, as measured on bulk material. The percent resin content by weight in a fiber prepreg may be between about 10% to about 60%, more preferably about 25% to about 50%, still more preferably between about 31% and about 45%, and most preferably about 38%+/−3%. The matrix material of the composite may be selected from thermosetting resins, thermoplastic resins, or combinations of such resins. As used herein, “thermosetting resins” are resins of a polymer or polymers that solidify or set irreversibly when heated or otherwise cured. Such resins do not tolerate thermal cycling and cannot be resoftened and reworked after molding, extruding or casting. As used herein, “thermoplastic resins” are resins of a polymer or polymers that soften when exposed to heat and return to their original condition when cooled to room temperature. Examples of thermosetting resins include phenolics, alkyds, amino resins, polyesters, epoxides, silicones, vinyl esters and urethanes. Examples of thermoplastic resins include polyvinyl chloride, nylons, fluorocarbons, linear polyethylenes, polyurethane prepolymers, polystyrenes, polypropylene, polyolefins and acrylic resins. The composite material comprising the reinforcement fibers and matrix material may be formed to a desired shape by any suitable forming technique, such as by using thermoforming, vacuum forming, transfer molding and other techniques. In one embodiment of the present invention, the matrix material comprises an epoxy resin. As used herein, an epoxy resin means a thermosetting resin containing the oxirane, or epoxy group, as the reactive functionality. The oxirane group may be derived from a number of diverse methods of synthesis, for example by the reaction of an unsaturated compound with a peroxygen compound such as peracetic acid; or by the reaction of epichlorohydrin with a compound having an active hydrogen, followed by dehydrohalogenation. Methods of synthesis are well known to those skilled in the art, and may be found, for example, in the Handbook of Epoxy Resins, Lee and Neville, Eds., McGraw Hill, 1967, in chapters 1 and 2 and the references cited therein. The epoxy resins useful in the practice of the subject invention are generally those that are commercially available and substantially di- or polyfunctional resins. In general, the functionality of the resins is from about 1.8 to about 8. Examples of the epoxy resins which are derived from amines include tetraglycidyl diaminodiphenylmethane, triglycidyl-p-aminophenol, triglycidyl-m-aminophenol and triglycidyl aminocresol. Among these, tetraglycidyl diaminodiphenylmethane is preferred because it has excellent thermal resistance. Examples of the epoxy resins derived from phenols include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, phenol novolak type epoxy resins, cresol novolak type epoxy resins and resorcinol type epoxy resins. Since liquid bisphenol A type epoxy resins and bisphenol F type epoxy resins have low viscosities, they are suited for blending other epoxy resins and additives. Examples of the epoxy resins derived from compounds having carbon—carbon double bonds include alicyclic epoxy resins. Brominated epoxy resins obtained by brominating these alicyclic epoxy resins are also preferred since the water absorption of the resin is decreased and environment resistance is promoted. The epoxy resin may be a mixture of two or more epoxy resins and may contain a mono-epoxy compound. The combination of a glycidylamine type epoxy resin and a glycidyl ether type epoxy resin is preferred because it simultaneously satisfies good thermal resistance, water resistance and processability. Another component constituting the epoxy resin composition used in the present invention is a curing agent. Any compound having active groups which can react with epoxy group may be employed as the curing agent. Compounds having amino groups, acid anhydride groups, azide groups and hydroxy groups may preferably be employed. For example, dicyandiamide, various isomers of diaminodiphenyl sulfone, aminobenzoates, various acid anhydrides, phenol novolak resins and cresol novolak resins may be employed. Dicyandiamide is preferred because it gives long shelf-life of prepreg. If an aromatic diamine is used as a curing agent, cured epoxy resin having good thermal resistance can be obtained. In particular, various isomers of diaminodiphenyl sulfone are best preferred in the present invention since they give cured resins with good thermal resistance. Diaminodiphenyl sulfone may preferably be used in an amount such that the amount of its active hydrogen is 0.7–1.2 equivalent with respect to the amount of the epoxy groups of the epoxy resin. As the aminobenzoates, trimethyleneglycol-di-p-aminobenzoate and neopentylglycol-di-p-aminobenzoate may preferably be used. Although the resins obtained by using those curing agents have lower thermal resistances than those obtained by using diaminodiphenylsulfone, since they excel in tensile strength and toughness, they may be selected depending on the intended use. If an acid anhydride represented by phthalic anhydride is used as a curing agent, cured resin with good thermal resistance is obtained, and an epoxy resin composition having low viscosity and so having excellent processability can be obtained. A phenol novolak resin or a cresol novolak resin may also preferably be used as a curing agent since ether bonds having good hydrolysis resistance are introduced into the molecular chains, so that the water resistance of the cured resin is promoted. Further, various curing catalysts may also be employed together with the above-mentioned curing agents. A representative example of the curing catalysts is monoethylamine complex of trifluoroboron. Cyanate resins (triazine resins) may also be employed together with the epoxy resin. In this case, a curing reaction takes place between the cyanate and the epoxy groups, so that a cured resin with low water absorption can be obtained. In one embodiment, the epoxy resin is used in combination with a another resin as the matrix material. For example, a cyanate functional or bismaleimide functional resin is combined with the epoxy resin. Cyanate resins are heat curable resins whose reactive functionality is the cyanate, or —OCN group. These resins are generally prepared by reacting a di- or poly-functional phenolic compound with a cyanogen halide. Bismaleimide resins are heat curable resins containing the maleimido group as the reactive functionality. The term bismaleimide as used herein includes mono-, bis-, tris-, tetrakis-, and higher functional maleimides and their mixtures. Bismaleimide resins thus defined are prepared by the reaction of maleic anhydride or a substituted maleic anhydride such as methylmaleic anhydride, with an aromatic or aliphatic di- or polyamine. Examples of useful epoxy resins include those described in U.S. Pat. Nos. 6,313,248, 6,265,491, 6,242,083, 6,139,942, 5,932,635, 5,605,745 and 5,532,296, the disclosures of which are hereby incorporated by reference. A preferred composite is an epoxy/quartz fiber composite of the type previously used successfully for many years in the construction of radomes. Radomes are used to house and protect radar components in aircraft from wind load and the elements, such as rain and bird strikes. In addition to their desirable electromagnetic properties, epoxy/quartz fiber composites have been found to provide superior resistance to hail impacts than prior composites such as the previously used Kevlar® fiber and glass fiber composites. While hail impacts pale in severity and magnitude to the impact conditions that occur during a fan blade-out condition in a jet engine, the applicant has discovered that quartz fiber composites and especially epoxy/quartz fiber composites afford advantages over other fiber composites previously used in fan cases. In one embodiment, the composite comprises an epoxy prepreg containing quartz fibers. Examples of useful epoxy prepregs include those commercially available from FiberCote Industries Inc. and particularly FiberCote E761, and the Bryte BT250E epoxy resin system. Another reinforced resin system is a polyether amide resin (PEAR) system. PEAR is a high-performance family of composite resins that offer excellent value and performance that combine strength, low weight, and chemical and temperature resistance. It doesn't burn easily, and gives off less toxins when subjected to flames, and its easy to formulate and process. Another reinforced resin system is reinforced thermoplastic laminate (RTL). Consolidated flat sheets of PPS or PEI thermoplastic resins having desired thicknesses may be formed into desired shapes, using thermoforming or other suitable processes. The cross-sections of fibers for use in accordance with the present invention may vary. The fibers may be of any suitable diameter. However, in one embodiment, the fibers may be from 8 to 16 microns in diameter, and more particularly from 9 to 14 microns in diameter. Preferred fibers are Quartzel® fibers available from Saint-Gobain Quartz. Quartzel Yarn is available in a variety of assemblies based upon two basic fiber (filament) diameters, 9 or 14 microns, and may be used in a variety of textile processes including weaving, braiding, knitting, etc. The fibers may be of circular or of flat or of oblong or of irregular or regular multi-lobal cross-section having one or more regular or irregular lobes projecting from the linear or longitudinal axis of the filament. It is particularly preferred that the fibers be of substantially circular, flat or oblong cross-section, most preferably the former. The fibers preferably are woven to form a fabric. The fibers may be prepregged before weaving or the fabric may be prepregged after weaving. One or more fabric layers or plies may be laid up to form a consolidated casing or other structure of desired shape and/or thickness suitable for the intended application. The present invention also contemplates nonwoven fiber networks of randomly oriented fibers, at least one of which comprises discontinuous fiber, preferably staple fiber, having a length ranging from about 0.25 to 10.0 inches (0.63 to 25.4 cm), more preferably from about 1.0 to 8.0 inches (2.54 to 20.3 cm), most preferably from about 2.0 to 6.0 inches (5.1 to 15.2 cm). There are several methods to lay such a completely random and discontinuous network of fibers, for example by carding or fluid laying (air or liquid), as are conventional in the art. Consolidation of the network for handling, i.e., bonding of the network of fibers, can occur by any of the following means: mechanically, e.g., needle punching; chemically, e.g., with an adhesive; and thermally, with a fiber to point bond or a blended fiber with a lower melting point. One consolidation method is needle punching, alone or followed by one of the other methods, and one nonwoven network is a needle punched discontinuous fiber length felt. The invention also contemplates continuous lengths of fiber wound circumferentially in relation to the axis of a containment shroud. However, fabrics generally are preferred. The casing 26 , casing 70 and/or composite wrap 32 may be formed by laying up or wrapping prepregged woven fibers networks or layers to form a multilayer structure that can be cured as by heating. Alternatively, a fiber prepreg may be wrapped circumferentially to form a containment ring structure. Although the use of prepregged fibers or fabrics is preferred, uncoated fibers or fiber fabrics/networks may be formed into a desired shape and then the resin added by suitable means. The overall thickness of the casing 26 , casing 70 , outer shell 28 and/or composite wrap 32 ( FIGS. 1 and 2 ) may be varied as needed to provide the desired strength and performance requirements for a given application. For example, a composite quartz/epoxy panel of about ¼ inch thick, made using 20 woven fabric plies with combined thickness of 0.24 inch and a weight of 2.07 lb/ft 2 yielded a performance comparable to Inconel 718 metal alloy during blade impact tests on curved and flat panels. More particularly, it was found that such panel had approximately the same stopping power and resistance to puncture as panels of similar thickness made from Iconel 718 metal alloy for the same areal weight. It was also found that there was no directional effect with respect to warp vs. fill of the quartz fiber fabric. Particularly useful quartz fiber fabrics are Astroquartz® II or III fabrics. These fabrics are woven from high tensile strength, high purity (99.95%) fused silica fiber yarns. Two fabric styles of Astroquartz® III fabrics are available, namely 4503 and 4581. Epoxy laminates made from these fabrics have near zero coefficient of thermal expansion and excellent mechanical properties in composites. Epoxies provide desirable performance for temperatures up to about 300° F. or higher. For high temperature applications of 600° F. or greater, the use of quartz fiber with high temperature resins such as polyimides is contemplated. The following is a table showing a comparison of various properties of various fibers including quartz fiber and other reinforcing fibers, including Spectra® fiber and Kevlar® fibers which previously have been used in containment shrouds. E-Glass S-Glass Quartz Spectra Kevlar 49 Kevlar 29 Steel Density (pci) 0.094 0.090 0.080 0.035 0.052 0.052 0.281 Tensile Strength 250 370 350 375 330 330 400 (ksi) Tensile Modulus 10.4 12.6 11.3 17.0 18.0 12.0 29.0 (msi) Elongation to 2.4 2.9 5.1 3.5 1.8 2.8 1.4 Break % Source 1 1 2 2 1 1 2 1 Mechanical Behavior and Properties of Composite Materials, Vol 1 2 Various Supplier Data Although the invention has been shown and described with respect to a certain preferred embodiment or embodiments, it is obvious that equivalent alterations and modifications will occur to others skilled in the art upon the reading and understanding of this specification and the annexed drawings. In particular regard to the various functions performed by the above described elements (components, assemblies, devices, compositions, etc.), the terms (including a reference to a “means”) used to describe such elements are intended to correspond, unless otherwise indicated, to any element which performs the specified function of the described element (i.e., that is functionally equivalent), even though not structurally equivalent to the disclosed structure which performs the function in the herein illustrated exemplary embodiment or embodiments of the invention. In addition, while a particular feature of the invention may have been described above with respect to only one or more of several illustrated embodiments, such feature may be combined with one or more other features of the other embodiments, as may be desired and advantageous for any given or particular application.
An engine fan containment shroud including a containment structure composed of a composite material including a reinforcing fiber having an elongation to break of at least about 3.6%. The preferred fiber is a quartz fiber having an elongation to break of at least about 5%. Additionally or alternatively, the reinforcing fiber, in particular quartz fiber, has a hardness of at least about 4 on the Mohs scale, as measured on bulk material, which resists cutting by an impacting object. The composite material and specifically an epoxy/quartz fiber composite provides for weight reduction while providing fan blade containment without loss of structural integrity and with improved resistance to impact and puncture.
5
BACKGROUND OF THE INVENTION The invention relates to an eyeglass frame with a hinge for bending of the eyeglass temples as well as a process for the production thereof. The invention further relates to a use of snap springs with a “snap frog” effect. Eyeglasses belong to the prior art and are known in many embodiments. Most eyeglasses are equipped with a hinge, one part of which is linked to the eyeglass rim and the other part of which is linked to the eyeglass temple. The two parts are inserted into each other and screwed together. Described in U.S. Pat. No. 4,898,460 are eyeglasses in which the eyeglass frame consists of a tube, which, at several points, has hinge bellows at which the tube can be bent to a shape that is adapted to the person wearing the eyeglasses. Further described in JP 10-039 261 A is an eyeglass frame for which the flexible eyeglass temples are held in an unfolded position by a spring mechanism. SUMMARY OF THE INVENTION The problem of the invention is to provide easy-to-produce, screwless eyeglasses with a hinge for bending of the eyeglass temples. The problem is solved by an eyeglass frame for which, in the middle of the hinge surface, the hinge has excess material, which, depending on the position of the excess material, leads to a bending of the hinge or holds the hinge in one plane. The hinge is so constructed that it forms a flat surface, which is angled at approximately a right angle from the frontal eyeglass rim. In this position of maximum temple contact angle, the excess material is on the face side of the plane that is formed by the hinge surface. If the eyeglass temple is then folded in, so that the temple contact angle is reduced, the excess material moves in the direction of the plane and thus leads to a locking of the eyeglass temple in a position having a smaller temple contact angle. This abrupt flipping of the eyeglass temple corresponds to the “snap frog effect.” As is the case for the sheet-metal snap frogs commonly used at Fasching [Shrovetide carnival], the pressure may be increased for a long time up to a certain point at which the sheet metal springs into a second position. A similar mechanism is also commonly used for some hair clips. At one end, the eyeglass temple preferably has a surface having excess material on one side of the surface. This excess material forms the hinge of the eyeglasses. The hinge of the eyeglass frame is based on a mechanism similar to that of the “snap frog effect.” Here, a snap spring is integrated (or pressed in) between the frontal eyeglass frame and the eyeglass temple in such a way that the frontal eyeglass frame and the eyeglass temple form nearly a right angle. If the eyeglass temple is then bent in the direction of the frontal eyeglass frame, it flips over at a certain point and remains in this folded-in position. When the eyeglass temple is unfolded, a certain resistance must first be surmounted as well. However, once a certain point has been reached, the eyeglass temple unfolds completely and remains in this unfolded position. In a preferred embodiment of the invention, the eyeglass frame is fabricated in one piece. This has the advantage that the entire eyeglass frame can be produced from a sheet metal or a carbon plate, which can be fabricated by punching, etching, eroding, or stamping of the hinge. In another preferred embodiment of the invention, the eyeglass temple can be removed. This has the advantage that the eyeglasses can be disassembled very flatly for transport. Also possible in this way is the exchange of various frontal eyeglass rims or various eyeglass temples. Thus, it is possible to respond quickly to changes in fashion or corrective lenses may be exchanged for tinted lenses. In particular for corrective lenses, it is important here that the frontal eyeglass rim can be opened in such a way that the eyeglass lenses can be easily exchanged. However, it is also possible to produce the eyeglass rim in a closed variant. In this case, the lenses are pressed into the eyeglass rim. The eyeglass temple consists preferably of a flat strip, which, at one end, separates into two strips that are angled apart from each other, the two angled strips being rejoined at their ends. When the two angled strips are rejoined, the inner side in each case is longer than the outer side and thus excess material is created, which, on being deformed by pressure, leads to the “snap frog effect.” Preferably, the strips that are angled from each other have, on their inner sides, mechanisms by means of which they can be joined to each other. Here, it is possible to use the most diverse mechanisms in order to join the two ends of the angled strips back together. Possible are hooks that enable the two ends to hook into each other. However, it is also possible to screw them together, to rivet them together, to weld them together, to glue them together, or to join them together with a snap fastener. Preferably, the mechanism prevents a displacement of the ends of the angled strips in two spatial directions. To this end, the angled strips have mechanisms that mutually engage and can be opened in only one spatial direction. A displacement in this spatial direction can then be prevented, as described above, by a connecting clip. Preferably, the mechanism is a dovetail-like linkage. This has the advantage that the linkage can be kept very flat. A connecting clip can also be slipped over the two ends to secure the linkage and, in addition, makes possible the linking to the frontal eyeglass rim. In order to enable the eyeglass frame to be folded over at a specific point, the hinge of the eyeglass frame must be made of a material that is inherently stable, but has a certain flexibility and resists certain stresses in the material. Therefore, the eyeglass frame is preferably made of metal, paper, cardboard, carbon fiber, and/or plastic. Furthermore, the problem of the invention is solved by a process for producing an eyeglass frame, in which, in a first step, the eyeglass frame is punched out, laser-cut, eroded out, or etched out of a flat material, and, in a second step, is deformed through the application of point pressure in such a way that a hinge is formed. Fabricated in this way from plates are blanks, which, then, are deformed under pressure to afford the desired eyeglass frame. In this way, it is possible to cut out the most diverse forms of eyeglass frames. In a preferred embodiment of the invention, metal or plastic is selected as the flat material. However, it is also possible to use other materials, such as, for example, paper, cardboard, or carbon fiber. In principle, any material that has the necessary flexibility for deformation of the hinge may be used. The use of metal or plastics has the advantage that these materials can be deformed under pressure. The hinge of the eyeglass frame is formed (surface-embedded) through point pressure. To this end, point pressure is applied to the material at a defined site of the eyeglass temple. At this site, the material is flattened and thus displaces the adjoining material, as a result of which the parallel-lying sheet-metal strips on the upper and lower parts of the temple are spread apart. This occurs at two opposite-lying sites, as a result of which a bulging protuberance (excess material) is formed in the middle of the strips. The inner side of the hinge is thereby pressed more strongly out of the plane of the hinge than the outer side, so that excess material forms in the middle of the hinge surface. A movement of the excess material through the plane of the hinge leads, then, to the transfer of the excess material from one plane of the hinge to the other and accordingly to a change in the angle between the eyeglass temple and the eyeglass rim. Preferably used is a flat material with a thickness of 0.1 to 5 mm and, especially preferably, of 0.4 to 0.8 mm. In this way, it is possible to produce a stable eyeglass frame, which nonetheless makes possible deformations at the hinge. However, it is also possible to make the flat material thicker in the region of the eyeglass rim in order to achieve a higher strength and to make the material thinner in the region from which the hinge is formed in order to achieve a greater flexibility. In another preferred embodiment of the invention, the surface of the eyeglass frame is coated, lacquered, etched, and/or engraved in a further operating step. In this way, it is possible, for example, by means of an electroplating or a lacquering, to protect the eyeglass frame from corrosion or to modify it optically. In a further operating step, preferably plastic, silicone, horn, or rubber pads are placed on the eyeglass bridge and/or at the ends of the eyeglass temples. This enables the eyeglasses, when they are worn, to be supported without any friction or pressure and thus increases the wearing comfort. Furthermore, the problem of the present invention is solved by a use of snap springs with “snap frog effect” as a hinge of an eyeglass frame. BRIEF DESCRIPTION OF THE DRAWINGS The invention will be described below in more detail on the basis of drawings. Shown individually are: FIG. 1 a cutout of the eyeglass frame with unfolded eyeglass temple; FIG. 2 another cutout of the eyeglass frame with unfolded eyeglass temple; FIG. 3 a cutout of the eyeglass frame with folded-in eyeglass temple; FIG. 4 a cutout of the eyeglass frame with folded-in eyeglass temple; FIG. 5 a an eyeglass temple; FIG. 5 b the linkage site of the two ends of the eyeglass temple; FIG. 6 a cutout of an eyeglass frame, which consists of one part; FIG. 7 a cutout of an eyeglass frame with angled strips; FIG. 8 a cutout of an eyeglass frame in which the ends of the angled strips are pressed together; FIG. 9 a cutout of an eyeglass frame made of several parts and with open eyeglass temple; FIG. 10 a cutout of an eyeglass frame having a hinge made of one surface; and FIGS. 11 a to 11 n various eyeglass temples having a hinge and a dovetail linkage. DETAILED DESCRIPTION OF THE INVENTION FIG. 1 and FIG. 2 show a cutout of the eyeglass frame 1 . The eyeglass frame 1 consists of the frontal eyeglass rim 2 , the eyeglass temple 3 , and the hinge 4 . The hinge 4 consists of two strips 5 , by means of which the eyeglass temples 3 are linked to the frontal eyeglass rim 2 . The strips 5 are longer on their inner side 6 than on their outer side 7 , so that they bend out of the plane formed by the eyeglass temple 3 (excess material). The excess material is produced here by point pressure on the deformation point 11 . If the eyeglass temples 3 are pressed in the direction of the frontal eyeglass rim 2 , then the excess material on the longer inner side 6 is pressed to the other side of the eyeglass temple 3 . This is depicted in FIGS. 3 and 4 . FIGS. 3 and 4 show the eyeglass temple 1 in a folded-in position. FIG. 5 a shows an eyeglass temple 3 and the hinge 4 . The hinge 4 consists of two strips 5 , which extend at an angle from the eyeglass temple 3 . Owing to the bending of the strips 5 , their inner side 6 is longer than their outer side 7 . If the two strips 5 are fastened together at their ends 8 , as depicted in FIG. 5 b , there is formed a tension in the strips 5 . As a result of this tension, the inner sides 6 of the strips 5 are pressed out of the plane formed by the eyeglass temple 3 . The excess material, which is formed by the inner sides 6 of the strips 5 , is accordingly pressed out of the plane formed by the eyeglass temple 3 . If the eyeglass temple 3 is bent as depicted in FIGS. 1 and 2 , the excess material is located on the one side of the eyeglass temple 3 and if the eyeglass temples 3 are folded together, as depicted in FIGS. 3 and 4 , then the excess material moves to other side of the eyeglass temple 3 . FIG. 6 shows another embodiment of the present invention, in which the eyeglass frame 1 is fabricated from one piece. Here, the hinge 4 is produced by pressing or stamping, by pressing the inner side 6 out of the plane. FIG. 7 shows a cutout of the eyeglass frame 1 according to the present invention in an exploded drawing. In this embodiment, the frontal eyeglass rim 2 is linked to the eyeglass temple 3 by a connecting clip 10 . One end of the eyeglass temple 3 is a hinge 4 , which is formed by two oppositely angled strips 5 , whose inner side 6 is longer than their outer side 7 . The inner side 6 and the outer side 7 are pressed together at their ends 8 by a connecting clip 10 . The connecting clip 10 is designed in such a way that it enables a secure linking between the ends 8 and the frontal eyeglass rim 2 . FIG. 8 shows the same embodiment as FIG. 7 , but, here, the ends 8 of the angled strips 5 are depicted in a pressed-together position. Owing to the longer inner side 6 of the angled strips 5 , excess material, which is pressed out, is thus formed. FIG. 9 shows the embodiment depicted in FIGS. 7 and 8 in a mounted form. Here, the hinge 4 is arched in one direction owing to the excess material. FIG. 10 shows another embodiment of the present invention, in which the hinge 4 does not have a hole, but rather consists of a surface in which excess material has been shaped. FIGS. 11 a to 11 n show a selection of various possible embodiments of the eyeglass temple 3 . The eyeglass temples 3 each have differently shaped, oppositely angled strips 5 , which form the hinge 4 . In addition, the angled strips 5 have, on their inner side 6 , a mechanism 9 by means of which they can be joined together. In FIG. 11 , the ends 8 of the angled strips 5 take the form of a dovetail linkage. However, other mechanisms 9 for linking the two angled strips 5 are also possible. In FIG. 11 m , the inner side 6 has a looped shape, which means a longer length of the inner side 6 in comparison to the outer side 7 . LIST OF REFERENCE NUMERALS 1 eyeglass frame 2 eyeglass rim 3 eyeglass temple 4 hinge 5 angled strip 6 inner side 7 outer side 8 end 9 mechanism 10 connecting clip 11 deformation point
An eyeglass frame with a hinge for angling the eyeglass temples, for which, in the middle of the hinge surface, the hinge has excess material, which, depending on the position of the excess material, leads to a bending of the hinge or holds the hinge in one plane.
8
RELATED APPLICATION [0001] This application is a continuation-in-part of U.S. patent application Ser. No. 09/927544 titled Self-stiffened welded wire lath assembly by Abe Sacks et al., filed on Aug. 13, 2001. FIELD OF THE INVENTION [0002] This invention relates to building technology, and in particular to wire lath which may be used to reinforce coatings, such as stucco, applied to soffits and other building surfaces. BACKGROUND OF THE INVENTION [0003] Some building construction techniques involve the application of a coating, such as stucco, to a surface. The coating may be desired, for example, to improve appearance, enhance fire resistance or to comply with building or fire codes. In the following disclosure the term “stucco” is used generally to apply to cementitious plasters or gypsum plasters, including stuccos as defined in applicable building codes. [0004] When applying a coating of stucco (or other similar material) it is generally desirable to provide a lath on the surface. The lath provides reinforcing for the stucco and holds the stucco in place. Difficulties can be encountered in applying stucco to overhanging surfaces such as soffits (i.e. the area under building eaves) and the undersides of exposed roof areas, such as porticos. In such areas gravity tends to cause the stucco to sag after it has been applied. [0005] The framing for soffits is typically open where the framing members typically extend transversely across the soffit opening at regular spacings (for example, 16 inches or 24 inches center-to-center). A lath is applied across the opening and attached to the framing members. Stucco is then applied to the lath. The lath supports the stucco and, after the stucco dries, reinforces the stucco. Stucco may be applied in various ways including by hand trowel, or by spraying onto the lath. In either case significant pressures can be imposed on the lath. [0006] The lath must meet several requirements. First, it must be rigid enough to withstand the stresses of the stucco being applied. If the lath is deflected significantly during installation, then stucco in areas adjacent to the deflected area will be disturbed and will likely fall out. Second, the lath must provide adequate reinforcement so that the stucco coating on the soffit will be able to withstand maximum expected wind pressures. The lath should have features which provide good keying and embedment of the stucco over the entire area of the lath. Third, the lath should be designed in such a way as to assist in making the layer of stucco even in thickness. A stucco layer which is uneven in thickness can be prone to cracking. [0007] In many applications it is desirable to have a backing membrane integrated with the lath. A backing membrane prevents stucco from blowing through the lath. Such a membrane is especially desirable in applications where stucco will be pumped or sprayed onto the lath. [0008] Various types of lath have been developed for soffit applications. Specialty expanded metal laths are very widely used. Such laths have been produced by companies such as Alabama Metal Industries Corporation of Birmingham, Ala. under the trade-mark (AMICO.TM). AMICO's expanded metal lath products currently include: ⅛″ Rib Lath (“Flat Rib”). This lath has eighteen ribs approximately ⅛ inch high, spaced {fraction (11/2)} inches on center to provide rigidity for horizontal applications. The lath has a large number of openings or “keys” which provide keying for either troweled or machine-applied stucco. ⅜″ Rib Lath (“High Rib”). This lath has seven longitudinal ribs, each ⅜ inch deep and eight small flat ribs to provide additional rigidity for horizontal applications. A herringbone mesh is located between the ribs to provide keys for good bonding of the stucco to the lath. Cal Spray Rib (“⅛ Inch Flat Rib”). This is a more rigid lath which includes strips of kraft paper attached between the ribs. The added rigidity makes this product well suited for horizontal applications, such as soffits. The paper helps reduce the amount of plaster waste and is not intended to be moisture resistant. A version of Cal Spray Rib having ⅜ inch high ribs is also available. Similar products have been available from California Expanded Metals Company (CEMCO.TM.) and others. [0011] Expanded metal lath products such as those described above can provide good rigidity and stiffness for their rated spans. They also provide good keying and hang on surfaces. However, these products have some disadvantages. First, at the locations of the stiffening ribs, the stucco is much thinner than it is at other locations. Furthermore, the ribs present unbroken surfaces which do not provide opportunity for embedment and keying of stucco. This typically results in a series of cracks forming along each of the ribs. [0012] Another disadvantage of prior expanded metal lath systems is that the keys are typically quite small. Correct installation practice requires the edges of adjacent sheets of lath to be overlapped. However, with small key openings it is difficult to force stucco adequately through the lath in the overlapping portions. This results in a weak zone in which the stucco is likely to crack at each point where sheets of the lath overlap. [0013] A third difficulty with expanded metal lath is that it is difficult to cut, especially if the ribs are high. When cut, expanded metal lath typically exhibits razor sharp edges. This makes current expanded metal lath products tedious and even dangerous to install. [0014] Another group of stucco laths sometimes used for soffits are wire fabric laths. Wire fabric laths typically comprise a rectangular mesh of wires which are welded at their intersections. Wire fabric laths have been available, for example, from the Georgetown Wire Company, Inc, of Fontana, Calif. under the trademark K-LATH.TM. Some examples of such laths include: [0015] Stucco-Rite™ standard. This product is a self-furring sheet of galvanized welded-wire-fabric lath, 16 gauge by 16 gauge, with 2 inch by 2 inch openings. A perforated absorbent carrier kraft paper is incorporated into the mesh, and a Grade D water proofed breather building paper is laminated to the back side of the kraft paper. A heavy duty version features an 11 gauge stiffener wire every 6 inches. [0016] Standard “Gun Lath”. This is a flat sheet welded wire lath, with 2 inch by 2 inch openings, 16 gauge by 16 gauge with a 13 gauge stiffener wire every 4 inches along length of the sheet. An absorbent, slot perforated kraft paper sheet is incorporated between the face and back wires. A heavy duty version features an 11 gauge stiffener wire every 6 inches on center. [0017] “Soffit Lath”. This product is similar to Gun Lath with 16 gauge by 16 gauge wires, but with grid spacing at 1.5 inches by 2 inches. The backing kraft paper has smaller perforated openings which are to provide a more positive keying for the soffit stucco. [0018] Wire fabric laths are more worker friendly than the expanded metal laths in that they are easy to cut, and do not present as many sharp edges when cut. They are also easy to overlap without blinding the openings at the overlap areas. This reduces cracking at overlaps of sheets. Further, there are no stiffening ribs that can cause cracking. Therefore, the overall finished stucco is much better since cracking is minimized. [0019] However, current paper-backed wire laths have two major disadvantages. First, the relatively large wire grid spacing provides little hang on surface area for the wet stucco to hang onto. The perforated backing kraft papers do prevent blow through, but do not have sufficient keying or suction capability to hang onto the wet stucco. [0020] A second disadvantage of current wire lath products is that they are not as rigid as is desirable. These laths tend to deflect as the plasterer applies force. After the force is removed the lath springs back. As this happens fresh plaster in adjoining areas can be dislodged and fall out. This exacerbates the stucco fall out problem. Therefore, plasterers must apply stucco to wire lath very carefully. This is a major disadvantage since it slows down speed of application. Even so, there is typically a high wastage of stucco. [0021] Rigidity can be increased somewhat by using larger diameter wires. However, increase in wire diameter does very little to increase stiffness. If wire diameters are increased enough to provide significant increases in rigidity then the large wires close to the stucco surface tend to cause the stucco to crack along the large wires. [0022] A third disadvantage of some current paper backed wire laths is that the installed stucco plaster has uneven thickness which may result in additional cracking of the stucco. This problem of cracking is exacerbated because the paper, which is tightly attached to the wire lath itself, prevents the stucco from totally surrounding the wires of the lath. As a result the attachment of the stucco to the lath is weaker than would be desired and the stucco can separate from the lath under certain loading conditions. [0023] Jaenson, U.S. Pat. No. 5,540,023 discloses an improved wire lath in which a layer of backing paper is held in place between two courses of horizontal wires. The backing paper is not tightly attached to the lath and allows good keying. However, this wire lath requires that the welds of the lath be made through perforated holes in the backing paper. The backing paper must have a hole at each intersection between two wires. As can be seen in FIG. 1 (prior art), the perforations exist in the backing paper along each longitudinal wire and have significant size. These holes are a disadvantage for producing laths with smaller grid spacings, since the amount of hole area required to accommodate welding becomes very large, leaving less and less paper area. This is a major disadvantage for soffit applications since increasing the hole area results in increased blow-through. Further the kraft paper could easily tear between holes resulting in even more blow-through. [0024] Japanese patent application No. 06047691 published on Sep. 9, 1995 (JP 07233611A2) discloses a multi-layer spray wall core body having a porous sheet between sheets of erected reinforcements. Japanese patent application No. 09347789 published on Jul. 6, 1999 (JP11181989A2) discloses another paper-backed wire lath. [0025] Despite the wide variety of lathing systems that are currently available there remains a need for a lath which avoids the disadvantages discussed above. SUMMARY OF THE INVENTION [0026] This invention provides a wire lath that can be made to be more rigid than current wire lath products, provides good keying, minimizes blow through, provides good embedment, and overcomes a number of disadvantages of expanded metal laths. [0027] Accordingly, in a preferred embodiment of the invention a welded wire lath comprising a plurality of generally parallel transverse wires lies substantially in a first plane. The transverse wires each depart from the first plane in a plurality of spaced-apart bent sections. Each bent section is defined between first and second shoulder portions. While the bent sections can have various shapes, a V-shape is preferred. The bent sections preferably have a height comparable to the width of the V-shape. The lath also comprises a plurality of generally parallel first longitudinal wires. The first longitudinal wires lie substantially in the first plane. They intersect with and are attached, preferably by welding, to the transverse wires. The first longitudinal wires include, for each of the plurality of bent sections, a longitudinal wire attached to each of the transverse wires in at least one of the shoulder portions corresponding to the bent section. [0028] The lath also comprises a plurality of generally parallel second longitudinal wires. The second longitudinal wires lie generally in a second plane parallel to and spaced apart from the first plane. The second longitudinal wires are attached to the transverse wires in approximately the middle of the bent sections. The second longitudinal wires in conjunction with the bent sections and those first longitudinal wires which are attached at the shoulders of the bent sections form trusses which provide rigidity to the wire lath. The trusses may also serve as furring spacers although separate furring spacers may be provided. [0029] In preferred embodiments of the invention the first longitudinal wires include, for each of the plurality of bent sections, a pair of longitudinal wires. One of the pair of longitudinal wires is attached to each of the transverse wires in a first one of the shoulder portions. The other one of the pair of longitudinal wires is attached to each of the transverse wires in the second one of the shoulder portions. [0030] While all longitudinal wires could be attached to all transverse wires to maximize the strength of the lath, several variations in the attachment locations are possible. In the first variation explained above, all longitudinal wires are attached to the transverse wires at each bent sections: two first longitudinal wires at the shoulders and one second longitudinal wires at the middle of the bent section. As a second variation, it is possible to include in the lath assembly, tertiary longitudinal wires located in the first plane and attached to the transverse wires at locations away from the bent sections and between the shoulder regions of adjacently located bent sections. As a third variation, it is possible to include some bent sections in the transverse wires at which, or near which, no longitudinal wires are attached. Yet another variation uses the bent sections as furring spacers. Other alternatives are possible that combine these four variations. [0031] The wire lath may incorporate a barrier layer disposed between the first and second planes. In the preferred embodiment apertures perforate the layer and the bent sections pass through the apertures. The barrier layer may comprise a suitable building paper, such as kraft paper, which may be surface treated to improve the adhesion of stucco. The barrier layer may have additional perforations, in the form of small apertures or slits, which do not coincide with intersections of the longitudinal wires and transverse wires. The additional perforations serve as “keys” for stucco. [0032] A backing layer, such as a layer of asphalt-coated paper may be adhesively affixed to the barrier layer. In this case the second longitudinal wires may extend between the backing layer and the barrier layer. [0033] The wires of a wire lath according to the invention do not need to be round. In some embodiments at least some of the first longitudinal wires are non-round in cross section. The non-round longitudinal wires may advantageously be flattened and oriented to lie generally in the first plane. This provides increased surface area for stucco adhesion, and also can facilitate the application of stucco. [0034] Further features, aspects and advantages of the present invention will be more fully understood when considered with respect to the following detailed description, appended claims, and accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS [0035] In drawings which illustrate non-limiting embodiments of the invention: [0036] FIG. 1 is a schematic perspective view of the Jaenson prior art wire lath and backing paper showing large perforations overlaying all intersections of the wire lath. [0037] FIG. 2 is a perspective view of a welded wire mesh lath in accordance with the invention; [0038] FIG. 3 is a cross-sectional view of the welded wire mesh lath of FIG. 2 ; [0039] FIG. 4 is a cross-sectional view of a welded wire mesh according to an alternative embodiment of the invention; [0040] FIG. 5 is a perspective view of a welded wire mesh lath according to the invention which incorporates a barrier layer; [0041] FIG. 6 is a cross-sectional view of the welded wire mesh lath and barrier layer taken along line 6 - 6 of FIG. 5 ; [0042] FIG. 7 is a cross-sectional view of a welded wire mesh lath according to the invention incorporating a barrier layer and a backing layer adhesively attached thereto; [0043] FIG. 8 is a cross-sectional view of a welded wire mesh lath according to the invention incorporating flattened longitudinal wires, mounted on a horizontal wooden member; and, [0044] FIG. 9 is a cross-sectional view of stucco being applied to a welded wire mesh lath comprising concave longitudinal wires. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [0045] Throughout the following description, specific details are set forth in order to provide a more thorough understanding of the invention. However, the invention may be practiced without some of these particulars. In other instances, well known elements have not been shown or described in detail to avoid unnecessarily obscuring the invention. Accordingly, the specification and drawings are to be regarded in an illustrative, rather than a restrictive, sense. [0046] Referring to FIG. 2 and FIG. 3 , lath 10 according to a currently preferred embodiment of the invention comprises a plurality of first generally parallel longitudinal wires 12 which intersect with a plurality of generally parallel transverse wires 14 . [0047] Wires 12 lie substantially in a first plane PI (best appreciated by reference to FIG. 3 ). Similarly, wires 14 lie substantially in plane PI, save that wires 14 are bent out of plane P 1 at truss locations 15 . [0048] Wires 12 and 14 are welded together at their intersections 11 . Wires 12 and 14 preferably extend generally perpendicularly to one another. The spacing of wires 12 and 14 can be such that square or rectangular grid openings are created. A set of second longitudinal wires 13 is also welded to transverse wires 14 as described below. Wires 12 , 13 and 14 may be made of any suitable materials, such as steel, aluminum, or the like. If made of steel, the wires are preferably galvanized. Wires 12 , 13 and 14 are preferably of the same or similar diameters. Preferably wires 12 , 13 and 14 have cross sectional areas which differ from one another by 25% or less. [0049] Longitudinally extending trusses 15 are formed at spaced locations across lath 10 . Transverse wires 14 have bent sections 20 at the location of each truss 15 . In each bent section 20 the transverse wire 14 bends out of plane P 1 at a first shoulder 16 , extends outwardly at least to plane P 2 and then bends back toward plane P 1 to the point where it rejoins plane PI at a second shoulder 17 . Certain ones of longitudinal wires 12 (indicated by the reference 12 A) are affixed in a shoulder portion at each of shoulders 16 and 17 . Preferably transverse wires 14 bend sharply away from plane PI at each shoulder 16 , 17 with a bend radius of no more than a few diameters of the transverse wires 14 . Preferably the radii of the bends at shoulders 16 and 17 are less than 5 diameters of transverse wire 14 and most preferably less than 2 diameters of transverse wire 14 . In each truss 15 , a longitudinal wire 13 of a plurality of second longitudinal wires is affixed to transverse wires 14 on bent sections 20 . Bent sections 20 are preferably generally V-shaped, as shown in FIG. 2 and FIG. 3 . In preferred embodiments of the invention each transverse wire 14 , including bent sections 20 , lies in a plane which is generally perpendicular to plane P 1 . [0050] Longitudinal wires 12 A are preferably attached to each transverse wire 14 at a point which is as close as practical to a point at which the transverse wire 14 bends out of plane P 1 . Longitudinal wires 12 A should be attached to transverse wires 14 at points which are spaced away from the points at which transverse wires 14 begin to bend out of plane P 1 by no more than about 5-8 times the diameters of transverse wires 14 (and preferably no more than 1-2 times the diameters of transverse wires 14 ). The term “shoulder region” includes those points which are close to shoulders 16 and 17 (i.e. are spaced away from the points at which transverse wires 14 leave plane PI by no more than about 8 times the diameter of transverse wires 14 ). [0051] It can be seen that lath 10 includes longitudinal wires in two groups. A first plurality of generally parallel longitudinal wires 12 (which includes wires 12 A and others of wires 12 which are not affixed at bent sections 20 ) lies generally in a first plane P 1 ( FIG. 3 ). A second plurality of generally parallel longitudinal wires 13 are affixed to transverse wires 14 on bent sections 20 and lie generally in a plane P 2 which is spaced apart from plane P 1 by a distance h. Preferably bent sections 20 of transverse wires 14 bend back toward plane P 1 at a distance of approximately h from plane P 1 (so that second longitudinal wires 13 are located at the “peaks” of bent sections 13 ). However, this is not essential. Bent sections 20 could extend away from plane P 1 to locations past plane P 2 before bending back toward plane P 1 . [0052] The depth h of the truss 15 is preferably equal to the distance w between the two longitudinal wires 12 A on either side of the truss, but may be have a dimension up to twice w in some applications. For example, if a truss 15 has a depth of ⅜ inches then the longitudinal wires 12 A along its shoulders can be spaced apart from ⅜ inch to ¾ inch. In a preferred embodiment of the invention, the wires 12 in plane P 1 are spaced apart by generally equal distances x (see FIG. 3 ) whereas wires 13 are spaced apart from adjacent wires 12 A by a smaller distance y. Preferably y is roughly ½ of x. In another embodiment of the invention x and y are equal. Each truss 15 has at least one longitudinal wire 13 which is displaced out of the plane of the other longitudinal wires 12 . Longitudinal wires 12 A extend along at least one of the shoulders of truss 15 . Preferably each truss 15 includes a pair of longitudinal wires 12 A, one attached to transverse wires 14 in the shoulder region on one side of the truss and the other attached to the transverse wires 14 in the shoulder region on the other side of the truss. [0053] It can be seen that trusses 15 enhance the rigidity of lath 10 in the longitudinal direction. Trusses 15 also make lath 10 self-furring. The number and depth of trusses 15 and the thickness of wires 12 , 13 and 14 may be selected to achieve a desired strength. Preferably: [0054] The spacing x between longitudinal wires 12 is in the range of about ½ inch to 2 inches; [0055] The spacing between adjacent transverse wires 14 is in the range of about 1 inch to 2 inches; [0056] The spacing between trusses 15 is in the range of about 1-{fraction (12)} inches to 6 inches. [heading-0057] For soffit lath applications, preferably: [0058] The spacing x between longitudinal wires 12 is in the range of about 0.5 to 0.6 inches; [0059] The spacing between adjacent transverse wires 14 is about 1-½ inches; and, [0060] The spacing between trusses 15 is about 2 inches. [heading-0061] In an example embodiment, lath 10 has: [0062] nominal spacing of about 0.6 inch between adjacent longitudinal wires 12 ; [0063] nominal spacing of about 1-½ inches between adjacent transverse wires 14 ; [0064] wires 12 , 13 and 14 formed from 17 gauge (0.051″) diameter wire; [0065] trusses 15 having a depth (i.e. the dimension h) of about ⅜ inch; and, [0066] trusses 15 spaced apart from one another by about 2 inches. [0067] Lath 10 may be applied over framing members, which are typically 16 inches or 24 inches on center. Lath 10 can be attached to the framing members at the bottom of trusses 15 . In horizontal applications, building codes generally require that a lath be attached every 3 inches. In vertical applications, the codes generally require attachment to the framing members every 6 inches. In either case, a 2 inch spacing of the corrugating ribs allows appropriate attachment points. Lath 10 is preferably applied in an orientation such that the side of lath 10 bearing second longitudinal wires 13 faces the framing members, each of the second longitudinal wires crosses a plurality of the framing members, and first longitudinal wires 12 are spaced apart from faces of the framing members by the distance h. The portions of lath 10 between the framing members can be substantially unsupported. [0068] A wire lath 10 can be produced in any desired dimensions but is preferably provided in sheets of widths of sizes that can be easily handled. For example, the sheets may have a width in the range of 2 feet to 5 feet. It can be appreciated that sheets of wire lath 10 can be compactly stacked together with the trusses 15 of one sheet being received within the trusses 15 of the next sheet of wire lath 10 in the stack. [0069] A wire lath 10 may be made by making a sheet of welded wire mesh and then bending transverse wires 14 at predetermined locations to form bent sections 20 such that trusses 15 are formed. Where each truss 15 is formed, a longitudinal wire 13 is displaced out of the plane of the longitudinal wires 12 . [0070] It can be appreciated that the provision of trusses 15 can make a lath according to this invention significantly more rigid than prior wire laths. This can be achieved without using jumbo-sized wires which can tend to cause cracking. Further, since trusses 15 are open, stucco is continuous at trusses 15 . This is a major advantage over prior ribbed expanded metal laths in which the ribs cannot be fully embedded in stucco. [0071] The wire lath of FIG. 2 and FIG. 3 may be varied in various ways within the scope of the invention. By way of example only, bent sections 20 may have shapes other than V-shaped. For example, bent sections 20 may be U-shaped, trapezoidal, square, generally rectangular, semi-circular, or the like. It is preferable that the sections 14 A of transverse wires 14 which extend between each wire 13 and an adjacent wire 12 A extend steeply to plane P 1 . Preferably angle υ is 45 degrees or less. Most preferably angle υ is 30 degrees or less. While it is not as structurally sound, a longitudinal wire 12 A could be provided along only one shoulder of each truss 15 instead of along both shoulders, as shown. [0072] More than one longitudinal wire 13 may be provided on each truss 15 . If two closely-spaced longitudinal wires 13 are provided on each truss 15 then lath 10 may be fastened to a building structure with fasteners such as nails or screws inserted between the two longitudinal wires 13 . [0073] In the embodiment of FIG. 3 , longitudinal wires 13 are on the opposite side of transverse wires 14 from the first longitudinal wires 12 . Conversely as shown in FIG. 4 , longitudinal wires 13 could also be located on the same side of transverse wires 14 as first longitudinal wires 12 . Similarly, all of longitudinal wires 12 and 13 could be on the same side of transverse wires 14 as bent sections 20 . [0074] A wire lath according to the invention can include a barrier layer 22 , such as a layer of kraft paper, disposed between planes P 1 and P 2 . FIG. 5 and FIG. 6 show a wire lath 10 A which includes a barrier layer 22 . Apart from the incorporation of layer 22 , lath 10 A is the same as lath 10 . Layer 22 has apertures 24 . Bent sections 20 pass through apertures 24 . Longitudinal wires 13 are on one side of layer 22 and longitudinal wires 12 are on the other side of layer 22 . Barrier layer 22 may comprise a layer of paper. The paper is preferably absorbent and may have a surface treatment such as sanding or microperforation to enhance its adhesion to stucco. [0075] It can be seen that layer 22 does not prevent stucco from fully embedding longitudinal wires 12 or transverse wires 14 due to the furring provided by the bent sections. The furring creates a space between plane P 1 and plane P 2 so that stucco can embed wires 12 by forcing layer 22 against longitudinal wires 13 as the stucco is applied. It can further be seen that layer 22 requires relatively few apertures 24 . Layer 22 provides protection against blow-through of stucco. Apertures 24 may be elongated. If so, then preferably apertures 24 would be oriented to be generally parallel to transverse wires 14 . [0076] Wire lath 10 A may be fabricated by first welding the plurality of first longitudinal wires 12 to transverse wires 14 , applying layer 22 and subsequently welding longitudinal wires 13 to bent sections 20 of transverse wires 14 . Bent sections 20 may be formed while applying layer 22 and welding longitudinal wires 13 to transverse wires 14 . Forming bent sections 20 reduces the width of the sheet of lath 10 A. By orienting the apertures 24 parallel to transverse wires 14 , the wires of lath 10 A can slide sideways without crumpling layer 22 . The amount of width reduction will be zero in the center of lath 10 A and will increase progressively towards the two outer edges. This can be accommodated by making apertures 24 in the form of elongated slots having lengths which are greater for trusses 15 located toward the outer edges of lath 10 A. [0077] If bent sections 20 could be fully formed before applying layer 22 then apertures 24 would not need to be elongated and could be, for example, round. This would serve to limit the overall size of the apertures and provide greater control over the keying of the stucco through the apertures. Accordingly, the preferred method of fabricating the lath according to the invention involves first producing a welded lath mesh that is substantially flat. The resulting lath is then processed through a continuous roll forming machine so as to provide spaced bends in the transverse wires 14 corresponding to shoulder wires 12 A. The bends extend portions of transverse wires 14 out of, and then back into, the principal plane of the lath P 1 . [0078] A sheet of a suitable barrier paper is provided in which a limited number of apertures are pre-cut in the paper to correspond only to the bent areas of transverse wires 14 . The lath and paper are then presented in overlapping relationship to a welding machine such that the pre-cut apertures in the paper overlap the bent sections of transverse wires 14 . Backing wires 13 are then welded to transverse wires 14 through the apertures to retain the paper onto the lath. [0079] It will be appreciated that whereas the first mentioned approach above requires apertures in the form of slots to avoid crumpling of the backing paper during the furring process, the preferred approach avoids the need for elongated apertures. Each approach however, avoids the need for an aperture at each wire intersection, such as is found in the prior art paper web welded lath structure exemplified by Jaenson U.S. Pat. No. 5,540,023. The preferred approach requires apertures only at the intersections of the transverse wires 14 and the backing wires 13 . A reduction in the mesh size of the Jaenson lath results in the apertures of each intersection being closer together and ultimately running into each other. This reduces the effectiveness of the barrier layer in limiting the amount of stucco flow-through. It also weakens the barrier layer and makes it more prone to tearing, particularly when subjected to the pressure of stucco being applied. The preferred embodiment of the present invention avoids such disadvantage by providing fewer apertures. [0080] In addition, the Jaenson design represented an improvement over the previous prior art in that two out of three longitudinal wires were fully exposed to the stucco. However, every third longitudinal strand of Jaenson is on the back side of the backing paper. According to the present invention, all of the longitudinal wires 12 are on the outer (stucco) side of the backing layer. This enhances the ability of the lath to provide to fully embed in the stucco as compared to Jaenson. [0081] Layer 22 may optionally include a series of additional perforations 25 . Perforations 25 provide further keying and assist in holding wet stucco to layer 22 . Perforations 25 may be extremely small, from micrometer to sub-millimeter size, or they could have larger dimensions up to the mesh grid size. When stucco is being applied, some of the stucco can force its way through perforations 25 . The perforations 25 trap some stucco, which will tend to mushroom out on the rear side of layer 22 (i.e. the side of layer 22 toward longitudinal wires 13 ). The blob of stucco on the rear side of layer 22 locks around the edge of perforation 25 thereby promoting adhesion of the wet stucco to lath 10 A. In one embodiment of the invention, perforations 25 comprise slits formed by cutting layer 22 without removing any material. Perforations 25 could be X-shaped, as shown, H-shaped, semi-circular, or some other shape. Perforations 25 could also comprise holes of various shapes in layer 22 . For example, the holes could be round, oval, elongated or other shapes. [0082] As shown in FIG. 7 , a wire lath 10 B according to another embodiment of the invention has a backing layer 30 of building paper or the like may be applied behind longitudinal wires 13 . Layer 30 may be affixed to layer 22 with a suitable adhesive. Layer 30 may comprise, for example, an asphalt-saturated-type building paper or one of the various building wraps. Where a backing layer 30 is provided then perforations 25 in layer 22 are not advantageous. FIG. 8 shows a wire lath 10 C according to another embodiment of the invention. Lath 10 C differs from laths 10 A and 10 B in that longitudinal wires 12 are replaced with shaped wires 12 ′. Shaped wires 12 ′ have shaped cross sections instead of circular cross-sections. Wires 12 ′ may be, for example, flattened, oval, square, half-round, concave or other non-round formed shapes. Lath 10 C has the advantage that the surface areas of wires 12 ′ is increased. This provides enhanced grip when stucco is applied. A further advantage of this embodiment is that the process of shaping longitudinal wires 12 ′ can work-harden wires 12 ′. This can increase their strength. Thus, a lath using shaped wires 12 ′ may use smaller wire sizes to obtain similar strengths. This, in turn, makes such a lath easier to cut to size, lighter and potentially less costly in materials. The lath of FIG. 8 is shown attached to a transversely-extending stud 36 by way of a nail 38 which captures longitudinal wire 13 against stud 36 . [0083] Another advantages of using flattened shaped wires 12 ′ is that appropriately shaped wires can help to direct stucco into lath 10 C as it is troweled into place. FIG. 9 illustrates an embodiment of the invention wherein shaped wires 12 ′ are flattened and have their edges curved slightly downwardly. As stucco 40 is troweled across lath 10 C using trowel 45 , in the direction indicated by arrow 42 shaped wires 12 ′ cut through the flowing stucco and tend to cause part of the stucco to flow upwardly, as indicated by arrows 44 . [0084] In the laths described above, trusses 15 play the dual role of providing rigidity and serving as furring spacers. It would be possible to add other furring spacers to transverse wires 14 at locations away from trusses 15 . The furring spacers may comprise, for example, additional bent sections in transverse wires 14 . Where the lath comprises a backing layer 22 the furring spacers pass through apertures in backing layer 22 in substantially the same manner that bent sections 22 pass through apertures 24 . The separate furring spacers provide points for attachment of a lath according to the invention to a building structure and are located away from trusses 15 . The use of separate furring spacers thus reduces the risk that trusses 15 may be damaged while a lath is being installed. The furring spacers may be formed, for example, by creating bent sections in transverse wires 14 such that selected ones of longitudinal wires 12 is displaced into or behind plane P 2 . The lath may then be installed, by attaching the furring spacers to a stud, for example, by nailing, stapling or screwing. [0085] This invention also includes a building structure comprised of parallel transverse framing members to which the lath constructed as described above, is attached such that the second longitudinal wires of the lath are crossing, and are adjacent to, the parallel transverse framing members, and the first longitudinal wires are spaced apart from the framing members. The framing members could be spaced apart by more than 1 2 inches leaving the wire lath substantially unsupported in its portions between the framing members. Such building structure could be located on an underside of a part of a building. [0086] The building structure could also comprise stucco such that a layer of solidified stucco encases the first longitudinal wires and at least substantially filling a space between the barrier layer and the first longitudinal wires. If perforations are made through the barrier layer, the stucco would flow through these perforation when it is still wet and would therefore extend beyond the barrier layer. [0087] The first longitudinal wires can be flattened and oriented with their wide dimension substantially parallel to the framing members. [0088] As will be apparent to those skilled in the art in the light of the foregoing disclosure, many alterations and modifications are possible in the practice of this invention without departing from the spirit or scope thereof. For example, a lath according to the invention could include additional longitudinal or transverse wires. Accordingly, the scope of the invention is to be construed in accordance with the substance defined by the following claims.
A self-furring wire lath comprises a mesh of transverse and longitudinal wires welded at their intersections. Stiffening trusses are formed by bent sections in the transverse wires and longitudinal wires attached to the shoulders of the bent sections. A barrier layer material is retained in the lath between the apex of the bent sections and the principal plane of the lath mesh. The barrier layer material has apertures that coincide with the intersections only at the bent sections to enable mesh size reduction without compromising the barrier layer but still allow the fabrication of the lath. The lath provides good embedment in the stucco, reduces cracking and wastage of stucco while remaining easy to work with.
4
BACKGROUND OF THE INVENTION [0001] The invention relates to a device for performing measurements and/or taking samples in molten metals with a sublance, which has a sublance body, on whose one end a lance holder is arranged for receiving an immersion probe. [0002] Such devices are sufficiently well known to those skilled in the art. They are used for measurements or taking samples in molten metals. Such sampling is partially automated, wherein a sublance is dipped into a melt container, after which the immersion probe arranged on the sublance is discarded, because it is used up, and a new immersion probe is placed on the sublance. In order to automate this procedure, the sublance must be able to be positioned exactly over a probe storage container. [0003] In practice, however, it has been shown that, due to the loads exerted on a sublance during use, these sublances become slightly deformed, so that the lance holder can no longer be placed exactly over an immersion probe and the probe cannot be received without problems. The immersion probes placed on the sublances do not have the same exact length. In particular, the contact part housed in the carrier tube cannot always be reached at the same depth by the counter contact in the sublance. As a result, splashes of the molten metal frequently settle onto parts of the sublance, which must remain free for forming the contact, so that trouble-free placement of the immersion probes is impossible. This can disrupt the entire steel making process. [0004] Sublances are known, for example, from European published patent application EP 69 433 A1. Here, an attempt is made to counteract the deformation of the sublance during the operation by rotating the sublance. The arrangement and function of sublances is further described in German published patent application DE 43 06 332 A1. Here, the exchanging procedure of the sample probes is also disclosed. Another sublance is known from European Patent EP 143 498 B1. The sublance described here has a seal, for example a rubber ring, at connection points, which prevents liquid metal from being able to penetrate into the mechanism. [0005] The invention is based on the problem of improving the known sublances and especially enhancing the fail-safe means in automatic operation. BRIEF SUMMARY OF THE INVENTION [0006] The problem is solved for the invention characterized above in that on the lance holder a contact piece is arranged for making contact with signal lines of the immersion probe, furthermore in that the sublance body is movably connected to the lance holder or to a part thereof and/or in that the lance holder has several parts relatively movable to each other, whereby the contact piece is arranged to be movable relative to the sublance. The sublance is pushed tight onto the upper part of the lance holder and is preferably held so that it cannot move. The lower part of the lance holder is movable with the contact piece, so that the probe can be brought into contact with the contact piece. The lance holding can thereby adapt to the already set sensor, so that a sufficient contact is possible even for slightly deformed components or even when molten metal adheres to the sublance. [0007] Different insertion depths of the sublance into the carrier tube of the immersion probe are likewise compensated in this manner. Preferably, the sublance body with the lance holder and/or the parts of the lance holder are arranged to be movable in the axial direction and/or in the radial direction. Furthermore, it is advantageous when the axial movement and the radial movement are realized by pairs of connection parts that are different from each other, in order to obtain the highest possible flexibility and adaptability. Especially for adhesion of molten metal on the sublance or for differently arranged contact parts of the immersion probe, an axial movement is important, in order to guarantee the correct contact with the immersion probe. In particular, it is advantageous when the movement is realized by elastic parts arranged between rigid parts, wherein the elastic parts can be formed as a spring, for example as a coil spring, or as an elastic ring. [0008] Furthermore, it is useful if a part of the lance holder has a receiving hole, in which a peg of a second part of the lance holder can move in the axial direction, wherein a coil spring is arranged between the first and the second parts of the lance holder. For this purpose, it is advantageous if the coil spring is arranged between a stopping surface arranged at the front end or on the peripheral surface of the peg and a second stopping surface is arranged at or in the hole. The components guaranteeing the movement are thereby protected themselves. [0009] It is useful if a part of the lance holder has a receiving hole, in which a peg of a second part of the lance holder is movable in the radial direction, wherein at least one elastic ring is arranged between the first and the second parts of the lance holder. The elastic ring can be arranged advantageously in the radial direction between the two parts of the lance holder. BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS [0010] The foregoing summary, as well as the following detailed description of the invention, will be better understood when read in conjunction with the appended drawings. For the purpose of illustrating the invention, there are shown in the drawings embodiments which are presently preferred. It should be understood, however, that the invention is not limited to the precise arrangements and instrumentalities shown. In the drawings: [0011] FIG. 1 is a schematic cross-sectional view of a converter furnace with a sublance; [0012] FIG. 2 is a partially broken away schematic side longitudinal view of a sublance with lance holder and immersion probe according to one embodiment of the invention; and [0013] FIG. 3 is a truncated schematic side longitudinal view of one embodiment of a lance holder in detail. DETAILED DESCRIPTION OF THE INVENTION [0014] In the converter furnace shown in FIG. 1 a blowing lance 1 is arranged, which blows oxygen into the molten slag 2 or molten steel 3 . Next to this lance a sublance 4 with an immersion probe 5 is arranged. The sublance 4 travels from above into the converter furnace until the immersion probe 5 is immersed in the molten steel 3 . After the measurement, the sublance is pulled up; the immersion probe 5 is destroyed. [0015] If the probe is designed as a measurement probe, then the measurement is performed during the immersion in the molten steel 3 . A sample chamber arranged in the immersion probe 5 was filled while in the molten steel 3 . The sample chamber is removed from the discarded immersion probe 5 , and the sample can be analyzed. For the next measurement, another immersion probe 5 is taken from a storage container, usually mechanically mounted on the sublance 4 , and inserted into the converter furnace for the measurement. [0016] FIG. 2 shows the immersion probe 5 arranged at the lower end of the sublance 4 . The immersion probe 5 has an immersion end, which is protected from the slag layer 2 lying on the molten steel 3 by a cap 6 , which exposes the sensor or the sample chamber only after being immersed in the molten steel 3 . The immersion probe 5 is fixed to the sublance 4 by means of the lance holder. The signal lines of the immersion probe 5 are contacted by a contact piece 7 arranged on the lance holder, so that the measurement signals can be led back through the sublance 4 to an analysis unit. [0017] In FIG. 3 the lance holder is shown in detail. The lance holder is a reusable part of the sublance 4 . It is used for holding the immersion probe 5 and as a contact connection with the immersion probe 5 . The lance holder is connected to the water-cooled part of the sublance 4 . The water cooling is not explained in more detail in the Figures. It is sufficiently well known from the prior art (for example, EP 69 433). [0018] The lance holder is arranged with its upper part 8 rigidly in the sublance 4 and with its lower part, beginning approximately at the separating line 9 , in the immersion probe 5 . In this way, the contact piece 7 guarantees the electrical contact with the signal lines of the immersion probe 5 . The conductance of the electrical signals and their transmission to a measurement or analysis station take place through the lance cable 10 , which is arranged at the upper end of the lance holder and which passes through the sublance 4 . [0019] A rubber ring 11 is arranged in the upper region of the lance holder. The rubber ring 11 enables the lower part of the lance holder to move in both the radial direction and the axial direction relative to the upper part 8 . The rubber ring 11 is held against a stop 17 by a screw 16 . The screw 16 has a through hole 18 in the axial direction, which expands conically in the direction towards the contact piece 7 . The upper part 8 of the sublance 4 is thereby movable relative to the lower part in the radial direction and also slightly in the axial direction. Instead of a rubber ring 11 , a metal spring, for example a coil spring, can also be used. [0020] The lower part of the lance holder with the contact piece 7 has a sealing sleeve 12 , into which a guide tube 13 projects. A coil spring 14 is arranged in the longitudinal direction between the guide tube 13 and an inner stopping surface of the sealing sleeve 12 . Movement of the contact piece 7 with the sealing sleeve 12 along the guide tube 13 is thereby guaranteed. This movement always ensures a secure contact between the signal lines of the immersion sensor 5 and the contact piece 7 , even with different lengths of the various immersion sensors 5 , which are mounted on the lance holder. [0021] A secure contact is then guaranteed even if foreign matter, such as molten metal or slag, has become fixed on the lance holder. This can occur in the upper part of the lance holder, where the sublance 4 and the immersion probe 5 contact each other. Even in such a case of contamination, a reliable contact between the contact piece 7 and the signal lines of the immersion probe 5 is guaranteed by the spring 14 . The spring 14 preferably has a spring tension that is greater than the attachment force of the contact piece 7 on the so-called connector within the immersion probe 5 , with whose help the signal lines make contact with the contact piece. [0022] Within the guide tube 13 coupling elements 15 can be provided, by which the lance cable 10 is connected to the contact piece 7 . In the manner shown, the contact piece 7 is arranged to be movable both in the longitudinal and the radial directions relative to the sublance 4 , and therefore can then be connected to the signal lines of the immersion probe, even if the lower end of the sublance 4 carrying the lance holder is slightly bent. A secure, mechanical holding of the immersion probe 5 is possible as well in practically every conceivable case. [0023] It will be appreciated by those skilled in the art that changes could be made to the embodiments described above without departing from the broad inventive concept thereof. It is understood, therefore, that this invention is not limited to the particular embodiments disclosed, but it is intended to cover modifications within the spirit and scope of the present invention as defined by the appended claims.
A device is provided for performing measurements and/or taking samples in molten metals with a sublance, which has a sublance body, on whose one end a lance holder is arranged for receiving an immersion probe. The sublance body is movably connected to the lance holder and/or the lance holder has several parts relatively movable to each other.
2
CROSS REFERENCE TO RELATED APPLICATIONS This application is the US National Stage of International Application No. PCT/EP2006/060835, filed Mar. 17, 2006 and claims the benefit thereof. The International Application claims the benefits of European Patent Office application No. 05012633.3 filed Jun. 13, 2005, both of the applications are incorporated by reference herein in their entirety. FIELD OF INVENTION The invention relates to a component having a thermal barrier coating and a metallic erosion-resistant, to a production process and to a method for operating a steam turbine. BACKGROUND OF INVENTION Thermal barrier coatings which are applied to components are known from the field of gas turbines, as described for example in EP 1 029 115. Thermal barrier coatings enable components to be used at higher temperatures than those permitted by the base material, or allow the service life to be extended. Known base materials (substrates) for gas turbines allow temperatures of use of at most 1000° C. to 1100° C., whereas a coating with a thermal barrier coating allows temperatures of use of up to 1350° C. The temperatures of use of components in a steam turbine are much lower, and consequently these demands are not imposed in this application. It is known from EP 1 029 104 A to apply a ceramic erosion-resistant layer to a ceramic thermal barrier coating of a gas turbine blade or vane. It is known from DE 195 35 227 A1 to provide a thermal barrier coating in a steam turbine in order to allow the use of materials which have worse mechanical properties but are less expensive for the substrate to which the thermal barrier coating is applied. U.S. Pat. No. 5,350,599 discloses an erosion-resistant ceramic thermal barrier coating. US 2003/0152814 A1 discloses a thermal barrier coating system comprising a substrate made from a superalloy, an aluminum oxide layer on the substrate and a ceramic as outer ceramic thermal barrier coating. EP 0 783 043 A1 discloses an erosion-resistant layer consisting of aluminum oxide or silicon carbide on a ceramic thermal barrier coating. U.S. Pat. No. 5,683,226 discloses a component of a steam turbine with improved resistance to erosion. U.S. Pat. No. 4,405,284 discloses an outer metallic layer which is considerably more porous than the underlying ceramic thermal barrier coating. In its discussion of the prior art, EP 0 783 043 A1 discloses the formation of an erosion-resistant coating in two layers, specifically comprising an inner metallic layer and an outer ceramic layer. U.S. Pat. No. 5,740,515 discloses a ceramic thermal barrier coating to which an outer, hard ceramic silicide coating has been applied. WO 00/70190 discloses a component wherein an outer metallic layer is applied, this layer containing aluminum in order to increase the oxidation resistance of the component. The thermal barrier coating is strongly eroded on account of impurities in a medium and/or high flow velocities of the flowing medium which flows past components having a thermal barrier coating. SUMMARY OF INVENTION Therefore, it is an object of the invention to provide a component, a process for producing the component and a suitable use of the layer system which overcomes this problem. The object is achieved by a component and a method as claimed in independent claims. The subclaims list further advantageous configurations of the components according to the invention. The measures listed in the subclaims can be combined with one another in advantageous ways. In particular in the case of components of turbines which are exposed to hot fluids for driving purposes, scaling often leads to mechanical impact of detached scale particles on a brittle ceramic layer, which could lead to material breaking off, i.e. to erosion. Although the ceramic layer is designed to withstand thermal shocks, it is susceptible to locally very limited occurrences of mechanical stresses, since a thermal shock has a more widespread effect on the overall layer. Therefore, a metallic erosion-resistant layer is particularly advantageous, since it is elastically and plastically deformable on account of its ductility. The thermal barrier coating does not necessarily serve only to shift the range of use temperatures upward, but rather is also advantageously used to reduce and/or make more even the thermal expansion caused by the temperature differences which are produced and/or present at the component. It is in this way possible to avoid or at least reduce thermomechanical stresses. BRIEF DESCRIPTION OF THE DRAWINGS Exemplary embodiments are illustrated in the figures, in which: FIG. 1 shows possible arrangements of a thermal barrier coating according to the invention on a component, FIGS. 2 , 3 show a porosity gradient within the thermal barrier coating of a component formed in accordance with the invention, FIGS. 4 , 5 show a steam turbine, FIGS. 6 , 7 , 8 show further exemplary embodiments of a component formed in accordance with the invention. DETAILED DESCRIPTION OF INVENTION FIG. 1 shows a first exemplary embodiment of a layer system 1 formed in accordance with the invention for a component. In the text which follows, the terms layer system 1 and component are used synonymously when the component includes the layer system 1 . The component 1 is preferably a component of a gas or steam turbine 300 , 303 ( FIG. 4 ), in particular a steam inflow region 333 of a steam turbine 300 , a turbine blade or vane 342 , 354 , 357 ( FIG. 4 ) or a housing part 334 , 335 , 366 ( FIGS. 4 , 5 ) and comprises a substrate 4 (supporting structure) and a thermal barrier coating 7 applied to the substrate, as well as an outer metallic erosion-resistant layer 13 on the thermal barrier coating 7 . At least one metallic bonding layer 10 is arranged between the substrate 4 and the thermal barrier coating 7 . The bonding layer 10 is used to protect the substrate 4 from corrosion and/or oxidation and/or to improve the bonding of the thermal barrier coating 7 to the substrate 4 . This applies in particular if the thermal barrier coating 7 consists of ceramic and the substrate 4 consists of a metal. The erosion-resistant layer 13 consists of a metal or a metal alloy and protects the component from erosion and/or wear, as is the case in particular for steam turbines 300 , 303 ( FIG. 4 ), which are subject to scaling, and in which mean flow velocities of approximately 50 m/s (i.e. 20 m/s-100 m/s) and pressures from 350 to 400 bar occur. The outer metallic erosion-resistant layer 13 (=outermost layer) is preferably formed to be denser than the thermal barrier coating 7 . In this context, the term denser means that the porosity of the outer metallic erosion-resistant layer 13 is in absolute terms at least 1%, in particular at least 3%, higher than that of the thermal barrier coating 7 (for example ρ(7)=90%, i.e. ρ(13)≧91%, in particular≧93%) The density of the thermal barrier coating 7 is preferably 80%-95% of the theoretical density, while the density ρ of the metallic erosion-resistant layer 13 is preferably at least 96%, preferably 98% of the theoretical density. The term metal is to be understood as encompassing not just elemental metals but also alloys, solid solutions or intermetallic compounds. According to the invention, the bonding layer 10 and the erosion-resistant layer 13 have an identical or similar composition. An identical composition means that the two layers 10 , 13 contain the same elements in the same amounts, preferably comprising an MCrAlX alloy or SC 21, SC 23 or SC 24. The preferred use of an identical composition for the erosion-resistant layer 13 simplifies procurement and also significantly improves the corrosion properties of the substrate 4 . A similar composition means that the two layers 10 , 13 contain the same elements but in slightly differing proportions, i.e. differences of at most 3% per element (for example layer 10 may have a chromium content of 30%, in which case the layer 13 may have a chromium content from at least 27% (30-3) to at most 33% (30+3)) and that up to 1 wt % of at least one further element may be present. SC 21 consists of (in wt %) 29%-31% nickel, 27%-29% chromium, 7%-8% aluminum, 0.5%-0.7% yttrium, 0.3%-0.7% silicon, remainder cobalt. SC 23 consists of (in wt %) 11%-13% cobalt, 20%-22% chromium, 10.5%-11.5% aluminum, 0.3%-0.5% yttrium, 1.5%-2.5% rhenium, remainder nickel. SC 24 consists of (in wt %) 24%-26% cobalt, 16%-18% chromium, 9.5%-11% aluminum, 0.3%-0.5% yttrium, 1.0%-1.8% rhenium, remainder nickel. The wear-/erosion-resistant layer 13 preferably consists of alloys based on iron, chromium, nickel and/or cobalt or for example NiCr 80/20 or NiCrSiB with admixtures of boron (B) and silicon (Si) or NiAl (for example: Ni: 95 wt %, Al 5 wt %). In particular, a metallic erosion-resistant layer 13 can be used for steam turbines 300 , 303 , since the use temperatures in steam turbines at the steam inflow region 333 are at most 450° C., 550° C., 650° C., 750° C. or 850° C. It is preferable to use a temperature of 750° C. For these temperature ranges, there are sufficient metallic layers which have a sufficiently high resistance to erosion over the service life of the component 1 combined, at the same time, with a good resistance to oxidation. Metallic erosion-resistant layers 13 in gas turbines on a ceramic thermal barrier coating 7 within the first stage of the turbine or within the combustion chamber are not appropriate, since metallic erosion-resistant layers 13 as an outer layer are unable to withstand the use temperatures of up to 1350° C. The bonding layer 10 for protecting a substrate 4 from corrosion and oxidation at a high temperature includes, for example, substantially the following elements (details of the contents in percent by weight): 11.5 to 20.0 wt % chromium, 0.3 to 1.5 wt % silicon, 0.0 to 1.0 wt % aluminum, 0.0 to 0.7 wt % yttrium and/or at least one equivalent metal selected from the group consisting of scandium and the rare earth elements, remainder iron, cobalt and/or nickel as well as manufacturing-related impurities. In particular the metallic bonding layer 10 consists of 12.5 to 14.0 wt % chromium, 0.5 to 1.0 wt % silicon, 0.1 to 0.5 wt % aluminum, 0.0 to 0.7 wt % yttrium and/or at least one equivalent metal selected from the group consisting of scandium and the rare earth elements, remainder iron and/or cobalt and/or nickel as well as manufacturing-related impurities. It is preferable if the remainder of these two bonding layers 10 is iron alone. The composition of the bonding layer 10 based on iron has particularly good properties, with the result that the bonding layer 10 is eminently suitable for application to ferritic substrates 4 . The coefficients of thermal expansion of substrate 4 and bonding layer 10 can be very well matched to one another (up to 10% difference) or may even be identical, so that no thermally induced stresses are built up between substrate 4 and bonding layer 10 (thermal mismatch), which could cause the bonding layer 10 to flake off. This is particularly important since in the case of ferritic materials, it is often the case that there is no heat treatment carried out for diffusion bonding, but rather the bonding layer 10 (ferritic) is bonded to the substrate 4 mostly or solely through adhesion. The composition of the outer erosion-resistant layer 13 is selected in such a way as to have a high ductility. In this context, the term high ductility means an elongation at break of 5% (an elongation of 5% leads to the formation of cracks) at the temperature of use. An erosion-resistant layer 13 having a ductility of this level may be present directly on a substrate 4 or on a ceramic thermal barrier coating 7 , in which case the composition of the bonding layer 10 is then no longer of importance. The thermal barrier coating 7 is in particular a ceramic layer which for example consists at least in part of zirconium oxide (partially stabilized or fully stabilized by yttrium oxide and/or magnesium oxide) and/or at least in part of titanium oxide and is, for example, thicker than 0.1 mm. By way of example, it is possible to use thermal barrier coatings 7 consisting 100% of either zirconium oxide or titanium oxide. The ceramic layer 7 can be applied by means of known coating processes, such as atmospheric plasma spraying (APS), vacuum plasma spraying (VPS), low-pressure plasma spraying (LPPS) and by chemical or physical coating methods (CVD, PVD). The substrate 4 is preferably a steel or other iron-base alloy (for example 1% CrMoV or 10-12% chromium steels) or a nickel- or cobalt-base superalloy. In particular, the substrate 4 is a ferritic base alloy, a steel or nickel- or cobalt-base superalloy, in particular a 1% CrMoV steel or a 10 to 12% chromium steel. Further advantageous ferritic substrates 4 of the layer system 1 consist of a 1% to 2% Cr steel for shafts ( 309 , FIG. 4 ): such as for example 30CrMoNiV5-11 or 23CrMoNiWV8-8, 1% to 2% Cr steel for housings (for example 335 , FIG. 4 ): G17CrMoV5-10 or G17CrMo9-10, 10% Cr steel for shafts ( 309 , FIG. 4 ): X12CrMoWVNbN10-1-1, 10% Cr steel for housings (for example 335 , FIG. 4 ): GX12CrMoWVNbN10-1-1 or GX12CrMoVNbN9-1. To optimize the efficiency of the thermal barrier coating 7 , the thermal barrier coating 7 at least in part has a certain open and/or closed porosity. It is preferable for the erosion-resistant layer 13 to have a higher density than the thermal barrier coating 7 , so that it ( 13 ) has a higher resistance to erosion. The metallic erosion-resistant layer 13 has a very low porosity and in particular has a relatively low roughness, so as to provide a good resistance to removal of material through erosion. The lower porosity and roughness of the metallic erosion-resistant layer can be achieved using varying techniques: 1. Use of a spray powder with the smallest possible grain size during the thermal spraying of the erosion-resistant layer 13 , 2. densification of the outer metallic erosion-resistant layer 13 after spraying by a blasting operation, for example by blasting with glass beads or steel grit or other mechanical densification or smoothing processes (rolling, vibratory finishing), 3. closing of the open pores by penetration agents, 4. heat treatment of the entire system, 5. fusion or remelting of the top layer or of the entire metallic erosion-resistant layer. By contrast, the bonding layer 10 , which is located between the substrate and the thermal barrier coating, is implemented in such a way as to have a sufficiently high roughness with undercuts, in order to effect secure bonding of the thermal barrier coating to the bonding layer 10 . In this case, the powder used during the spraying operation can be significantly coarser than that used for the erosion-resistant layer 13 . FIG. 2 shows a porous thermal barrier coating 7 with a porosity gradient. Pores 16 are present in the thermal barrier coating 7 . The density ρ of the thermal barrier coating 7 increases in the direction of an outer surface. Therefore, the layer 7 can be used as a thermal barrier in the region where the porosity is greater and if appropriate can also be used to protect against erosion in the region where the porosity is lower. Therefore, there is preferably a greater porosity toward the bonding layer 10 than in the region of an outer surface or the contact surface with the erosion-resistant layer 13 . In FIG. 3 , the gradient of the density ρ of the thermal barrier coating 7 is opposite to that shown in FIG. 2 . The erosion-resistant layer 13 is preferably only applied locally, and is preferably applied to the component 1 where the angle at which eroding particles impinge on the component 1 is between 60° and 120°, preferably between 70° and 110° or preferably around 80° and 100°. It is particularly useful to coat the locations where the eroding particles impinge at an angle of 90°+/−2°. A metallic erosion-resistant layer 13 offers the best protection against erosion with this virtually perpendicular impingement of eroding particles on the surface of a component 1 . The perpendicular to the surface of the component 1 constitutes the 90° axis. FIG. 4 illustrates, by way of example, a steam turbine 300 , 303 with a turbine shaft 309 extending along an axis of rotation 306 . The steam turbine has a high-pressure part-turbine 300 and an intermediate-pressure part-turbine 303 , each having an inner housing 312 and an outer housing 315 surrounding the inner housing. The high-pressure part-turbine 300 is, for example, of pot-like design. The intermediate-pressure part-turbine 303 is of two-flow design. It is also possible for the intermediate-pressure part-turbine 303 to be of single-flow design. Along the axis of rotation 306 , a bearing 318 is arranged between the high-pressure part-turbine 300 and the intermediate-pressure part-turbine 303 , the turbine shaft 309 having a bearing region 321 in the bearing 318 . The turbine shaft 309 is mounted on a further bearing 324 next to the high-pressure part-turbine 300 . In the region of this bearing 324 , the high-pressure part-turbine 300 has a shaft seal 345 . The turbine shaft 309 is sealed with respect to the outer housing 315 of the intermediate-pressure part-turbine 303 by two further shaft seals 345 . Between a high-pressure steam inflow region 348 and a steam outlet region 351 , the turbine shaft 309 in the high-pressure part-turbine 300 has the high-pressure rotor blading 354 , 357 . This high-pressure rotor blading 354 , 357 , together with the associated rotor blades (not shown in more detail), constitutes a first blading region 360 . The intermediate-pressure part-turbine 303 has a central steam inflow region 333 . Assigned to the steam inflow region 333 , the turbine shaft 309 has a radially symmetrical shaft shield 363 , a cover plate, on the one hand for dividing the flow of steam between the two flows of the intermediate-pressure part-turbine 303 and also for preventing direct contact between the hot steam and the turbine shaft 309 . In the intermediate-pressure part-turbine 303 , the turbine shaft 309 has a second blading region 366 having the intermediate-pressure rotor blades 354 , 342 . The hot steam flowing through the second blading region 366 flows out of the intermediate-pressure part-turbine 303 from an outflow connection piece 369 to a low-pressure part-turbine (not shown) which is connected downstream in terms of flow. The turbine shaft 309 is composed of two turbine part-shafts 309 a and 309 b , which are fixedly connected to one another in the region of the bearing 318 . In particular, the steam inflow region 333 has a thermal barrier coating 7 and an erosion-resistant layer 13 . FIG. 5 shows an enlarged illustration of a region of the steam turbine 300 , 303 . In the region of the inflow region 333 , the steam turbine 300 , 303 comprises an outer housing 334 , which is exposed to temperatures of between 250° and 350° C. Temperatures of from 450° to 800° C. are present at the inflow region 333 as part of an inner housing 335 . This results in a temperature difference of at least 200° C. At the inner housing 335 , which is exposed to the high temperatures, the thermal barrier coating 7 , together with the erosion-resistant layer 13 , is applied to the inner side 336 (for example not to the outer side 337 ). The thermal barrier coating 7 is locally present only at the inner housing 335 (and for example not in the blading region 366 ). The application of a thermal barrier coating 7 with the erosion-resistant layer 13 reduces the introduction of heat into the inner housing 335 , with the result that the thermal expansion properties are influenced. As a result, all the deformation properties of the inner housing 335 and the steam inflow region 333 can be set in a controlled way. This can be achieved by varying the thickness of the thermal barrier coating 7 or applying different materials at different locations of the surface of the inner housing 335 . It is also possible for the porosity to be different at different locations of the inner housing 335 . The thermal barrier coating 7 can be applied locally, for example in the inner housing 335 in the region of the inflow region 333 . It is also possible for the thermal barrier coating 7 to be applied locally only in the blading region 366 ( FIG. 6 ). The use of an erosion-resistant layer 13 is required in particular in the inflow region 333 . If the thermal barrier coating 7 (TBC) with erosion-resistant layer 13 is present in the inflow region 333 , a thermal barrier coating 7 without erosion-resistant layer may be present in the blading region 366 and/or the turbine blades or vanes. Inflow region Blading region Turbine blade or vane TBC Yes + 13 No No TBC Yes + 13 Yes No TBC Yes + 13 No Yes TBC Yes + 13 Yes + 13 No TBC Yes Yes + 13 No TBC Yes No Yes + 13 FIG. 7 shows a further exemplary embodiment of a component 1 according to the invention. In this case, the thickness of the thermal barrier coating 7 is configured to be thicker in the inflow region 333 than in the blading region 366 of the steam turbine 300 , 303 . The locally differing thickness of the thermal barrier coating 7 is used for controlled setting of the introduction of heat and therefore the thermal expansion and consequently the expansion properties of the inner housing 334 , comprising the inflow region 333 and the blading region 366 . Since higher temperatures are present in the inflow region 333 than in the blading region 366 , the thicker thermal barrier coating 7 in the inflow region 333 reduces the introduction of heat into the substrate 4 to a greater extent than in the blading region 366 , where the temperatures are lower. Therefore, the introduction of heat can be kept at approximately equal levels in the inflow region 333 and the adjoining blading region 366 , resulting in an approximately equal thermal expansion. It is also possible for a different material to be used in the region of the inflow region 333 than in the blading region 366 . Here, the thermal barrier coating 7 is applied throughout the entire hot zone, i.e. everywhere, and includes the erosion-resistant layer 13 . FIG. 8 shows another application example for the use of a thermal barrier coating 7 . The component 1 , in particular a housing part, is in this case a valve housing 31 , into which a hot steam flows through an inflow passage 46 . The inflow passage 46 mechanically weakens the valve housing. The valve housing 31 comprises, for example, a pot-shaped housing part 34 and a cover 37 . Inside the housing part 31 there is a valve comprising a valve cone 40 and a spindle 43 . Component creep leads to uneven axial deformation of the housing 31 and cover 37 . The valve housing 31 would expand to a greater extent in the axial direction in the region of the passage 46 , leading to tilting of the cover together with the spindle 43 , as indicated by dashed lines. As a result, the valve cone 34 is no longer seated correctly, which reduces the leak tightness of the valve. The application of a thermal barrier coating 7 to an inner side 49 of the housing 31 makes the deformation properties more uniform, so that both ends 52 , 55 of the housing 31 and of the cover 37 expand evenly. Overall, the application of the thermal barrier coating 7 serves to control the deformation properties and therefore to ensure the leak tightness of the valve. The thermal barrier coating 7 once again includes the erosion-resistant layer 13 .
There are described components of a steam turbine, comprising a thermally insulating layer and a metallic anti-erosion layer on said thermally insulating layer. The anti-erosion layer is provided with the same material as the metallic connecting layer.
8
This Application is a Divisional Application of Ser. No 09/077,787, filed Sep. 29, 1998, now U.S. Pat. No. 6,184,381, which is a 371 of PCT/JP96/03523 filed Dec. 6, 1996. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing optically active compounds such as optically active alcohols and optically active amines. More specifically, the present invention relates to a novel, highly practical method for producing optically active compounds useful for various utilities such as intermediates for synthesizing pharmaceutical chemicals, liquid crystal materials and agents for optical resolution. 2. Description of the Related Art Various methods for producing optically active compounds have been known conventionally. As the method for asymmetrically synthesis of optically active alcohol compounds, for example, the following methods have been known; (1) a method by using enzymes such as baker's yeast; and (2) a method for asymmetric hydrogenation of carbonyl compounds by using metal complex catalysts. For the method (2), in particular, a great number of examples of asymmetric catalytic reactions have been reported for example as follows; (1) an asymmetric hydrogenation of carbonyl compounds with functional groups, by means of optically active ruthenium catalysts, as described in detail in Asymmetric Catalysis in organic Synthesis, Ed. R. Noyori., pp. 56-82 (1994); (2) a method through hydrogen transfer-type reduction by means of chiral complex catalysts of ruthenium, rhodium or iridium, as described in Chem. Rev., Vol. 92, pp. 1051-1069 (1992); (3) a process of asymmetric hydrogenation tartaric acid by means of a modified nickel catalyst with tartaric acid as described in Oil Chemistry, pp.882-831 (1980) and Advances in Catalysis, Vol.32, pp.215 (1983), Ed. Y. Izumi; (4) an asymmetric hydrosilylation method, as described in Asymmetric Synthesis, Vol.5, Chap.4 (1985), Ed. J. D. Morrison and J. Organomet. Chem. Vol.346, pp.413-424 (1988); and (5) a borane reduction process in the presence of chiral ligands as described J. Chem. Soc., Perkin Trans.1, pp.2039-2044 (1985) and J. Am. Chem. Soc., Vol.109, pp. 5551-5553 (1987). By the conventional method by means of enzymes, however, alcohols can be recovered at a relatively high optical purity, but the reaction substrate therefor is limited and the absolute configuration in the resulting alcohols is limited to specific one. By the asymmetric hydrogen hydrogenation method by means of transition metal complex catalysts, optically active alcohols can be produced at a high selectivity, but a pressure-resistant reactor is required therefor because hydrogen gas is used as the hydrogen source, which is disadvantageous in terms of operational difficulty and safety. Furthermore, the method through such asymmetric hydrogen transfer-type reduction by using conventional metal complex catalysts is limited in that the method requires reaction conditions under heating and the reaction selectivity is insufficient, disadvantageously in practical sense. Accordingly, it has been desired conventionally that a new, very general method for synthesizing optically active alcohols by using a highly active and highly selective catalyst with no use of hydrogen gas be achieved. But no highly efficient and highly selective method for producing such secondary alcohols through asymmetric synthetic reaction by using catalysts similar to those described above has been established yet. As to the optically active secondary alcohols, a method for synthesizing optically active secondary alcohols via optional resolution of racemic secondary alcohols has been known for some reaction substrate which can hardly be reduced, although an excellent optical purity is hardly attained. (Asymmetric Catalysis in Organic Synthesis, Ed. R. Noyori). Because hydrogen transfer-type reduction is a reversible reaction according to the method, dehydrogenation-type oxidation as its adverse reaction is used according to the method. Therefore, the method is called as kinetic optical resolution method. According to the method, however, no process of producing optically active secondary alcohols with catalysts at a high efficiency has been reported yet. As the method for synthetically producing optically active amine compounds, furthermore, a process of optically resolving once produced racemic compounds by using optically active acids and a process through asymmetric synthetic reaction have been known. By the optical resolution process, however, optically active acids should be used at an equal amount or more to amine compounds disadvantageously and complex procedures such as crystallization, separation and purification are required so as to recover optically active amine compounds. As the method through asymmetric synthesis, alternatively, the following processes have been known; (1) an enzymatic process; (2) a process by using metal hydride compounds; and (3) a process of asymmetric hydrogenation by using metal complex catalysts. As to the process by using metal hydride compounds as described above in (2), a great number of reports have been issued about a process of asymmetrically reducing carbon-nitrogen multiple bonds by using an metal hydrides with chiral modifiers. As a general process thereof, for example, it has been known a stoichiometric reduction process of imine compounds and oxime compounds by using a metal hydrides with an optically active ligand, as described in Comprehensive Organic Synthesis, EdS. B. M. Trost and I. Flemming, Vol.8, p.25 (1991), Organic Preparation and Procedures Inc. O. Zhu, R. O. Hutchins, and M. K. Huchins, Vol.26(2), pp.193-235 (1994) and Japanese Patent Laid-open No. 2-311446. The process includes a number of processes with excellent reaction selectivity, but these processes are disadvantageous because that these processes require the use of a reaction agent at an equivalent weight or more to a reaction substrate, along with neutralization treatment after the reaction and additionally in that these processes require laborious purification procedures to recover optically active substances. As the process of asymmetric hydrogenation of carbon-nitrogen multiple bonds by using metal complex catalysts as the method (3), it has been known an asymmetric hydrogenation process of imine compounds with functional groups, by means of optically active metal complex catalysts, as described in Asymmetric Catalysis inorganic Synthesis, pp.82-85 (1994), Ed. R. Noyori. But the process has a drawback in terms of reaction velocity and selectivity. By the method by using enzymes as the method (1), furthermore, amines at a relatively high optical purity can be recovered, but the reaction substrates are limited and the resulting amines have only specific absolute configurations. Furthermore, at a process of asymmetric hydrogenation by means of complex catalysts of transition metals using hydrogen gas, optically active amines have not yet been recovered at a high selectivity or pressure-resistant reactors are essentially required because hydrogen gas is used as the hydrogen source. Hence, such process is disadvantageous because of technically difficult operation and safety problems. Accordingly, it has been demanded that a novel method for synthesizing an optically active amine by using a very common, highly active and highly selective catalyst be realized. Alternatively, a great number of transition metal complexes have been used conventionally as catalysts for organic metal reactions; particularly because rare metal complexes are highly active and stable with the resultant ready handleability despite of high cost, synthetic reactions using the complexes have been developed. The progress of such synthetic reactions using chiral complex catalysts is innovative, and a great number of reports have been issued, reporting that highly efficient organic synthetic reactions have been realized. Among them, a great number of asymmetric reactions using chiral complexes catalysts with optically active phosphine ligands as the catalysts therefor have already been developed, and some of them have been applied industrially (Asymmetric Catalysis in Organic Synthesis, Ed. R. Noyori). As complexes of optically active nitrogen compounds coordinated with transition metals such as ruthenium, rhodium and iridium, a great number of such complexes additionally having excellent properties as catalysts for asymmetric synthetic action have been known. So as to enhance the properties of these catalysts, a great number of propositions concerning the use of optically active nitrogen compounds of specific structures have been done (Chem. Rev., Vol.92, pp.1051-1069 (1992)). For example, reports have been issued about (1) optically active 1,2-diphenylethylenediamines and rhodium-diamine complexes with ligands of cyclohexanediamines, as described in Tetrahedron Asymmetry, Vol.6, pp.705-718 (1995); (2) ruthenium-imide complex with ligands of optically active bisaryliminocyclohexanes, as described in Tetrahedron, Vol. 50, pp.4347-4354 (1994); (3) iridium-pyridine complex with ligands of pyridines, as described in Japanese Patent Laid-open Nos. 62-281861 and 63-119465; (4) optically active 1,2-diphenylethylenediamines or iridium-diamine complex with ligands of cyclohexanediamines, as described in Japanese Patent Laid-open No.62-273990; (5) ruthenium-diamine complex of RuCl[p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH 2 ] (arene) (chloro-(N-p-toluenesulfonyl-1,2-diphenylethylenediamine)(arene)ruthenium) (arene represents benzene which may or may not have a substituent), which is produced by coordinating ruthenium with optically active N-p-toluenesulfonyl-1,2-diphenylethylenediamine [referred to as “p-TsNHCH(C 6 H 5 )CH(C 6 H 5 )NH 2 ” hereinabove and below], as described in J. Am. Chem. Soc., Vol.117, pp.7562-7563(1995); J. Am. Chem. Soc., Vol.118, pp.2521-2522 (1996) and J. Am. Chem. Soc., Vol.118, pp.4916-4917 (1996). Even if these complexes are used, however, problems currently remain to be overcome for practical use, including insufficient catalyst activities, sustainability and optical purities, depending on the subjective reactions and reaction substrates. SUMMARY OF THE INVENTION So as to overcome the aforementioned problems, the present invention is to provide a method for producing optically active compounds, comprising subjecting a compound represented by the following formula (I); (wherein Ra and Rb independently represent a linear or cyclic hydrocarbon group or heterocyclic group which may or may not have a substituent; W 1 represents oxygen atom, N-H, N-Rc, N-OH or N-O-Rd; and Rc and Rd represent the same hydrocarbon group or heterocyclic group as described above) to transfer-type asymmetric reduction in the presence of a transition metal complex and an optically active nitrogen-containing compound or a transition metal complex with an optically active nitrogen-containing compound as an asymmetric ligand, along with a hydrogen-donating organic or inorganic compound, to produce an optically active compound represented by the following formula (II); (wherein W 2 represents OH, NH2, NH-Rc, NH-OH or NH-O-Rd; and Ra, Rb, Rc and Rd independently represent the same as those described above). Additionally, the present invention is to provide a method for producing an optically active alcohol according to the aforementioned method, comprising asymmetrically reducing a carbonyl compound represented by the following formula (III); (wherein R 1 represents an aromatic hydrocarbon group, a saturated or unsaturated aliphatic hydrocarbon group or cyclic aliphatic hydrocarbon group, which may or may not have a substituent, or a heterocyclic group which may or may not have a substituent and contains hetero atoms such as nitrogen, oxygen, sulfur atoms and the like as atoms composing the ring; R 2 represents hydrogen atom, a saturated or unsaturated aliphatic hydrocarbon group or cyclic aliphatic hydrocarbon group which may or may not have a substituent, or an aromatic hydrocarbon group, or the same heterocyclic group as described above; and R 1 and R 2 may satisfactorily be bonded together to form a ring), to produce an optically active alcohol represented by the following formula (IV); (wherein R 1 and R 2 are the same as described above). Furthermore, the present invention is to provide a method for producing an optically active amine, comprising asymmetrically reducing an imine compound represented by the following formula (V); (wherein R 3 represents an aromatic hydrocarbon group, a saturated or unsaturated aliphatic hydrocarbon group or cyclic aliphatic hydrocarbon group, which may or may not have a substituent, or a heterocyclic group which may or may not have a substituent and contains hetero atoms such as nitrogen, oxygen, sulfur atoms and the like as atoms composing the ring; R 4 represents hydrogen atom, a saturated or unsaturated aliphatic hydrocarbon group or cyclic aliphatic hydrocarbon group which may or may not have a substituent, or an aromatic hydrocarbon group, or the same heterocyclic group as described above; R 5 represents hydrogen atom, or a saturated or unsaturated aliphatic hydrocarbon group or cyclic aliphatic hydrocarbon group, which may or may not have a substituent, or an aromatic hydrocarbon group, or the same heterocyclic group as described above, or the hydrocarbon group or heterocyclic group bonded together via hydroxyl group or oxygen atom; and R 3 and R 4 , R 3 and R 5 or R 4 and R 5 , are bonded together to form a ring), to produce optically active amines represented by the following formula (VI); (wherein R 3 , R 4 and R 5 are the same as described above). Still furthermore, the present invention is to provide a method for producing optically active secondary alcohols, comprising subjecting racemic secondary alcohols or meso-type diols to hydrogen transfer reaction by using a catalyst of an optically active ruthenium-diamine complex represented by the following general formula (VII); (wherein * represents an asymmetric carbon atom; R 01 and R 02 are the same or different, independently representing alkyl group, or phenyl group or cycloalkyl group which may or may not have an alkyl group; or R 01 and R 02 together form an alicyclic ring unsubstituted or substituted with an alkyl group; R 03 represents methanesulfonyl group, trifluoromethanesulfonyl group, naphthylsulfonyl group, camphor sulfonyl group, or benzenesulfonyl group which may or may not be substituted with an alkyl group, an alkoxyl group or halogen atom, alkoxycarbonyl group, or benzoyl group which may or may not be substituted with an alkyl group; R 04 represents hydrogen atom or alkyl group; X represents an aromatic compound which may or may not be substituted with an alkyl group; and m and n together represent 0 or 1). DESCRIPTION OF THE PREFERRED EMBODIMENTS In accordance with the present invention, the characteristic methods for producing optically active compounds and catalysts therefor as described above are provided. The detail is described below. Firstly, the method for producing an optically active alcohol of the general formula (I) wherein W 1 is oxygen atom and of the general formula (II) wherein R 2 is OH (hydroxyl group) is described. In the formulas (I) and (II), Ra and Rb independently represent a linear or cyclic hydrocarbon or heterocyclic group which may or may not have a substituent, and the carbonyl compound represented by Ra, Rb and W 1 (oxygen atom) are represented by the following formula (III) as described above, and the optically active alcohol compound produced by the hydrogen transfer-type asymmetric reduction of the carbonyl compound represented by the formula (III) may satisfactorily be represented by the formula (IV). Herein, R 1 represents a monocyclic or polycyclic aromatic hydrocarbon group, a saturated or unsaturated aliphatic hydrocarbon group or cyclic aliphatic hydrocarbon group, which may or may not have a substituent, or a heterocyclic group which may or may not have a substituent and contains hetero atoms such as nitrogen, oxygen, sulfur atoms and the like as atoms composing the ring. The cyclic aliphatic hydrocarbon group and heterocyclic group may satisfactorily be monocyclic or polycyclic like the aromatic hydrocarbon group. The cyclic hydrocarbon (aromatic or alicyclic) and the heterocyclic groups are of condensed series or non-condensed series if they are polycyclic. For example, R 1 specifically includes aromatic monocyclic or polycyclic groups such as phenyl group, 2-methylphenyl, 2-ethylphenyl, 2-isopropylphenyl, 2-tert-butylphenyl, 2-methoxyphenyl, 2-chlorophenyl, 2-vinylphenyl, 3-methylphenyl, 3-ethylphenyl, 3-isopropylphenyl, 3-methoxyphenyl, 3-chlorophenyl, 3-vinylphenyl, 4-methylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-vinylphenyl, cumenyl (cumyl), mesityl, xylyl, 1-naphthyl, 2-naphthyl, anthryl, phenanthryl, and indenyl; hetero monocyclic or polycyclic groups such as thienyl, furyl, pyranyl, xanthenyl, pyridyl, pyrrolyl, imidazolynyl, indolyl, carbazoyl, and phenanthronylyl; and ferrocenyl group. Like these examples, the compound may satisfactorily have various substituents as the substituent, which may be hydrocarbon groups such as alkyl, alkenyl, cycloalkyl and cycloalkenyl; halogen atoms; oxygen-containing groups such as alkoxy group, carboxyl group and ester group; nitro group; amino group and the like. Alternatively, R 2 represents hydrogen atom, a saturated or unsaturated aliphatic hydrocarbon group or cyclic aliphatic hydrocarbon group which may or may not have a substituent or an aromatic hydrocarbon group, or the same heterocyclic group containing hetero atoms, as described above. These are for example alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl and heptyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl; unsaturated hydrocarbon such as vinyl and allyl; and the same as those for R 1 . Furthermore, R 2 may satisfactorily include derivatives of β-keto acid with a functional group at position β. When R 1 and R 2 are bonded together to form a ring, R 2 is for example a saturated or unsaturated alicyclic group to form cyclic ketones, such as cyclopentanone, cyclohexanone, cycloheptane, cyclopentenone, cyclohexenone, and cycloheptenone; and saturated and unsaturated alicyclic groups with a linear or cyclic hydrocarbon substituent group containing alkyl group, aryl group, unsaturated alkyl group and hetero atom on individual carbons. According to the method for producing optically active alcohol compounds through asymmetric reduction of carbonyl compounds, an asymmetric reduction catalyst system of a transition metal complex and an optically active nitrogen-containing compound is used for the asymmetric reduction. As the metal catalyst, then, use is made of various transition metals because they have ligands; particularly preferably; use is made of a transition metal complex represented by the following general formula (a); MXmLn  (a) (wherein M represents transition metals of group VIII, such as iron, cobalt, nickel, ruthenium, rhodium, iridium, osmium, palladium and platinum; X represents hydrogen, halogen atom, carboxyl group, hydroxy group and alkoxy group and the like; L represents neutral ligands such as aromatic compounds and olefin compounds; and m and n represent an integer). As the transition metals in these transition metal catalysts, ruthenium is one of preferable examples. When the neutral ligands are aromatic compounds, a monocyclic aromatic compound represented by the following general formula (b) can be illustrated. Herein, R 0 's are all the same or different substituent groups, including hydrogen atom, a saturated or unsaturated hydrocarbon group, allyl group or a functional group containing hetero atoms. For example, R 0 includes alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, and heptyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl; groups of unsaturated hydrocarbons such as benzyl, vinyl, and allyl; functional groups containing hetero atoms, such as hydroxyl group, alkoxy group, and alkoxycarbonyl group. The number of the substituents R 0 's is an appropriate number of 1 to 6, and the substituents can occupy any position. The transition metal catalysts of the group VIII and the like are used to an amount variable, depending on the size, mode and economy of the reactor, but the catalysts may satisfactorily be used within a molar ratio range of approximately 1/100 to 1/100,000, preferably 1/500 to 1/5,000 to the reaction substrate carbonyl compound. In accordance with the present invention, use is made of optically active nitrogen-containing compounds in the asymmetric catalyst system, and it is possibly assumed that the compounds are present as asymmetric ligands to the transition metal complexes or serve as such. For more easily understandable expression, such optically active nitrogen-containing compounds may also be illustrated as “optically active amine compounds”. The optically active amine compounds are optically active diamine compounds represented by the following general formula (c); (wherein R 9 , R 10 , R 15 and R 16 are independently hydrogen, a saturated or unsaturated hydrocarbon group, urethane group or sulfonyl group; R 11 , R 12 , R 13 and RL 14 are the same or different so that the carbon bonded with these substituent groups might occupy the asymmetric center, including hydrogen atom, an aromatic group, a saturated or unsaturated aliphatic hydrocarbon group or cyclic aliphatic hydrocarbon group; even in this case, the aromatic or cyclic aliphatic group may be monocyclic or polycyclic; the polycyclic aromatic group is any of condensed series or non-condensed series; and furthermore, any one of R 11 and R 12 and any one of R 13 and R 14 are bonded together to form a ring. For example, such compounds include optically active diamine compounds such as optically active 1,2-diphenylethylenediamine, 1,2-cyclohexanediamine, 1,2-cycloheptanediamine, 2,3-dimethylbutanediamine, 1-methyl-2,2-diphenylethylenediamine, 1-isobutyl-2,2-diphenylethylenediamine, 1-isopropyl-2,2-diphenylethylenediamine, 1-methyl-2,2-di(p-methoxyphenyl)ethylenediamine, 1-isobutyl-2,2-di(p-methoxyphenyl)ethylenediamine, 1-isopropyl-2,2-di(p-methoxyphenyl)ethylenediamine, 1-benzyl-2,2-di(p-methoxyphenyl)ethylenediamine, 1-methyl-2,2-dinaphthyldiamine, 1-isobutyl-2,2-dinaphthylethylenediamine, 1-isopropyl-2,2-dinaphthylethylenediamine and the like. Additionally, optically active diamine compounds wherein any one or two of substituents R 9 through R 15 are sulfonyl group, acyl group or urethane group are illustrated. Preferably, furthermore, use may be made of optically active diamine compounds with one sulfonyl group. Furthermore, the optically active diamine (compounds) for potential use are not limited to the illustrated optically active ethylenediamine derivatives, and use may be made of optically active propanediamine, butanediamine, and phenylenediamine derivatives. As the optically active amine compounds, use is made of optically active amino alcohol compounds represented by the following general formula (d). Herein, at least one of R 17 and R 18 is hydrogen atom, and the remaining one is hydrogen atom, a saturated or unsaturated hydrocarbon group, urethane group or sulfonyl group; R 19 , R 20 , R 21 and R 22 are the same or different so that the carbon bonded with these substituent groups might occupy the asymmetric center, including hydrogen atom, a monocyclic or polycyclic aromatic group, a saturated or unsaturated aliphatic hydrocarbon group, and a cyclic aliphatic hydrocarbon group; R 23 represents hydrogen atom, a monocyclic or polycyclic aromatic group, a saturated or unsaturated aliphatic hydrocarbon group and cyclic aliphatic hydrocarbon group. Furthermore, any one of R 19 and R 20 and any one of R 21 and R 22 may satisfactorily be bonded together to form a ring. Additionally, any one of R 17 and R 18 and any one of R 20 and R 21 may satisfactorily be bonded together to form a ring. More specifically, use may satisfactorily be made of optically active amino-alcohols shown in the examples described below. As the optically active amine compounds, furthermore, use may be made of aminophosphine compounds represented by the following general formula (e); Herein, R 24 and R 25 are hydrogen atom, a saturated or unsaturated hydrocarbon group, urethane group, sulfonyl group and acyl group; (CR 2 26 ) n are the same or different so that the carbon bonded with these substituent groups might occupy the asymmetric center, including hydrogen atom, a monocyclic or polycyclic aromatic group, a saturated or unsaturated hydrocarbon group, and a cyclic hydrocarbon group; R 27 and R 28 represent hydrogen atom, and a saturated or unsaturated hydrocarbon group. More specifically, use may be made of the optically active aminophosphines shown in the examples. The optically active amine compounds as illustrated above are generally used for example at an amount at approximately 0.5 to 20 equivalents, and preferably used for example within a range of 1 to 4 equivalents, to the transition metal complex. In the aforementioned catalyst system to be used for the method for producing optically active alcohols through asymmetric reduction of carbonyl compounds, advantageously, an additional basic substance is advantageously present currently. Such basic substance includes for example metal salts or quaternary ammonium compounds represented by the following formula (f); M 1 Y  (f) (wherein M 1 represents an alkali metal or alkali earth metal; and Y represents hydroxy group, alkoxy group, mercapto group and naphthyl group). More specifically, M 1 includes KOH, KOCH 3 , KOCH(CH 3 ) 2 , KOC(CH 3 ) 3 , KC 10 H 8 , LiOH, LiOCH 3 , LiOCH(CH 3 ) 2 , LiOC(CH 3 ) 3 , NaOH, NaOCH 3 , NaOCH(CH 3 ) 2 , NaC 10 H 8 , NaOC(CH 3 ) 3 , and the like. Furthermore, quaternary ammonium salts may be used satisfactorily. The amount of the base to be used is generally about 0.5 to 50 equivalents, preferably 2 to 10 equivalents to the transition metal complex. As has been described above, the basic substance is used for smoothly progressing the asymmetric reduction. Therefore, the base is an important component so as to give optically active alcohol compounds with a high a optical purity. For the method for producing optically active alcohol compounds through hydrogen transfer-type asymmetric reduction in accordance with the present invention, it is inevitable to use hydrogen-donating organic or inorganic compounds. By these are meant compounds capable of donating hydrogen via thermal action or catalytic action, and the types of such hydrogen-donating compounds are not specifically limited, but preferably include alcohol compounds such as methanol, ethanol, 1-propanol, 2-propanol, butanol, and benzyl alcohol; formic acid and salts thereof, for example those in combination with amines; an unsaturated hydrocarbon and heterocyclic compounds having in part a saturated carbon bond, such as tetralin and decalin; hydroquinone or phosphorous acid or the like. Among them, alcohol compounds are preferable, and 2-propanol and formic acid are more preferable. The amount of an organic compound to be used and function as a hydrogen source is determined on the basis of the solubility and economy of the reaction substrate. Generally, the substrate concentration may be about 0.1 to 30% by weight for some type of substrates, but preferably, the concentration is 0.1 to 10% by weight. When using formic acid and a combination of formic acid with amine as a hydrogen source, no solvent is necessarily used. If any solvent is intentionally used, use is made of aromatic compounds such as toluene and xylene; halogen compounds such as dichloromethane, organic compounds such as DMSO, DMF or acetonitrile. According to the method for producing optically active alcohol compounds in accordance with the present invention, hydrogen pressure is essentially not required, but depending on the reaction conditions, hydrogen pressure may satisfactorily be loaded. Even if hydrogen pressure is loaded, the pressure may satisfactorily be about 1 atom. to several atm. because the catalyst system is extremely highly active. The reaction temperature is about −20° C. to 100° C. from the economical standpoint. More practically, the reaction can be carried out around room temperature of 25 to 40° C. The reaction time varies, depending on the reaction conditions such as the concentration of a reaction substrate, temperature and pressure, but the reaction is on completion from several minutes to 100 hours. For use, the metal complex is preliminarily mixed with an optically active amine compound as an optically active nitrogen-containing compound, but an a chiral metal complex may be synthesized preliminarily by the following method, and the resulting complex may be used. More specifically, the method comprises adding an optically active amine compound, a transition metal complex and a complex into for example alcohol, and subsequently heating the resulting mixture in an inactive gas under agitation. Then, the resulting solution is cooled and treated under reduced pressure, prior to recrystallization, to prepare an asymmetric complex catalyst. Together with the method for producing optically active alcohol compounds as described above, the present invention is to provide a method for producing optically active amine compounds represented by the general formula (II) as described above, wherein W 1 is OH, NH 2 , NH-Rc, NH-OH or NH-O-Rd, comprising asymmetric reduction by using an imine compound represented by the general formula (I) wherein W 1 is NH, N-Rc, N-OH or N-O-Rd (Rc and Rd independently represent a linear or cyclic hydrocarbon group which may or may not have a substituent, or a heterocyclic group). More specifically, for example, the present invention is to provide a method for producing an optically active amine compound of the following formula (VI), comprising asymmetric reduction of an imine compound of the following formula (V). Herein, R 3 and R 4 are almost the same as those in the case of the carbonyl compounds and the optically active alcohol compounds of the formulas (III) and (IV), respectively. For example, R 3 is an aromatic monocyclic or polycyclic hydrocarbon group, unsubstituted or substituted, a saturated or unsaturated aliphatic hydrocarbon group or cyclic hydrocarbon group, unsubstituted or substituted, or a hetero monocyclic or polycyclic group containing hetero atoms such as nitrogen, oxygen, sulfur atoms and the like; more specifically, R 3 includes aromatic monocyclic or polycyclic hydrocarbon groups such as phenyl group, 2-methyphenyl, 2-ethylphenyl, 2-isopropylphenyl, 2-tert-butylphenyl, 2-methoxyphenyl, 2-chlorophenyl, 2-vinylphenyl, 3-methylphenyl, 3-ethylphenyl, 3-isopropylphenyl, 3-methoxyphenyl, 3-chlorophenyl, 3-vinylphenyl, 4-methyphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-vinylphenyl, cumenyl, mesityl, xylyl, 1-naphthyl, 2-naphthyl, anthryl, phenanthryl, and indenyl groups; hetero monocyclic or polycyclic groups such as thienyl, furyl, pyranyl, xanthenyl, pyridyl, pyrrolyl, imidazolyl, indolyl, carbazoyl, and phenanthronylyl; and ferrocenyl group. Like these examples, R 3 may contain any of various substituents, which may satisfactorily be hydrocarbon groups such as alkyl, alkenyl, cycloalkyl, and cycloalkenyl; halogen atom; oxygen-containing groups such as alkoxy group, carboxyl group and ester group; nitro group; cyano group and the like. Furthermore, R 4 represents hydrogen atom, a saturated or unsaturated hydrocarbon group, aryl group, hetero atom-containing functional groups, including for example alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl; unsaturated hydrocarbons such as vinyl and allyl; and the same as those for R1. Additionally, R 5 represents hydrogen atom, a saturated and unsaturated hydrocarbon group, aryl group, a hetero atom-containing heterocyclic group, or the hydrocarbon group or heterocyclic group bonded together via hydroxyl group or oxygen atom, including for example alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl and heptyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl; unsaturated hydrocarbon groups such as benzyl, vinyl and allyl; hydroxyl group; alkyl ether groups; aryl ether groups; and the like. Furthermore, a saturated or unsaturated cyclic imine compound formed by bonding together R 3 and R 4 , R 3 and R 5 or R 4 and R 5 , is illustrated. Non-cyclic imine compounds can be synthesized readily from the corresponding ketone and amines. In this case, the syn-form and anti-form or a mixture enriched with either one of these syn- and anti-forms may be used satisfactorily, but a purified product of the mixture may be used singly or a mixture thereof with another imine compound may also be used. Even by the method for producing optically active amine compounds, like the method for producing optically active alcohol compounds, use is made of an asymmetric reduction catalyst composed of a transition metal complex and an optically active nitrogen-containing compound. In the transition metal complex among them, various transition metals with ligands are used, and particularly preferably, use is made of those similar to a transition metal complex represented by the general formula (a); MXmLn  (a) (wherein M is a transition metal of group VIII, such as iron, cobalt, nickel, ruthenium, rhodium, iridium, osmium, palladium and platinum; X represents hydrogen, halogen atom, carboxyl group, hydroxy group and alkoxy group and the like; L represents neutral ligands such as aromatic compounds and olefin compounds; m and n represent an integer). The transition metal in the transition metal complex is preferably rare metal, and specifically, ruthenium is one of preferable examples. Like the method for producing optically active alcohols, a monocyclic aromatic compound represented by the general formula (b) is illustrated for the aromatic compound as the neutral ligand. Herein, R 0 's are the same or different substituent-groups, representing hydrogen atom, a saturated or unsaturated hydrocarbon group, aryl group, and functional groups containing hetero atoms, for example alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, and heptyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl; unsaturated hydrocarbon groups such as benzyl, vinyl, and allyl; hetero atom-containing functional groups such as hydroxyl group, alkoxy group and alkoxycarbonyl group. The number of the substituents R 0 's is an optional number of 1 to 6, and the substituents each can occupy any position. The transition metal catalysts are used at an amount variable, depending on the size, mode and economy of the reactor, but the catalysts may satisfactorily be used within a molar ratio range of approximately 1/100 to 1/100,000, preferably 1/200 to 1/5,000 to the reaction substrate imine compound. According to the method for producing optically active amine compounds in accordance with the present invention, additionally, use is made of optically active nitrogen-containing compounds in the asymmetric catalyst system, and it is possibly assumed that the compounds may be present as asymmetric ligands in the transition metal complexes or may serve as such. For more easily understandable expression, such optically active nitrogen-containing compounds are illustrated as “optically active amine compounds”. As described above, the optically active amine compounds are optically active diamine compounds represented for example by the following general formula (c); (wherein R 9 , R 10 , R 15 , and R 16 are independently hydrogen, a saturated or unsaturated hydrocarbon group, urethane group or sulfonyl group; R 11 , R 12 , R 13 and R 14 are the same or different so that the carbon bonded with these substituent groups might occupy the asymmetric center, including hydrogen atom, aromatic monocyclic and polycyclic groups, a saturated or unsaturated hydrocarbon group or cyclic hydrocarbon group; even in this case, the aromatic, or cyclic, or cyclic aliphatic group may be monocyclic or polycyclic; the polycyclic aromatic group is any of condensed series or non-condensed series; and furthermore, any one of R 11 and R 12 may satisfactorily form a ring. For example, such compounds include optically active diamine compounds such as optically active 1,2-diphenylethylenediamine, 1,2-cyclohexanediamine, 1,2-cycloheptanediamine, 2,3-dimethylbutanediamine, 1-methyl-2,2-diphenylethylenediamine, 1-isobutyl-2,2-diphenylethylenediamine, 1-isopropyl-2,2-diphenylethylenediamine, 1-methyl-2,2-di(p-methoxyphenyl)ethylenediamine, 1-isobutyl-2,2-di(p-methoxyphenyl)ethylenediamine, 1-isopropyl-2,2-di(p-methoxyphenyl)ethylenediamine, 1-benzyl-2,2-di(p-methoxyphenyl)ethylenediamine, 1-methyl-2,2-dinaphthylethylenediamine, 1-isobutyl-2,2-dinaphthylethylenediamine, 1-isopropyl-2,2-dinaphthylethylenediamine and the like. Additionally, optically active diamine compounds wherein any one or two of substituents R 9 through R 15 are sulfonyl group, acyl group or urethane group may also be used. Preferably, furthermore, use may be made of optically active diamine compounds with one sulfonyl group. Furthermore, optically active diamine (compounds) to be possibly used are not limited to the illustrated optically active ethylenediamine derivatives, and use may be made of optically active propanediamine, butanediamine, and phenylenediamine derivatives. As the optically active amine compound, use is made of an optically active amino alcohol compound represented by the following general formula (d); Herein, at least one of R 17 and R 19 is hydrogen atom, and the remaining one is hydrogen atom, a saturated or unsaturated hydrocarbon group, urethane group or sulfonyl group; R 19 , R 20 , R 21 and R 22 are the same or different so that the carbon bonded with these substituent groups might occupy the asymmetric center, including hydrogen atom, an aromatic monocyclic or polycyclic group, a saturated or unsaturated hydrocarbon group, or a cyclic hydrocarbon group; R 23 represents hydrogen atom, an aromatic monocyclic or polycyclic group, a saturated or unsaturated hydrocarbon group and a cyclic hydrocarbon group. Furthermore, any one of R 19 and R 20 and any one of R 21 and R 22 may satisfactorily be bonded together to form a ring, or any one of R 17 and R 18 and any one of R 20 and R 21 may satisfactorily be bonded together to form a ring. More specifically, use is made of optically active amino alcohols shown in the examples described below. As the optically active amine compound, furthermore, use is made of aminophosphine compound represented by the following general formula (e). Herein, R 24 and R 25 are hydrogen atom, a saturated or unsaturated hydrocarbon group, urethane group, sulfonyl group and acyl group; (CR 2 16 ) n are the same or different so that the carbon bonded with these substituent groups might occupy the asymmetric center, including hydrogen atom, an aromatic monocyclic or polycyclic group, a saturated or unsaturated hydrocarbon group, and a cyclic hydrocarbon group; R 27 and R 28 represent hydrogen atom, a saturated or unsaturated hydrocarbon group, and allyl group. More specifically, use is made of the optically active aminophosphines shown in the examples. The optically active amine compounds as illustrated above are used at an amount for example of approximately 0.5 to 20 equivalents, and preferably within a range of 1 to 2 equivalents, to the transition metal complex. The transition metal catalyst to be used as the catalyst as described above and the optically active amine compound are essential components to progress the asymmetric reduction in a smooth manner thereby attaining a higher asymmetric yield, and amine compounds at a higher optical purity cannot be recovered at a sufficiently high reaction activity, if either one of the two is eliminated. For the method for producing optically active amines through hydrogen transfer-type asymmetric reduction in accordance with the present invention, the presence of a hydrogen-donating organic or inorganic compound is indispensable. These compounds mean compounds capable of donating hydrogen through thermal action or catalytic action, and the types of these hydrogen-donating compounds are not limited, but preferably include alcohol compounds such as methanol, ethanol, 1-propanol, 2-propanol, butanol, and benzyl alcohol; formic acid and salts thereof, such as those in combination with amines; unsaturated hydrocarbons and heterocyclic compounds having saturated carbon bonds in part, such as tetralin and decalin; hydroquinone or phosphorous acid or the like. Among them, alcohol compounds are preferable, and 2-propanol is more preferable. The amount of an organic acid to be used as a hydrogen source is determined, depending on the solubility and economy of the reaction substrate. Generally, the substrate is used at a concentration of approximately 0.1 to 30% by weight, depending on the type of the substrate to be used, and is preferably at a concentration of 0.1 to 10% by weight. When using formic acid and a combination of formic acid with amine as a hydrogen source, no solvent is necessarily used, but use may satisfactorily be made of aromatic compounds such as toluene and xylene; halogen compounds such as dichloromethane, or organic compounds such as DMSO, DMF or acetonitrile, if it intended to use any solvent. Hydrogen pressure is essentially not required, but depending on the reaction conditions, hydrogen pressure may satisfactorily be loaded. Even if hydrogen pressure is loaded, the pressure may satisfactorily be about 1 atm to 50 atm. The reaction temperature is about −20° C. to 100° C. from the economical standpoint. More practically, the reaction can be carried out around room temperature of 25 to 40° C. The reaction time varies, depending on the reaction conditions such as the concentration of a reaction substrate, temperature and pressure, but the reaction is on completion from several minutes to 100 hours. The metal complex to be used in accordance with the present invention is preliminarily mixed with an optically active amine compound, but an asymmetric metal complex may be preliminarily synthesized by the following method, and the resulting complex may be used. More specifically, for example, a method is illustrated, comprising suspending a ruthenium-arene complex, an optically active amine compound and triethylamine in 2-propanol, heating the resulting mixture in argon or nitrogen gas stream under agitation, and cooling then the resulting reaction mixture, from which the solvent is then removed, and re-crystallizing the resulting mixture in an alcohol solvent to prepare an asymmetric complex. The catalyst system to be used for the hydrogen transfer-type asymmetric reduction in accordance with the present invention is very characteristic and has never been known up to now. The optically active ruthenium-diamine complex represented by the following formula (VII) as described above as one metal complex composed of a transition metal and an optically active nitrogen-containing compound ligand is useful as a catalyst for producing optically active secondary alcohol compounds, comprising subjecting racemic secondary alcohol or meso-type diols to hydrogen transfer reaction, and therefore, the complex draws higher attention. In the formula, * represents an asymmetric carbon atom; R 01 and R 02 are the same or different, independently representing alkyl group, or phenyl group or cycloalkyl group which may or may not have an alkyl group; or R 01 and R 02 together form an alicyclic ring unsubstituted or substituted with an alkyl group; R 03 represents methanesulfonyl group, trifluoromethanesulfonyl group, naphthylsulfonyl group, camphor sulfonyl group, or benzenesulfonyl group which may or may not be substituted with an alkyl group, an alkoxyl group or halogen atom, alkoxycarbonyl group, or benzoyl group which may or may not be substituted with an alkyl group; R 04 represents hydrogen atom or alkyl group; X represents an aromatic compound which may or may not be substituted with an alkyl group; and m and n simultaneously represent 0 or 1. For more description of the optically active ruthenium-diamine complex of the formula (VII), the aromatic compound which may or may not have an alkyl group represented by X, for example alkyl groups with C1 to C4, means for example benzene, toluene, xylene, mesitylene, hexamethylbenzene, ethylbenzene, tert-butylbenzene, p-cymene, and cumene and preferably includes benzene, mesitylene and p-cymene. R 01 and R 02 represent a linear or branched alkyl group, if they represent an alkyl group, for example alkyl groups with C1 to C4. More specifically, the alkyl group includes methyl, ethyl, n-propyl, isopropyl, n-, iso-, sec- and tert-butyl. More preferably, the group includes methyl, ethyl, n-propyl or iso-propyl. If R 01 and R 02 are bonded together to form an alicyclic group, the group may satisfactorily be a C5 to C7-membered ring. The alkyl group which may or may not be a substituent therefor, for example alkyl substituent group with C1 to C4, includes methyl group, ethyl group, n-propyl group, isopropyl group, and n-, iso-, sec- and tert-butyl groups. Preferably, the alkyl group is methyl. R 1 and R 2 as phenyl group wherein R 01 and R 02 may have an alkyl group, for example methyl group, specifically include phenyl, o-, m- and p-tolyl groups. R 01 and R 02 representing cycloalkyl group contain carbon atoms in 5 to 6-membered rings, preferably including cyclopentyl or cyclohexyl. In more preferable examples, R 01 and R 02 are independently phenyl or R 01 and R 02 together mean tetramethylene (-(CH 2 ) 4 -). R 03 represents methanesulfonyl group, trifluoromethanesulfonyl group, naphthylsulfonyl group, camphor sulfonyl group, or benzenesulfonyl group which may or may not be substituted with alkyl group, for example alkyl group with C1 to C3, alkoxy group for example alkoxy group with C1 to C3, or halogen atom, or benzoyl group which may or may not be substituted with alkyl group, for example C1 to C4 alkoxycarbonyl groups, or alkyl group, for example C1 to C4 alkyl group. More specifically, R 03 representing benzenesulfonyl group which may or may not be substituted with C1 to C3 alkyl group, C1 to C3 alkoxyl group or halogen atom, includes benzenesulfonyl, o-, m- and p-toluenesulfonyl, o-, m-, and p-ethylbenzenesulfonyl, o-, m-, and p-methoxybenzenesulfonyl, o-, m-, and p-ethoxybenzenesulfonyl, o-, m-, and p-chlorobenzenesulfonyl, 2, 4, 6-trimethylbenzenesulfonyl, 2,4,6-triisopropylbenzenesulfonyl, p-fluorobenzenesulfonyl, and pentafluorobenzenesulfonyl, and more preferably includes benzenesulfonyl or p-toluenesulfonyl. Specifically, R 03 representing C1 to C4 alkoxycarbonyl groups includes methoxycarbonyl, ethoxycarbonyl, isopropyloxycarbonyl, and tert-butoxycarbonyl, preferably including methoxycarbonyl or tert-butoxycarbonyl. R 03 representing benzoyl group which may or may not be substituted with C1 to C4 alkyl groups specifically includes benzoyl, o-, m-, and p-methylbenzoyl, o-, m-, and p-ethylbenzoyl, o-, m-, and p-isopropylbenzoyl, and o-, m-, and p-tert-butylbenzoyl, preferably including benzoyl or p-methylbenzoyl. In the most preferable example, R 03 is methanesulfonyl, trifluoromethanesulfonyl, benzenesulfonyl or p-toluenesulfonyl. R 04 representing hydrogen atom or alkyl group, for example C1 to C4 alkyl groups, specifically includes for example hydrogen, methyl, ethyl, n-propyl, isopropyl, n-, iso-, sec- and tert-butyl, and more preferably includes hydrogen atom or methyl group. The optically active ruthenium-diamine complex is used for the method for producing optically active secondary alcohols from ketones as descried above in accordance with the present invention, and in this case, the racemic secondary alcohols as the raw material compounds in accordance with the present invention are illustrated by the following formula (VIII). It is needless to say that the racemic alcohols are not limited to those represented by the formula. R 4 represents an aromatic monocyclic or polycyclic hydrocarbon group, unsubstituted or substituted or a hetero monocyclic or polycyclic group containing hetero atoms including nitrogen, oxygen, sulfur atoms and the like, specifically representing aromatic monocyclic or polycyclic groups such as phenyl group, 2-methylphenyl, 2-ethylphenyl, 2-isopropylphenyl, 2-tert-butylphenyl, 2-methoxyphenyl, 2-chlorophenyl; 2-vinylphenyl, 3-methylphenyl, 3-ethylphenyl, 3-isopropylphenyl, 3-methoxyphenyl, 3-chlorophenyl, 3-vinylphenyl, 4-methylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-vinylphenyl, cumenyl, mesityl, xylyl, 1-naphthyl, 2-naphthyl, anthryl, phenanthryl, and indenyl; hetero monocyclic or polycyclic groups such as thienyl, furyl, pyranyl, xanthenyl, pyridyl, pyrrolyl, imidazolyl, indolyl, carbazoyl, and phenthronylyl; and ferrocenyl group. Furthermore, R 7 represents hydrogen atom, a saturated or unsaturated hydrocarbon group, or a functional group containing hetero atoms, including for example alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, and heptyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl; and unsaturated hydrocarbons such as benzyl, vinyl, and allyl. R 6 and R 7 may be bonded together to form a ring, and in this case, R 7 includes for example a saturated or unsaturated alicyclic group giving a cyclic ketone such as cyclopentanone, cyclohexanone, cycloheptane, cyclopentenone, cyclohexenone, and cycloheptenone; or a saturated and unsaturated alicyclic group with a substituent group having an alkyl group, an aryl group, a unsaturated alkyl group or a linear or cyclic hydrocarbon group on each of the individual carbons. Additionally, the meso-type diols are represented for example by the following formula (IX). It is needless to say that the meso-diols are not limited to them. In this case, R 8 and R 9 are the same and represent a saturated or unsaturated hydrocarbon group which may or may not have a substituent group, or R 8 and R 9 may be bonded together to form a saturated or unsaturated alicyclic group which may or may not have a substituent group. More specifically, the ruthenium-diamine complex of the present invention is for example such that m and n are simultaneously zero in the formula (VII). Herein, η is used to represent the number of carbon atoms bonded to a metal in unsaturated ligands, and therefore, hexahapto (six carbon atoms bonded to metal) is represented by η 6 ; p-Ts represents p-toluenesulfonyl group; Ms represents methanesulfonyl group; and Tf represents trifluoromethanesulfonyl group. Ru[(S, S)-p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH](η 6 -benzene)(((S, S)-N-p-toluenesulfonyl-1,2-diphenylethylenediamine)(η 6 -benzene)ruthenium) Ru[(R, R)-p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH](η 6 -benzene) (((R, R)-N-p-toluenesulfonyl-1,2-diphenylethylenediamine) (η 6 -benzene) ruthenium) Ru[(S, S)-p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH](η 6 -p-cymene)(((S, S)-N-p-toluenesulfonyl-1,2-diphenylethylenediamine) (η 6 -p-cymene)ruthenium) Ru[(R, R)-p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH](η 6 -p-cymene)(((R, R)-N-p-toluenesulfonyl-1, 2-diphenylethylenediamine) (η 6 -p-cymene)ruthenium) Ru[(S, S)-p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH](η 6 -mesitylene)(((S, S)-N-p-toluenesulfonyl-1,2-diphenylethylenediamine) (η 6 -mesitylene)ruthenium) Ru[(R, R)-p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH](η 6 -mesitylene)(((R, R)-N-p-toluenesulfonyl-1,2-diphenylethylenediamine)(η 6 -mesitylene)ruthenium) Ru[(S, S)-MsNCH(C 6 H 5 )CH(C 6 H 5 )NH](η 6 -benzene)(((S, S)-N-methanesulfonyl-1,2-diphenylethylenediamine) (η 6 -benzene)ruthenium) Ru[(R, R)-MsNCH(C 6 H 5 )CH(C 6 H 5 )NH](η 6 -benzene)(((R, R)-N-methanesulfonyl-1,2-diphenylethylenediamine)(η 6 -benzene)ruthenium) Ru[(S, S)-MsNCH(C 6 H 5 )CH(C 6 H 5 )NH](η 6 -p-cymene)(((S, S)-N-methanesulfonyl-1,2-diphenylethylenediamine)(η 6 -p-cymene)ruthenium) Ru[(R, R)-MSNCH(C 6 H 5 )CH(C 6 H 5 )NH](η 6 -p-cymene)(((R, R)-N-methanesulfonyl-1,2-diphenylethylenediamine)(η 6 -p-cymene)ruthenium) Ru[(S, S)-MSNCH(C 6 H 5 )CH(C 6 H 5 )NH](η 6 -mesitylene)(((S, S)-N-methanesulfonyl-1,2-diphenylethylenediamine)(η 6 -mesitylene)ruthenium) Ru[(R, R)-MsNCH(C 6 H 5 )CH(C 6 H 5 )NH](η 6 -mesitylene)(((R, R)-N-methanesulfonyl-1,2-diphenylethylenediamine)(η 6 -mesitylene)ruthenium) Ru[(S, S)-TfNCH(C 6 H 5 )CH(C 6 H 5 )NH](η 6 -benzene)(((S S)-N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine)(η 6 -benzene)ruthenium) Ru[(R, R)-TfNCH(C 6 H 5 )CH(C 6 H 5 )NH](η 6 -benzene) ((R, R)-N-trifluoromethanesulfonyl-1, 2-diphenylethylenediamine)(η 6 -benzene)ruthenium) RU[(S, S)-TfNCH(C 6 H 5 )CH(C 6 H 5 )NH](η 6 -p-cymene)(((S, S)-N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine)(η 6 -p-cymene)ruthenium) Ru[(R, R)-TfNCH(C 6 H 5 )CH(C 6 H 5 )NH](η 6 -p-cymene)(((R, R)-N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine)(η 6 -p-cymene)ruthenium) Ru[(S, S)-TfNCH(C 6 H 5 )CH(C 6 H 5 )NH](η 6 -mesitylene)(((S, S)-N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine)(η 6 -mesitylene)ruthenium) Ru[(R, R)-TfNCH(C 6 H 5 )CH(C 6 H 5 )NH](η 6 -mesitylene)(((R, R)-N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine)(η 6 -mesitylene)ruthenium) Ru[(S, S)-C 6 H 5 SO 2 NCH(C 6 H 5 )CH(C 6 H 5 )NH](η 6 -benzene)(((S, S)-N-benzenesulfonyl-1,2-diphenylethylenediamine)(η 6 -benzene) ruthenium) Ru[(R, R)-C 6 H 5 SO 2 NCH(C 6 H 5 )CH(C 6 H 5 )NH](η 6 -benzene)(((R, R)-N-benzenesulfonyl-1,2-diphenylethylenediamine)(η 6 -benzene) ruthenium) Ru[(S, S)-C 6 H 5 SO 2 NCH(C 6 H 5 )CH(C 6 H 5 )NH](η 6 -p-cymene)(((S, S)-N-benzenssulfonyl-1,2-diphenylethylenediamine)(η 6 -p-cymene)ruthenium) Ru[(R, R)-C 6 H 5 SO 2 NCH(C 6 H 5 )CH(C 6 H 5 )NH](η 6 -p-cymene)(((R, R)-N-benzenesulfonyl-1,2-diphenylethylenediamine)(η 6 -p-cymene)ruthenium) Ru[(S, S)-C 6 H 5 SO 3 NCH(C 6 H 5 )CH(C 6 H 5 )NH](η 6 -mesitylene)(((S, S)-N-benzenesulfonyl-1,2-diphenylethylenediamine)(η 6 -mesitylene)ruthenium) Ru[(R, R)-C 6 H 5 SO 2 NCH(C 6 H 5 )CH(C 6 H 5 )NH](η 6 -mesitylene)(((R, R)-N-benzenesulfonyl-1,2-diphenylethylenediamine)(η 6 -mesitylene)ruthenium) Ru[(S, S)-N-p-Ts-1,2-cyclohexanediamine](η 6 -benzene) (((S, S)-N-p-toluenesulfonyl-1,2-cyclohexanediamine)(η 6 -benzene)ruthenium) Ru[(R, R)-N-p-Ts-1,2-cyclohexanediamine](η 6 -benzene) (((R, R)-N-p-toluenesulfonyl-1,2-cyclohexanediamine)(η 6 -benzene)ruthenium) Ru[(S, S)-N-p-Ts-1,2-cyclohexanediamine](η 6 -p-cymene) (((S, S)-N-p-toluenesulfonyl-1,2-cyclohexanediamine) (η 6 -p-cymene)ruthenium) Ru[(R, R)-N-p-Ts-1,2-cyclohexanediamine](η 6 -p-cymene) (((R, R)-N-p-toluenesulfonyl-1,2-cyclohexanediamine)(η 6 -p-cymene)ruthenium) Ru[(S, S)-N-p-Ts-1,2-cyclohexanediamine](η 6 -mesitylene) (((S, S)-N-p-toluenesulfonyl-1,2-cyclohexanediamine)(η 6 -mesitylene)ruthenium) Ru[(R, R)-N-p-Ts-1,2-cyclohexanediamine](η 6 -mesitylene) (((R, R)-N-p-toluenesulfonyl-1,2-cyclohexanediamine)(η 6 -mesitylene)ruthenium) Ru[(S, S)-N-Ms-1,2-cyclohexanediamine](η 6 -benzene) (((S, S)-N-methanesulfonyl-1,2-cyclohexanediamine)(η 6 -benzene)ruthenium) Ru[(R, R)-N-Ms-1,2-cyclohexanediamine](η 6 -benzene) ((R, R)-N-methanesulfonyl-1,2-cyclohexanediamine)(η 6 -benzene) ruthenium) Ru[(S, S)-N-Ms-1,2-cyclohexanediamine](η 6 -p-cymene) (((S, S)-N-methanesulfonyl-1,2-cyclohexanediamine)(η 6 -p-cymene)ruthenium) Ru[(R, R)-N-Ms-1,2-cyclohexanediamine](η 6 -p-cymene) (((R, R)-N-methanesulfonyl-1,2-cyclohexanediamine)(η 6 -p- cymene)ruthenium) Ru[(S, S)-N-Ms-1,2-cyclohexanediamine](η 6 -mesitylene) ((S, S)-N-methanesulfonyl-1,2-cyclohexanediamine)(η 6 -mesitylene)ruthenium) Ru[(R, R)-N-Ms-1,2-cyclohexanediamine](η 6 -mesitylene)(((R, R)-N-methanesulfonyl-1,2-cyclohexanediamine)(η 6 -mesitylene)ruthenium) Ru[(S, S)-N-Tf-1,2-cyclohexanediamine](η 6 -benzene)(((S, S)-N-trifluoromethanesulfonyl-1,2-cyclohexanediamine)(η 6 -benzene)ruthenium) Ru[(R, R)-N-Tf-1,2-cyclohexanediamine](η 6 -benzene)(((R, R)-N-trifluoromethanesulfonyl-1,2-cyclohexanediamine)(η 6 -benzene)ruthenium) Ru[(S, S)-N-Tf-1,2-cyclohexanediamine] (η 6 -p-cymene) (((S, S)-N-trifluoromethanesulfonyl-1,2-cyclohexanediamine)(η 6 -p-cymene)ruthenium) Ru[(R, R)-N-Tf-1,2-cyclohexanediamine] (η 6 -p-cymene) (((R, R)-N-trifluoromethanesulfonyl-1,2-cyclohexanediamine)(η 6 -p-cymene)ruthenium) Ru[(S, S)-N-Tf-1,2-cyclohexanediamine](η 6 -mesitylene) (((S, S)-N-trifluoromethanesulfonyl-1,2-cyclohexanediamine)(η 6 -mesitylene)ruthenium) Ru[(R, R)-N-Tf-1,2-cyclohexanediamine](η 6 -mesitylene)(((R, R)-N-trifluoromethanesulfonyl-1,2-cyclohexanediamine)(η 6 -mesitylene)ruthenium) Ru[(S, S)-N-C 4 H 5 SO 2 -1,2-cyclohexanediamine](η 6 -benzene)(((S, S)-N-benzenesulfonyl-1,2-cyclohexanediamine)(η 6 -benzene)ruthenium) Ru[(R, R)-N-C 6 H 5 SO 2 -1,2-cyclohexanediamine](η 2 -benzene) (((R, R)-N-benzenesulfonyl-1,2-cyclohexanediamine)(η 6 -benzene)ruthenium) Ru[(S, S)-N-C 6 H 5 SO 2 -1,2-cyclohexanediamine](η 6 -p-cymene) (((S, S)-N-benzenesulfonyl-1,2-cyclohexanediamine) (η 6 -p-cymene)ruthenium) Ru[(R, R)-N-C 6 H 5 SO 2 -1,2-cyclohexanediamine](η 6 -p-cymene) (((R, R)-N-benzeneesulfonyl-1,2-cyclohexanediamine)(η 6 -p-cymene)ruthenium) Ru[(S, S)-N-C 6 H 5 SO 2 -1,2-cyclohexanediamine](η 6 -mesitylene)(((S, S)-N-benzenesulfonyl-1,2-cyclohexanediamine) (η 6 -mesitylene)ruthenium) Ru[(R, R)-N-C 6 H 5 SO 2 -1,2-cyclohexanediamine](η 6 -mesitylene)(((R, R)-N-benzenesulfonyl-1,2-cyclohexanediamine) (η 6 -mesitylene)ruthenium) Those of the formula (VII) wherein m and n are simultaneously 1 are illustrated as follows. Herein, η is used to represent the number of carbon atoms bonded to a metal in unsaturated ligands, and therefore, hexahapto (six carbon atoms bonded to metal) is represented by η 6 ; p-Ts represents p-toluenesulfonyl group; Ms represents methanesulfonyl group; and Tf represents trifluoromethanesulfonyl group. RuH[(S, S)-p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH 2 ](η 6 -benzene) (hydride-((S, S)-N-p-toluenesulfonyl-1,2-diphenylethylenediamine)(η 6 -benzene)ruthenium) RuH[(R, R)-p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH 2 ](η 6 -benzene) (hydride-((R, R)-N-p-toluenesulfonyl-1,2-diphenylethylenediamine)(η 6 -benzene)ruthenium) RuH[(S, S)-p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH 2 ](η 6 -p-cymene)(hydride-((S, S)-N-p-toluenesulfonyl-1,2-diphenylethylenediamine)(η 6 -p-cymene)ruthenium) RuH[(R, R)-p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH 2 ](η 6 -p-cymene)(hydride-((R, R)-N-p-toluenesulfonyl-1,2-diphenylethylenediamine)(η 6 -p-cymene)ruthenium) RuH[(S, S)-p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH 2 ](η 6 -mesitylene) (hydride-((S, S)-N-p-toluenesulfonyl-1,2-diphenylethylenediamine)(η 6 -mesitylene)ruthenium) RuH[(R, R)-p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH 2 ](η 6 -mesitylene) (hydride-((R, R)-N-p-toluenesulfonyl-1,2-diphenylethylenediamine)(η 6 -mesitylene)ruthenium) RuH[(S, S)-MsNCH(C 6 H 5 )CH(C 6 H 5 )NH 2 ](η 6 -benzene)(hydride-((S, S)-N-methanesulfonyl-1,2-diphenylethylenediamine)(η 6 -benzene)ruthenium) RuH[(R, R)-MsNCH(C 6 H 5 )CH(C 6 H 5 )NH 2 ](η 6 -benzene)(hydride-((R, R)-N-methanesulfonyl-1,2-diphenylethylenediamine)(η 6 -benzene)ruthenium) RuH[(S, S)-MSNCH(C 6 H 5 )CH(C 6 H 5 )NH 2 ](η 6 -p-cymene)(hydride-((S, S)-N-methanesulfonyl-1,2-diphenylethylenediamine) (η 6 -p-cymene)ruthenium) RuH[(R, R)-MsNCH(C 6 H 5 )CH(C 6 H 5 )NH 2 ](η 6 -p-cymene)(hydride-((R, R)-N-methanesulfonyl-1,2-diphenylethylenediamine)(η 6 -p-cymene)ruthenium) RuH[(S, S)-MsNCH(C 6 H 5 )CH(C 6 H 5 )NH 2 ](η 6 -mesitylene)(hydride-((S, S)-N-methanesulfonyl-1,2-diphenylethylenediamine)(η 6 -mesitylene)ruthenium) RUH[(R, R)-MsNCH(C 6 H 5 )CH(C 6 H 5 )NH](η 6 -mesitylene)(hydride-((R, R)-N-methanesulfonyl-1,2-diphenylethylenediamine)(η 6 -mesitylene)ruthenium) RuH[(S, S)-TfNCH(C 6 H 5 )CH(C 6 H 5 )NH 2 ](η 6 -benzene)(hydride-((S, S)-N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine) (η 6 -benzene)ruthenium) RuH[(R, R)-TfNCH(C 6 H 5 )CH(C 6 H 5 )NH 2 ](η 6 -benzene) (hydride-((R, R)-N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine) (η 6 -benzene) ruthenium) RuH[(S, S)-TfNCH(C 6 H 5 )CH(C 6 H 5 )NH 2 ](η 6 -p-cymene)(hydride-((S, S)-N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine) (η 6 -p-cymene)ruthenium) RuH[(R, R)-TfNCH(C 6 H 5 )CH(C 6 H 5 )NH 2 ](η 6 -p-cymene)(hydride-((R, R)-N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine) (η 6 -p-cymene)ruthenium) RuH[(S, S)-TfNCH(C 6 HS)CH(C 6 H 5 )NH 2 ](η 6 -mesitylene)(hydride-((S, S)-N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine) (η 6 -mesitylene) ruthenium) RuH[(R, R)-TfNCH(C 6 H 5 )CH(C 6 H 5 )NH 2 ](η 6 -mesitylene)(hydride-((R, R)-N-trifluoromethanesulfonyl-1,2-diphehylethylenediamine) (η 6 -mesitylene)ruthenium) RuH[(S, S)-C 6 H 5 SO 2 NCH(C 6 H 5 )CH(C 6 H 5 )NH 2 ](η 6 -benzene)(hydride-((S, S)-N-benzenesulfonyl-1,2-diphenylethylenediamine)(η 6 -benzene)ruthenium) RuH[(R, R)-C 6 H 5 SO 2 NCH(C 6 H 5 ) CH(C 6 H 5 )NH 2 ](η 6 -benzene) (hydride-((R, R)-N-benzenesulfonyl-1,2-diphenylethylenediamine)(η 6 -benzene)ruthenium) RuH[(S, S)-C 6 H 5 SO 2 NCH(C 6 H 5 )CH(C 6 H 5 )NH 2 ](η 6 -p-cymene)(hydride-((S, S)-N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine)(η 6 -p-cymene)ruthenium) RuH[(R, R)-C 6 H 5 SO 2 NCH(C 6 H 5 )CH(C 6 H 5 )NH 2 ](η 6 -p-cymene)(hydride-((R, R)-N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine) (η 6 -p-cymene)ruthenium) RuH[(S, S)-C 6 H 5 SO 2 NCH(C 6 H 5 )CH(C 6 H 5 )NH 2 ](η 6 -mesitylene)(hydride-((S, S)-N-benzenesulfonyl-1,2-diphenylethylenediamine) (η 6 -mesitylene)ruthenium) RuH[(R, R)-C 6 H 5 SO 2 NCH(C 6 H 5 )CH(C 6 H 5 )NH 2 ](η 6 -mesitylene)(hydride-((R, R)-N-benzenesulfonyl-1,2-diphenylethylenediamine)(η 6 -mesitylene)ruthenium) RuH[(S, S)-N-p-Ts-1,2-cyclohexanediamine](η 6 -benzene)(hydride-((S, S)-N-p-toluenesulfonyl-1,2-cyclohexanediamine)(η 6 -benzene)ruthenium) RuH[(R, R)-N-p-Ts-1,2-cyclohexanediamine](η 6 -benzene)(hydride-((R, R)-N-p-toluenesulfonyl-1,2-cyclohexanediamine)(η 6 -benzene)ruthenium) RuH[(S, S)-N-p-Ts-1,2-cyclohexanediamine](η 6 -p-cymene)(hydride-((S, S)-N-p-toluenesulfonyl-1,2-cyclohexanediamine)(η 6 -p-cymene)ruthenium) RuH[(R, R)-N-p-Ts-1,2-cyclohexanediamine](η 6 -p-cymene)(hydride-((R, R)-N-p-toluenesulfonyl-1,2-cyclohexanediamine)(η 6 -p-cymene)ruthenium) RuH[(S, S)-N-p-Ts-1,2-cyclohexanediamine](η 6 -mesitylene)(hydride-((S, S)-N-p-toluenesulfonyl-1,2-cyclohexanediamine)(η 6 -mesitylene)ruthenium) RuH[(R, R)-N-p-Ts-1,2-cyclohexanediamine](η 6 -mesitylene) (hydride-((R, R)-N-p-toluenesulfonyl-1,2-cyclohexanediamine)(η 6 -mesitylene)ruthenium) RuH[(S, S)-N-Ms-1,2-cyclohexanediamine](η 6 -benzene)(hydride-((S, S)-N-methanesulfonyl-1,2-cyclohexanediamine) (η 6 -benzene)ruthenium) RuH[(R, R)-N-Ms-1,2-cyclohexanediamine](η 6 -benzene)(hydride-((R, R)-N-methanesulfonyl-1,2-cyclohexanediamine) (η 6 -benzene)ruthenium) RuH[(S, S)-N-Ms-1,2-cyclohexanediamine](η 6 -p-cymene)(hydride-((S, S)-N-methanesulfonyl-1,2cyclohexanediamine) (η 6 -p-cymene)ruthenium) RuH[(R, R)-N-Ms-1,2-cyclohexanediamine](η 6 -p-cymene)(hydride-((R, R)-N-methanesulfonyl-1,2-cyclohexanediamine) (η 6 -p-cymene)ruthenium) RuH[(S, S)-N-Ms-1,2-cyclohexanediamine](η 6 -mesitylene)(hydride-((S, S)-N-methanesulfonyl-1,2-cyclohexanediamine) (η 6 -mesitylene) ruthenium) RuH[(R, R)-N-MS-1,2-cyclohexanediamine](η 6 -mesitylene) (hydride-((R, R)-N-methanesulfonyl-1,2-cyclohexanediamine)(η 6 -mesitylene)ruthenium) RuH[(S, S)-N-Tf-1,2-cyclohexanediamine](η 6 -benzene)(hydride-((S, S)-N-trifluoromethanesulfonyl-1,2-cyclohexanediamine)(η 6 -benzene)ruthenium) RuH[(R, R)-N-Tf-1,2-cyclohexanediamine](η 6 -benzene)(hydride-((R, R)-N-trifluoromethanesulfonyl-1,2-cyclohexanediamine) (η 6 -benzene)ruthenium) RuH[(S, S)-N-Tf-1,2-cyclohexanediamine](η 6 -p-cymene)(hydride-((S, S)-N-trifluoromethanesulfonyl-1,2-cyclohexanediamine)(η 6 -p-cymene)ruthenium) RuH[(R, R)-N-Tf-1,2-cyclohexanediamine](η 6 -p-cymene) (hydride-((R, R)-N-trifluoromethanesulfonyl-1,2-cyclohexanediamine)(η 6 -p-cymene) ruthenium) RuH[(S, S)-N-Tf-1,2-cyclohexanediamine](η 6 -mesitylene)(hydride-((S, S)-N-trifluoromethanesulfonyl-1,2-cyclohexanediamine)(η 6 -mesitylene)ruthenium) RuH[(R, R)-N-Tf-1,2-cyclohexanediamine](η 6 -mesitylene) (hydride-((R, R)-N-trifluoromethanesulfonyl-1,2-cyclohexanediamine)(η 6 -mesitylene)ruthenium) RuH[(S, S)-N-C 6 H 5 SO 2 -1,2-cyclohexanediamine](η 6 -benzene)(hydride-((S, S)-N-benzenesulfonyl-1,2-cyclohexanediamine)(η 6 -benzene) ruthenium) RuH[(R, R)-N-C 6 H 5 SO 2 -1,2-cyclohexanediamine](η 6 -benzene) (hydride-((R, R)-N-benzenesulfonyl-1,2-cyclohexanediamine)(η 6 -benzene)ruthenium) RuH[(S, S)-N-C 6 H 5 SO 2 -1,2-cyclohexanediamine](η 6 -p-cymene)(hydride-((S, S)-N-benzenesulfonyl-1,2-cyclohexanediamine)(η 6 -p-cymene) ruthenium) RuH[(R, R)-N-C 6 H 5 SO 2 -1,2-cyclohexanediamine](η 6 -p-cymene)(hydride-((R, R)-N-benzeneesulfonyl-1,2-cyclohexanediamine)(η 6 -p-cymene)ruthenium) RuH[(S, S)-N-C 6 H 5 SO 2 -1,2-cyclohexanediamine](η 6 -mesitylene)(hydride-((S, S)-N-benzenesulfonyl-1,2-cyclohexanediamine) (η 6 -mesitylene)ruthenium) RuH[(R, R)-N-C 6 H 5 SO 2 -1,2-cyclohexanediamine](η 6 -mesitylene)(hydride-((R, R)-N-benzenesulfonyl-1,2-cyclohexanediamine) (η 6 -mesitylene)ruthenium) Among the compounds represented by the general formula (VII) in accordance with the present invention, the complex of the formula (VII) wherein m and n are simultaneously 0 can be produced as follows. More specifically, Ru[(S, S)-, (R, R)-TsNCH(R 01 )CH(R 02 ) NH[(η 6 -p-cymene)(((S, S) and (R, R)-N-toluenesulfonyl-1,2-disubstituted ethylenediamine)(η 6 -p-cymene)ruthenium (wherein R 01 and R 02 are the same as described above and Ts is p-toluenesulfonyl group), is readily synthesized by reacting a raw material [RuCl 2 (η 6 -p-cymene) 2 (tetrachlorobis(η 6 -p-cymene)diruthenium) prepared by the method described in a reference J. Chem. Soc., Dalton Trans., pp.233-241(1974) with (S, S)-, (R, R)-TSNHCH(R 01 )CH(R 02 )NH 2 ((S, S) and (R, R)-N-p-toluenesulfonyl-1,2-disubstituted ethylenediamine) in the presence of alkali metal hydroxide or alkali metal alcolate in a solvent. The reaction is generally carried out quantitatively, by reacting a raw material [RuCl 2 (η 6 -p-cymene)] 2 (tetrachlorobis(η 6 -p-cymene)diruthenium (1 mole) and (S, S)-, (R, R)-TsNHCH(R 01 )CH(R 02 )NH,(((S, S) and (R, R)-N-p-toluenesulfonyl-1,2-disubstituted ethylenediamine)(2 moles) with alkali metal hydroxide or alkali metal alcolate in the stream of inactive gases such nitrogen, helium or argon in an inactive solvent at a temperature of −10 to 50° C. for 30 minutes to 3 hours, and leaving the reaction product to stand alone, prior to liquid separation procedure to remove the aqueous phase, and subsequently removing the solvent under reduced pressure. The alkali metal hydroxide or alkali metal alcolate specifically includes NaOH, NaOCH 3 , NaOC 2 H 5 , KOH, KOCH 3 , KOC 2 H 5 , LiOH, LiOCH 3 , and LiOC 2 H 5 , preferably including NaOH or KOH. The amount of the alkali metal hydroxide or alkali metal alcolate is 5 to 10 fold the amount of ruthenium. The inactive solvent appropriately includes for example hydrocarbons such as benzene, toluene, xylene, cyclohexane, and methylcyclohexane; ethers such as dimethyl ether, diethyl ether, diisopropyl ether, methyl-tert-butyl ether, tetrahydrofuran, 1,3-dioxolanee, and 1,4-dioxane; halogenated hydrocarbons such as chloroform, methylene chloride and chlorobenzene. The complex can be produced by another method. Specifically, Ru[(S, S)-, (R, R)-TsNCH(R 01 )CH(R 02 )NH](η 6 -p-cymene)(((S, S) and (R, R)-N-toluenesulfonyl-1,2-disubstituted ethylenediamine)(η 6 -p-cymene)ruthenium (wherein R 01 and R 02 are the same as described above and Ts is p-toluenesulfonyl group), is readily synthesized by reacting a raw material RuCl[(S, S)-, (R, R)- TsNCH(R 01 )CH(R 02 )NH 2 ](η 6 -p-cymene)(chloro-((S, S) and (R, R)-N-p-toluenesulfonyl-1,2-disubstituted ethylenediamine)(η 6 -p-cymene)ruthenium prepared through the reaction of [RUCl 2 (η 6 -p-cymene) 2 (tetrachlorobis(η 6 -p-cymene)diruthenium, (S, S)-, (R, R)-TsNHCH(R 01 )CH(R 02 )NH 2 ((S, S) and (R, R)-N-p-toluenesulfonyl-1,2-disubstituted ethylenediamine) with a tertiary amine (for example, triethylamine) for example by the method described in J. Am. Chem. Soc., Vol.117, pp.7562-7563 (1995), J. Am. Chem. Soc., Vol.118, pp.2521-2522 (1996) and J. Am. Chem. Soc., Vol.118, pp.4916-4917 (1996), in the presence of alkali metal hydroxide or alkali metal alcolate in a solvent. The reaction is generally carried out quantitatively, by reacting a raw material RUCl[(S, S)-, (R, R)-TsNCH(R 01 )CH(R 02 )NH 2 ](η 6 -p-cymene)(chloro-((S, S) and (R, R)-N-p-toluenesulfonyl-1,2-disubstituted ethylenediamine) (η 6 -p-cymene)ruthenium) (1 mole) with alkali metal hydroxide or alkali metal alcolate in the stream of inactive gases such nitrogen, helium or argon in an inactive solvent at a temperature of −10 to 50° C. for 30 minutes to 3 hours, and leaving the reaction product to stand alone, prior to liquid separation procedure to remove the aqueous phase, and subsequently removing the solvent under reduced pressure. The alkali metal hydroxide or alkali metal alcolate specifically includes NaOH, NaOCH 3 , NAOC 2 H 5 , KOH, KOCH 3 , KOC 2 H 5 , LiOH, LiOCH 3 , and LiOC 2 H 5 , preferably including NaOH or KOH. The amount of the alkali metal hydroxide or alkali metal alcolate is 1 to 2-fold in mole the amount of ruthenium. The inactive solvent appropriately includes for example hydrocarbons such as benzene, toluene, xylene, cyclohexane, and methylcyclohexane; ethers such as dimethyl ether, diethyl ether, diisopropyl ether, methyltert-butyl ether, tetrahydrofuran, 1,3-dioxolane, and 1,4,-dioxane; and halogenated hydrocarbons such as chloroform, methylene chloride and chlorobenzene. In accordance with the present invention, the complex represented by the general formula (V) wherein m and n are simultaneously 1 can be produced as follows. More specifically, RuH[(S, S)-, (R, R)-TsNCH(R 01 )CH(R 02 )NH 2 ](η 6 -p-cymene)(hydride-((S, S) and (R, R)-N-toluenesulfonyl-1,2-disubstituted ethylenediamine) (η 6 -p-cymene)ruthenium) (wherein R 01 and R 02 are the same as described above and Ts is p-toluenesulfonyl group), is readily synthesized, by reacting a raw material Ru[(S, S)-, (R, R)-TSNCH(R 01 )CH(R 02 )NH] (η 6 -p-cymene)(((S, S) and (R, R)-N-toluenesulfonyl-1,2-disubstituted ethylenediamine) (η 6 -p-cymene) ruthenium)(wherein R 01 and R 02 are the same as defined above; and Ts represents p-toluenesulfonyl group) in an alcohol solvent. The reaction is generally carried out quantitatively, by reacting a raw material Ru[(S, S)-, (R, R)-TsNCH(R 01 )CH(R 02 )NH] (η 6 -p-cymene)(((S, S) and (R, R)-N-toluenesulfonyl-1,2-disubstituted ethylenediamine) (η 6 -p-cymene)ruthenium) (wherein R 01 and R 02 are the same as defined above; and Ts represents p-toluenesulfonyl group) in an inactive gas stream in an alcohol solvent at a temperature of 0 to 100° C. for 3 minutes to 1 hour for hydrogen transfer reaction, and subsequently removing the solvent under reduced pressure. Appropriate alcohol solvents include for example methanol, ethanol, n-propanol, isopropanol, n-butanol, iso-butanol, and sec-butanol. The complex can be produced by another method. Specifically, RuH[(S, S)-, (R, R)-TSNCH(R 01 )CH(R 02 )NH 2 ](η 6 -p-cymene)(hydride-((S, S) and (R, R)-N-p-toluenesulfonyl-1,2-disubstituted ethylenediamine) (η 6 -p-cymene)ruthenium) (wherein R 01 and R 02 are the same as described above and Ts is p-toluenesulfonyl group), is readily synthesized, by reacting for example a raw material Ru[(S, S)-, (R, R)-TsNCH(R 01 )CH(R 02 )NH] (η 6 -p-cymene)(((S, S) and (R, R)-N-toluenesulfonyl-1,2-disubstituted ethylenediamine) (η 6 -p-cymene) ruthenium) (wherein R 01 and R 02 are the same as defined above; and Ts represents p-toluenesulfonyl group), in a solvent in pressurized hydrogen. The reaction is generally carried out quantitatively, by hydrogenating a raw material RuH[(S, S)-, (R, R)-TsNCH(R 01 )CH(R 02 )NH 2 (η 6 -p-cymene)(hydride-((S, S) and (R, R)-N-toluenesulfonyl-1,2-disubstituted ethylenediamine) (η 6 -p-cymene)ruthenium)(wherein R 01 and R 02 are the same as defined above; and Ts represents p-toluenesulfonyl group), in an inactive solvent at a temperature of 0 to 50° C. for 30 minutes to 24 hours (preferably 1 to 10 hours) in pressurized hydrogen and subsequently removing the solvent under reduced pressure. The hydrogen pressure is within a range of 1 to 150 atm, preferably 20 to 100 atm. Appropriate inactive solvents include for example hydrocarbons such as benzene, toluene, xylene, hexane, heptane, cyclohexane, and methylcyclohexane; and ethers such as dimethyl ether, diethyl ether, diisopropyl ether, methyl-tert-butyl ether, tetrahydrofuran, 1,3-dioxolane and 1,4-dioxane. An optically active diamine of the formula (S, S)-, (R, R)-R 03 NHCH(R 01 )CH(R 02 )NH 2 ((S, S) and (R, R)-N-substituted-1,2-disubstituted ethylenediamines) (wherein R 01 R 02 and R 03 are the same as described above) is synthesized, by using raw materials (S, S)-, (R, R)-NH 2 CH(R 01 )CH(R 02 )NH 2 ((S, S) and (R, R)-1,2-disubstituted ethylenediamines in a conventional manner [Protective Groups in Organic Synthesis, Vol.2, pp.309-405(1991)]. More specifically, (S, S)-, (R, R)-TsNHCH(R 01 )CH(R 02 )NH 2 ((S, S) and (R, R)-N-P-toluenesulfonyl-1,2-disubstituted ethylenediamines) (wherein R 01 and R 02 are the same as defined above; and Ts represents p-toluenesulfonyl group) are readily synthesized, by reacting for example (S, S)-, (R, R)-NH 2 CH(R 01 )CH(R 02 )NH 2 ((S, S) and (R, R)-1,2-disubstituted ethylenediamines) as raw materials with TsCl (p-toluenesulfonyl chloride) in the presence of an alkali (for example, tertiary amine, alkali metal salts and the like) in a solvent. The reaction is generally carried out quantitatively, by reacting together (S, S)-, (R, R)-NH 2 CH(R 01 )CH(R 02 )NH 2 ((S, S) and (R, R)-1,2-disubstituted ethylenediamines) (1 mole) and TsCl (p-toluenesulfonyl chloride) (1 mole) with an alkali (for example, triethylamine) in an inactive solvent (for example, toluene, tetrahydrofuran, and methylene chloride) in an inactive gas stream such as nitrogen, helium or argon or the like at a temperature of 0 to 50° C. for 30 minutes to 3 hours, subsequently adding water to the resulting mixture to gently leave the reaction product to stand, prior to liquid separation procedure, to remove the aqueous phase, and evaporating the solvent under reduced pressure. The optically active diamine (S, S)-, (R, R)—NH 2 CH(R 01 )CH(R 02 )NH 2 ((S, S) and (R, R)-1,2-disubstituted ethylenediamines)(wherein R 01 and R 02 are the same as defined above), is known and is sometimes commercially available or can be produced in a conventional manner or by conventional resolution process of racemates (Tetrahedron Lett., Vol.32, pp.999-1002) (1991), Tetrahedron Lett., Vol.34, pp.1905-1908 (1993)]. (S, S) and (R, R)-1,2-diphenylethylenediamines and (S, S) and (R, R)-1,2-cyclohexanediamines are commercially available. For example, the optically active diamine of the general formula (e) can be produced by the following method (Tetrahedron Lett., Vol.32, pp.999-1002 (1991)]. The optically active diamine of the general formula (e) ((S, S) and (R, R)-1,2-disubstituted ethylenediamines) can be produced readily at a high yield, by preparing cyclophosphate from raw materials optically active 1,2-disubstituted ethylene diols, which is then reacted with amidine to recover imidazoline, and ring opening the imidazoline by using an acid catalyst. The ruthenium-diamine complex of the present invention may be isolated and used, but while generating the complex in a reaction solution, the resulting complex is used as a catalyst for asymmetric synthesis and the like. The method for producing optically active secondary alcohols by utilizing the complex of the present invention as a hydrogen transfer-type oxidation catalyst will now be described below. The racemic secondary alcohols or meso-type diols to be used as the reaction substrates for producing optically active secondary alcohols are represented by the aforementioned formulas (VIII) and (IXI). In the formula (VIII), the racemic secondary alcohols in this case specifically include 1-phenylethanol, 1-(2-methylphenyl)ethanol, 1-(2-ethylphenyl)ethanol, 1-(2-isopropylphenyl)ethanol, 1-(2-tert-butylphenyl)ethanol, 1-(2-methoxyphenyl)ethanol, 1-(2-ethoxyphenyl)ethanol, 1-(2-isopropoxyphenyl)ethanol, 1-(2-tert-butoxyphenyl)ethanol, 1-(2-dimethylaminophenyl)ethanol, 1-(3-methylphenyl)ethanol, 1-(3-ethylphenyl)ethanol, 1-(3-isopropylphenyl)ethanol, 1-(3-tert-butylphenyl)ethanol, 1-(3-methoxyphenyl)ethanol, 1-(3-ethoxyphenyl)ethanol, 1-(3-isopropoxyphenyl)ethanol, 1-(3-tert-butoxyphenyl)ethanol, 1-(3-dimethylaminophenyl)ethanol, 1-(4-methylphenyl)ethanol, 1-(4-ethylphenyl)ethanol, 1-(4-isopropylphenyl)ethanol, 1-(4-tert-butylphenyl)ethanol, 1-(4-methoxyphenyl)ethanol, 1-(4-ethoxyphenyl)ethanol, 1-(4-isopropoxyphenyl)ethanol, 1-(4-tert-butoxyphenyl)ethanol, 1-(4-dimethylaminophenyl)ethanol, 1-cumenylethanol, 1-mesitylethanol, 1-xylylethanol, 1-(1-naphthyl)ethanol, 1-(2-naphthyl)ethanol, 1-phenanthrylethanol, 1-indenylethanol, 1-(3,4-dimethoxyphenyl)ethanol, 1-(3,4-diethoxyphenyl)ethanol, 1-(3,4-methylenedioxyphenyl)ethanol, 1-ferrocenylethanol, 1-phenylpropanol, 1-(2-methylphenyl)propanol, 1-(2-ethylphenyl)propanol, 1-(2-isopropylphenyl)propanol, 1-(2-tert-butylphenyl)propanol, 1-(2-methoxyphenyl)propanol, 1-(2-ethoxyphenyl)propanol, 1-(2-isopropoxyphenyl)propanol, 1-(2-tert-butoxyphenyl)propanol, 1-(2-dimethylaminophenyl)propanol, 1-(3-methylphenyl)propanol, 1-(3-ethylphenyl)propanol, 1-(3-isopropylphenyl)propanol, 1-(3-tert-butylphenyl)propanol, 1-(3-methoxyphenyl)propanol, 1-(3-ethoxyphenyl)propanol, 1-(3-isopropoxyphenyl)propanol, 1-(3-tert-butoxyphenyl)propanol, 1-(3-dimethylaminophenyl)propanol, 1-(4-methylphenyl)propanol, 1-(4-ethylphenyl)propanol, 1-(4-isopropylphenyl)propanol, 1-(4-tert-butylphenyl)propanol, 1-(4-methoxyphenyl)propanol, 1-(4-ethoxyphenyl)propanol, 1-(4-isopropoxyphenyl)propanol, 1-(4-tert-butoxyphenyl)propanol, 1-(4-dimethylaminophenyl)propanol, 1-cumenylpropanol, 1-mesitylpropanol, 1-xylylpropanol, 1-(1-naphthyl) propanol, 1-(2-naphthyl)propanol, 1-phenanthrylpropanol, 1-indenylpropanol, 1-(3,4-dimethoxyphenyl) propanol, 1-(3,4-diethoxyphenyl) propanol, 1-(3,4-methylenedioxyphenyl) propanol, 1-ferrocenylpropanol, 1-phenylbutanol, 1-(2-methylphenyl)butanol, 1-(2-ethylphenyl)butanol, 1-(2-isopropylphenyl)butanol, 1-(2-tert-butylphenyl)butanol, 1-(2-methoxyphenyl)butanol, 1-(2-ethoxyphenyl)butanol, 1-(2-isopropoxyphenyl)butanol, 1-(2-tert-butoxyphenyl)butanol, 1-(2-dimethylaminophenyl)butanol, 1-(3-methylphenyl)butanol, 1-(3-ethylphenyl)butanol, 1-(3-isopropylphenyl)butanol, 1-(3-tert-butylphenyl)butanol, 1-(3-methoxyphenyl)butanol, 1-(3-ethoxyphenyl)butanol, 1-(3-isopropoxyphenyl)butanol, 1-(3-tert-butoxyphenyl)butanol, 1-(3-dimethylaminophenyl)butanol, 1-(4-methylphenyl)butanol, 1-(4-ethylphenyl)butanol, 1-(4-isopropylphenyl)butanol, 1-(4-tert-butylphenyl)butanol, 1-(4-methoxyphenyl)butanol, 1-(4-ethoxyphenyl)butanol, 1-(4-isopropoxyphenyl)butanol, 1-(4-tert-butoxyphenyl)butanol, 1-(4-dimethylaminophenyl)butanol, 1-cumenylbutanol, 1-mesitylbutanol, 1-xylylbutanol, 1-(1-naphthyl)butanol, 1-(2-naphthyl)butanol, 1-phenanthrylbutanol, 1-indenylbutanol, 1-(3,4-dimethoxyphenyl)butanol, 1-(3,4-diethoxyphenyl)butanol, 1-(3,4-methylenedioxyphenyl)butanol, 1-ferrocenylbutanol, 1-phenylisobutanol, 1-(2-methylphenyl)isobutanol, 1-(2-ethylphenyl)isobutanol, 1-(2-isopropylphenyl)isobutanol, 1-(2-tert-butylphenyl)isobutanol, 1-(2-methoxyphenyl)isobutanol, 1-(2-ethoxyphenyl)isobutanol, 1-(2-isopropoxyphenyl)isobutanol, 1-(2-tert-butoxyphenyl)isobutanol, 1-(2-dimethylaminophenyl)isobutanol, 1-(3-methylphenyl)isobutanol, 1-(3-ethylphenyl)isobutanol, 1-(3-isopropylphenyl)isobutanol, 1-(3-tert-butylphenyl)isobutanol, 1-(3-methoxyphenyl)isobutanol, 1-(3-ethoxyphenyl)isobutanol, 1-(3-isopropoxyphenyl)isobutanol, 1-(3-tert-butoxyphenyl)isobutanol, 1-(3-dimethylaminophenyl)isobutanol, 1-(4-methylphenyl)isobutanol, 1-(4-ethylphenyl)isobutanol, 1-(4-isopropylphenyl)isobutanol, 1-(4-tert-butylphenyl)isobutanol, 1-(4-methoxyphenyl)isobutanol, 1-(4-ethoxyphenyl)isobutanol, 1-(4-isopropoxyphenyl)isobutanol, 1-(4-tert-butoxyphenyl)isobutanol, 1-(4-dimethylaminophenyl)isobutanol, 1-cumenylisobutanol, 1-mesitylisobutanol, 1-xylylisobutanol, 1-(1-naphthyl)isobutanol, 1-(2-naphthyl)isobutanol, 1-phenanthrylisobutanol, 1-indenylisobutanol, 1-(3,4-dimethoxyphenyl)isobutanol, 1-(3,4-diethoxyphenyl)isobutanol, 1-(3,4-methylenedioxyphenyl)isobutanol, 1-ferrocenylisobutanol, 1-phenylpentanol, 1-(2-methylphenyl)pentanol, 1-(2-ethylphenyl)pentanol, 1-(2-isopropylphenyl)pentanol, 1-(2-tert-butylphenyl)pentanol, 1-(2-methoxyphenyl)pentanol, 1-(2-ethoxyphenyl)pentanol, 1-(2-isopropoxyphenyl)pentanol, 1-(2-tert-butoxyphenyl)pentanol, 1-(2-dimethylaminophenyl)pentanol, 1-(3-methylphenyl)pentanol, 1-(3-ethylphenyl)pentanol, 1-(3-isopropylphenyl)pentanol, 1-(3-tert-butylphenyl)pentanol, 1-(3-methoxyphenyl)pentanol, 1-(3-ethoxyphenyl)pentanol, 1-(3-isopropoxyphenyl)pentanol, 1-(3-tert-butoxyphenyl)pentanol, 1-(3-dimethylaminophenyl)pentanol, 1-(4-methylphenyl)pentanol, 1-(4-ethylphenyl)pentanol, 1-(4-isopropylphenyl)pentanol, 1-(4-tert-butylphenyl)pentanol, 1-(4-methoxyphenyl)pentanol, 1-(4-ethoxyphenyl)pentanol, 1-(4-isopropoxyphenyl)pentanol, 1-(4-tert-butoxyphenyl)pentanol, 1-(4-dimethylaminophenyl)pentanol, 1-cumenylpentanol, 1-mesitylpentanol, 1-xylylpentanol, 1-(1-naphthyl)pentanol, 1-(2-naphthyl)pentanol, 1-phenanthrylpentanol, 1-indenylpentanol, 1-(3,4-dimethoxyphenyl)pentanol, 1-(3,4-diethoxyphenyl)pentanol, 1-(3,4-methylenedioxyphenyl)pentanol, 1-ferrocenylpentanol, 1-indanol, 1, 2, 3, 4-tetrahydro-1-naphthol, 2-cyclopenten-1-ol, 3-methyl-2-cyclopenten-1-ol, 2-cyclohexen-1-ol, 3-methyl-2-cyclohexen-1-ol, 2-cycloheptan-1-ol, 3-methyl-2-cycloheptan-1-ol, 2-cyclooctan-1-ol, 3-methyl-2-cyclooctan-1-ol, and 4-hydroxy-2-cyclopenten-1-one. Additionally, the meso-type diol represented by the formula (IX) specifically represents meso-2-cyclopenten-1,4-diol, meso-2-cyclohexane-1,4-diol, meso-2-cycloheptane-1,4-diol, meso-2-cyclooctan-1,4-diol, 5,8-dihyroxy-1,4,4a, 5, 8, 8a-hexahydro-endo-1,4-methanonaphtharene and the like. As the ruthenium-diamine complex to be used for the hydrogen transfer-type oxidation of the present invention, the optically active ligand diamine of the general formula (VII), namely (R, R) form or (S, S) form, may satisfactorily be used. Depending on the selection, an objective compound of the desired absolute configuration can be produced. Such ruthenium-diamine complex can be used at 1/10,000 to 1/10 fold in mole, preferably 1/2,000 to 1/200 fold in mole to the substrate compound. For carrying out the reaction, the substrate compound and the ruthenium-diamine complex are added to ketone alone or an appropriate mixture of ketone with an inactive solvent, to prepare a homogenous solution, for reaction at a reaction temperature of 0 to 100° C., preferably 10 to 50° C., for 1 to 100 hours, preferably 3 to 50 hours. Ketones including for example acetone, ketone, diethyl ketone, diisopropyl ketone, methyltert-butyl ketone, cyclopentanone, and cyclohexanone are used. More preferably, acetone is better. These ketones may satisfactorily be used singly or in a mixture with an inactive solvent. Ketones can be used at an amount of 0.1 to 30 fold (volume/weight), depending on the type of the substrate, but preferably at an amount of 2,to 5 fold (volume/weight). Appropriate inactive solvents include for example hydrocarbons such as benzene, toluene, xylene, hexane, heptane, cyclohexane, and methylcyclohexane; and ethers such as dimethyl ether, diethyl ether, diisopropyl ether, methyltert-butyl ether, tetrahydrofuran, 1,3-dioxolane, and 1,4-dioxane. In accordance with the present invention, the reaction may be carried out in a batchwise manner or a continuous manner. The resulting product can be purified by known processes such as silica gel column chromatography. EXAMPLES Example A Production of Optically Active Alcohols Production examples of optically active alcohols are shown below, and the inventive method will further be described in detail. Tables 1, 2 and 3 collectively show reaction substrates, transition metal complexes and optically active amine compounds as chiral ligands, which are to be used as typical examples. The instrumental analysis was done by using the following individual systems. NMR: JEOL GSX-400/Varian Gemini-200 ( 1 H-NMR sample: TMS, 31 P-NMR standard sample phosphoric acid) GLC: SHIMADZU GC-17A(column: chiral CP-Cyclodextrin-b-236-M19) HPLC: JASCO GULLIVER (column: CHIRALCEL OJ, OB-H, OB, OD) TABLE 1 Carbonyl compounds TABLE 2 Asymmetric metal complexes TABLE 3 Examples 1 through 19 To dry 2-propanol (5.0 ml) were added various amino alcohol compounds (0.05 mmol) as chiral ligands of optically active amine compounds as shown in Table 3 and the ruthenium arene complex (0.0125 mmol) shown in Table 2, for agitation in argon or nitrogen gas atmosphere at 80° C. for 20 minutes, and the resulting mixture was cooled to room temperature, to which were then added frozen and degassed dry 2-propanol (45.0 ml), various carbonyl compounds (5 mmol) deaerated and distilled as shown in Table 1, and a solution of 0.05M KOH in 2-propanol (2.5 ml; 0.125 mmol) in this order, for subsequent agitation at room temperature. After completion of the reaction, dilute hydrochloric acid was added to adjust the resulting mixture to acidity, from which most of 2-propanol was evaporated off under reduced pressure, followed by addition of saturated sodium chloride solution. The resulting product was extracted into ethyl acetate, rinsed with saturated sodium chloride solution several times and dried over anhydrous sodium sulfate. The solvent was distilled off from the product. The final product was analyzed by 1 H-NMR (CDC 3 ), to calculate the conversion. Then, the product was purified by thin-layer silica gel chromatography, and the isolated alcohol fraction was used to determine the optical purity and absolute configuration by HPLC or GLC. The results are collectively shown in Table 4. Furthermore, the conversion and optical purity of the sampled reaction solution can be calculated simultaneously by GLC. Examples 20 to 23 Using the same method as in Example 1, aminophosphine compound was used as an optically active amine compound for the reaction. The results are collectively shown in Table 4. TABLE 4 Exam- [RuCl 2 Li- Carbonyl % ples (arene)] 2 gands compounds Time conv % ee config. 1 13 19 1a 1 64 52 S 2 13 20 1a 1 91 17 S 3 14 20 1a 1 97 59 S 4 14 21 1a 1 97 56 S 5 15 20 1a 1 97 56 S 6 15 21 1a 1 62 52 S 7 16 17 1a 1 95 91 S 8 16 20 1a 1 94 92 S 9 16 21 1a 1 59 55 S 10 16 22 1a 1 96 75 S 11 16 20 1b 2 95 82 S 12 16 20 1c 15 93 5 S 13 16 20 1d 20 22 40 R 14 16 20 o-1e 6 96 83 S 15 16 18 o-1f 1 99 89 S 16 16 20 p-1g 4 73 79 S 17 16 20 3 2 99 93 S 18 16 18 4 3 93 75 S 19 16 16 7 4 62 94 S 20 13 23 1a 1 65 0.4 S 21 13 24 1a 1 61 61 R 22 13 25 1a 1 70 23 13 26 1a 1 73 4 S Examples 24 to 41 By using the same method as described in Example 1 and using optically active amine compounds, the chiral Ru complexes shown in Table 2 were synthesized. The complex catalysts and carbonyl compounds were added to a mixture of formic acid and triethylamine (5:2), for reaction at room temperature for a given period. After completion of the reaction, the reaction mixture was diluted with water, to extract the product in ethyl acetate. After drying the organic phase over anhydrous sodium sulfate and evaporating the solvent off, 1 H-NMR (CDCl 3 ) was analyzed to calculate the conversion. The optical purity and absolute configuration were determined by HPLC or GLC. The results are collectively shown in Table 5. The conversion and optical purity of each sampled reaction solution can be calculated simultaneously by GLC. In accordance with the present invention, optically active alcohols can be produced at a high optical purity and a high synthetic yield. TABLE 5 Carbonyl Examples Ru complex compounds Time % conv % ee config. 24 27(S, S) 1a 24 >99 98 S 25 27(S, S) 1b 60 >99 97 S 26 27(S, S) m-1f 21 >99 97 S 27 27(S, S) p-1f 24 >99 95 S 28 27(S, S) m-1g 20 >99 98 S 29 27(S, S) p-1g 50 >99 97 S 30 27(S, S) p-1h 14 >99 90 S 31 27(S, S) 1i 60 >99 95 S 32 27(S, S) 2 60 93 83 S 33 27(S, S) 3 22 >99 96 S 34 27(S, S) 5 60 >54 66 S 35 27(S, S) 6 48 >99 99 S 36 27(S, S) 7 48 >99 99 S 37 27(S, S) 8 60 70 82 S 38 27(S, S) 9 40 47 97 S 39 28(R, R) 10 40 95 99 R 40 28(R, R) 11 65 95 98 R 41 28(R, R) 12 72 68 92 R Example B Production of Optically Active Amines Production examples of optically active amines are shown below and the present inventive method will be described in detail. Tables 6 and 7 show reaction substrates and asymmetric metal catalysts to be possibly used as typical examples. The instrumental analysis was done by using the following individual systems. NMR: JEOL GSX-400/Varian Gemini-200 ( 1 H-NMR sample: TMS, 31 P-NMR standard sample: phosphoric acid) GLC: SHIMADZU GC-17A(column: chiral CP-Cyclodextrin-b-236-M19) HPLC: JASCO GULLIVER (column: CHIRALCEL OJ, OB-H, OB, OD) The absolute configurations of the resulting optically active amine compounds were determined on the basis of optical rotation and by HPLC and X-ray structural analysis. Blanks are not definitely shown. TABLE 6 Imine compounds Enamine compounds TABLE 7 Asymmetric metal complexes Example 42 6,7-Dimethoxy-1-methyl-3,4-dihydroxyisoquinoline (Table 6-2a) (1.03 g, 5 mmol) and a ruthenium catalyst (Table 7) (R, R)-1a (16 mg, 0.025 mmol) were dissolved in acetonitrile (10 ml), followed by addition of a mixture of formic acid-triethylamine (5:2), for agitation at 28° C. for 3 hours. To the reaction mixture was added an aqueous sodium carbonate solution to extract the product in ethyl acetate. After evaporation of the solvent, 1 H-NMR(CDCl 3 ) of the resulting product was measured to calculate the conversion. Then, the product was purified by silica gel chromatography, to determine the optical purity and absolute configuration of the resulting optically active amine by HPLC or GLC. As collectively shown in Table 8, (S)-6,7-dimethoxy-1-methyl-1,2,3,4-tetrahydroisoquinoline (1.02 g, yield of 99%, 96% ee) was obtained. Examples 43 to 69 By using the same reactor as in Example 42 but using different reaction substrates, catalysts, reaction solvents and ratios of reaction substrates/catalysts, the same experimental procedures as in Example 42 were carried out. The results are collectively shown in Table 8. Example 70 Using the same reactor as in Example 42, the enamine compound was used for the same experimental procedures as in Example 42, so that the reaction progressed in a smooth manner, to recover the corresponding optically active amine compound. The results are collectively shown in Table 8. Comparative Example 1 Under the same conditions as in Example 42, ruthenium-arene catalysts with no optically active amine ligands were used as catalysts, so that the reaction was facilitated, to recover a racemic amine compound quantitatively. Comparative Example 2 Under the same conditions as in Example 51, ruthenium-arene catalysts with no optically active amine ligands were used as catalysts, so that no reaction was never facilitated. As has been described above in detail, in accordance with the present invention, optically active amines can be produced at a high yield and an excellent optical purity. TABLE 8 Amines yield ee absolute Examples Imines Catalysts S/C Solvents Time, h % % configuration 42 2a (R,R)-1a 200 CH 2 CN 3 99 96 S 43 2a (R,R)-1a 200 CH 2 Cl 2 3 99 94 S 44 2a (S,S)-1a 200 CH 2 Cl 2 3 99 93 R 45 2a (R,R)-1a 200 acetone 3 99 95 S 46 2a (R,R)-1a 200 DMF 3 99 95 S 47 2a (R,R)-1a 200 DMSO 3 99 95 S 48 2a (R,R)-1a 1000 CH 2 Cl 2 98 99 90 S 49 2b (S,S)-1a 200 CH 2 Cl 2 8 81 87 R 50 2c (S,S)-1b 200 CH 2 Cl 2 16 99 92 R 51 2d (S,S)-1c 200 CH 2 Cl 2 8 99 84 R 52 2e (S,S)-1c 100 CH 2 Cl 2 12 96 84 R 53 2f (R,R)-1e 200 CH 2 Cl 2 18 68 82 54 2g (R,R)-1e 200 CH 2 Cl 2 14 94 98 55 3 (S,S)-1a 200 CH 2 Cl 2 16 99 84 56 4a (S,S)-1a 200 DMF 5 86 97 R 57 4b (S,S)-1a 200 DMF 5 83 96 R 58 5 (R,R)-1e 200 CH 2 Cl 2 48 59 78 59 6 (S,S)-1c 200 CH 2 Cl 2 39 22 47 S 60 7 (S,S)-1c 200 CH 2 Cl 2 40 100  34 61 8 (S,S)-1c 100 CH 2 Cl 2 6 90 89 S 62 9 (S,S)-1c 100 CH 2 Cl 2 12 64 88 S 63 10  (S,S)-1d 200 CH 2 Cl 2 36 72 77 S 64 11  (R,R)-1e 200 CH 2 Cl 2 15 13 36 65 12a (R,R)-1e 200 CH 2 Cl 2 37 43 46 66 12b (R,R)-1e 200 CH 2 Cl 2 109 35 36 67 12c (R,R)-1e 200 CH 2 Cl 2 65 67 25 68 13  (S,S)-1c 200 CH 2 Cl 2 16 82 64 69 14  (S,S)-1e 200 CH 2 Cl 2 67 71 12 R 70 15  (S,S)-1e 200 CH 2 Cl 2 12 69 43 [In the table, s/c means the molar ratio of substrate/ruthenium-optically active diamine complex.] Example C Production of Optically Active Secondary Alcohols by Kinetic Resolution Method of Alcohols Production examples of optically active secondary alcohols are shown below, and the inventive method will further be described in detail. However, the invention is not limited to these examples. Collectively, Table 9 shows racemic secondary alcohols or meso-type diols to be used as typical examples and Table 10 shows ruthenium-diamine complexes. Abbreviations used in the present Example are as follows. η:representing the number of carbon atoms bonded to the metal of unsaturated ligand; and hexahapto (6 carbon atoms bonded to metal) is expressed as η 6 . The instrumental analysis was done by using the following individual systems. NMR: JEOL GSX-400/Varian Gemini-200 ( 1 H-NMR internal standard: TMS) GLC: SHIMADZU GC-17A(column: chiral CP-cyclodextrin-b-236-M19) HPLC: JASCO GULLIVER (column: CHIRALCEL OJ, OB-H, OB, OD-H, OD) 81 TABLE 9 TABLE 10 Reference Example 1 Synthesis of RuCl[(S, S)-p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH 2 ](η 6 -p-cymene)(chloro((S, S)-N-p-toluenesulfonyl-1,2-diphenylethylenediamine)(η 6 -p-cymene)ruthenium [-RuCl 2 (η 6 -p-cymene)] 2 (tetrachlorobis (η 6 -p-cymene)diruthenium) (1.53 g; 2.5 mmol) and (S, S)-p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH 2 ((S, S)-N-p-toluenesulfonyl-1,2-diphenylethylenediamine) (1.83 g; 5.0 mmol) and triethylamine (1.4 ml; 10 mmol) are dissolved in 2-propanol (50 ml) in a Schlenk's reactor which is preliminarily dried in vacuum and of which the inside is then substituted with argon. The reaction solution was agitated at 80° C. for 1 hour and is then condensed, to recover crystal, which was then filtered and rinsed with a small amount of water, followed by drying under reduced pressure to recover orange crystal (2.99 g). The yield is 94%. m.p.>100° C. (decomposed) IR(KBr) [cm −1 ]:3272, 3219, 3142, 3063 3030, 2963, 2874 1 H-NMR (400 MHz, 2 H-chloroform, δ): ppm 1.32 (d, 3H), 1.34 (d, 3H), 2.19 (s, 3H), 2.28 (s, 3H), 3.07 (m, 1H), 3.26 (m, 1H), 3.54 (m, 1H), 3.66 (d, 1H), 5.68 (d, 1H), 5.70 (d, 1H), 5.72 (d, 1H), 5.86 (d, 1H), 6.61 (m, 1H), 6.29-7.20 (m, 14H) Elemental Analysis (C 35 H 35 ClN 2 O 2 Rus) C H N Cl Ru Theoretical values (%) 58.53 5.54 4.40 5.57 15.89 Elemental values (%) 58.37 5.44 4.36 5.75 18.83 The present catalyst was tested by X-ray crystallography. It was indicated that the complex was of a structure satisfying the analysis results. Reference Example 2 Synthesis of RuCl[(S, S)-p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH 2 ](η 6 -Mesitylene)(Chloro((S, S)-N-p-Toluenesulfonyl-1,2-Diphenylethylenediamine) (η 6 -Mesitylene)Ruthenium Instead of [RuCl 2 (η 6 -p-cymene)] 2 (tetrachlorobis(η 6 -p-cymene)diruthenium), [RuCl 2 (η 6 -mesitylene)] 2 (tetrachlorobis(η 6 -mesitylene)diruthenium) was used, and by the same procedures as in the Reference Example 1, the aforementioned catalyst was recovered as orange crystal. The yield was 64%. m.p. 218.6-222.5 (decomposed) 1 H-NMR (400 MHz, 2 H-chloroform, δ): ppm 2.24 (3H), 2.38 (s, 9H), 3.69 (dd, 1H), 3.79 (d, 1H), 3.99 (dd, 1H), 4.19 (brd, 1H), 5.30 (s, 3H), 6.65-6.93 (m, 9H), 7.06-7.15 (m, 3H), 7.35 (d, 2H) Reference Example 3 Synthesis of RuCl[(S, S)-N-p-TS-Cyclohexane-1,2-Diamine](η 6 -p-Cymene)(Chloro-((S, S)-N-p-Toluenesulfonyl-1,2-Cyclohexanediamine)(η 6 -p-Cymene)Ruthenium) Instead of (S, S)-p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH 2 ((S, S)-N-p-toluenesulfonyl-1,2-diphenylethylenediamine), (S, S)-N-p-Ts-cyclohexane-1,2-diamine)((S, S)-N-p-toluenesulfonyl-1,2-cyclohexanediamine) was used, and by the same procedures as in the Reference Example 1, the aforementioned catalyst was recovered as orange crystal. The yield is 60%. Reference Example 4 Synthesis of RuCl[(S, S)-N-p-Ts-Cyclohexane-1,2-Diamine](η 6 -Mesitylene)(Chloro-((S, S)-N-p-Toluenesulfonyl-1,2-Cyclohexanediamine)(η 6 -Mesitylene)Ruthenium Instead of (S, S)-p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH 2 ((S, S)-N-p-toluenesulfonyl-1,2-diphenylethylenediamine), (s, S)-N-p-Ts-cyclohexane-1,2-diamine)((1S, 2S)-N-p-toluenesulfonyl-1,2-cyclohexanediamine) was used, and by the same procedures as in the Reference Example 2, the aforementioned catalyst was recovered as orange crystal. The yield is 58%. Example 71-a Synthesis of Ru[(S, S)-p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH](η 6 -p-Cymene)((S, S)-N-p-Toluenesulfonyl-1,2-Diamine)(η 6 -p- Cymene)Ruthenium) [RuCl 1 (η 6 -p-cymene)] 2 (tetrachlorobis(η 6 -p-cymene)diruthenium) (306.2 mg; 0.5 mmol) and (S, S)-p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH 2 ((S, S)-N-p-toluenesulfonyl-1,2-diphenylethylenediamine) (366.4 mg; 1.0 mmol) and potassium hydroxide (400 mg; 7.1 mmol) are dissolved in methylenechloride (7 ml) in a Schlenk's reactor which is preliminarily dried in vacuum and of which the inside is then substituted with argon. The reaction solution was agitated at room temperature for 5 minutes, and by adding water (7 ml) to the reaction solution, the color of the reaction solution turned from orange to deep purple. The organic phase was separated and rinsed in water (7 ml). The organic phase was dried over calcium hydroxide, from which the solvent was distilled off. Then, the resulting product was dried under reduced pressure, to recover catalyst No.10 of deep purple crystal (522 mg) in Table 10. The yield is 87%. m.p.>80° C. (decomposed) IR(KBr)[cm −1 ]:3289, 3070, 3017, 2968 2920, 2859 1 H-NMR (400 MHz, 2 H-toluene, δ): ppm 1.20 (d, 3H), 1.25 (d, 3H), 2.05 (s, 3H), 2.22 (s, 3H), 2.53 (m, 1H), 4.08 (d, 1H), 4.89 (s, 1H), 5.11 (d, 1H), 5.27 (d, 1H), 5.28 (d, 1H), 5.39 (d, 1H), 5.64 (brd, 1H), 6.87(d, 2H), 7.67 (d, 2H), 7.2-7.7 (m, 10H) Elemental Analysis (C 31 H 34 N 2 O 2 ,RuS) C H N Ru Theoretical values (%) 62.09 5.71 4.67 16.85 Elemental values (%) 62.06 5.77 4.66 16.47 The present catalyst was tested by X-ray crystallography. It was indicated that the complex was of a structure satisfying the analysis results. Example 71-b Alternative Synthesis of Ru[(S, S)-p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH](η 6 -p-Cymene)((S, S)-N-p-Toluenesulfonyl-1,2-Diphenylethylenediamine)(η 6 -p-Cymene)Ruthenium) RuCl[(1S, 2S)-p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH 2 ] (η 6 -p-cymene)(chloro-(1S, 2S)-N-p-toluenesulfonyl-1,2-diphenylethylenediamine)(η 6 -p-cymene)ruthenium) (318.6 mg; 0.5 mmol) and potassium hydroxide (200 mg; 3.5 mmol) are dissolved in methylene chloride (7 ml) in a Shlenk's reactor which is preliminarily vacuum dried and of which the inside is substituted with argon. The reaction solution was agitated at room temperature for 5 minutes, and by adding water (7 ml) to the reaction solution, the color of the reaction solution turned from orange to deep purple. The organic phase was separated and rinsed in water (7 ml). The organic phase was dried over calcium hydroxide, from which the solvent was distilled off. Then, the resulting product was dried under reduced pressure, to recover crystal in deep purple crystal (522 mg). The yield is 87%. Example 72-a Synthesis of Ru[(S, S)-p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH](η 6 -Mesitylene)(((S, S)-N-p-Toluenesulfonyl-1,2-Diphenylethylenediamine) (η 6 -Mesitylene)Ruthenium) Instead of (RuCl 2 (η 6 -p-cymene)] 2 (tetrachlorobis(η 6 -p-cymene)diruthenium), [RuCl 2 (η 6 -mesitylene)] 2 (tetrachlorobis(η 6 -mesitylene)diruthenium) was used, and by the same procedures as in the Example 71-a, the catalyst in purple crystal as No.11 in Table 10 was recovered. The yield is 80%. 1 H-NMR (400 MHz, 2 H-chloroform, δ) ppm 1.91 (s. 9H). 1.99 (s. 3H). 3.83 (d. 1H). 4.51 (s. 1H). 4.95 (s. 3H). 5.92 (brd. 1H). 6.38-7.71 (m. 14H) Example 72-b Alternative Synthesis of Ru((S, S)-p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH](η 6 -Mesitylene)(((S, S)-N-p-Toluenesulfonyl-1,2-Diphenylethylenediamine)(η 6 -Mesitylene)Ruthenium) Instead of RuCl[(S, S)-p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH 2 ](η 6 -p-cymene)(chloro-((S, S)-N-p-toluenesulfonyl-1,2- diphenylethylenediamine)(η 6 -p-cymene)ruthenium), RuCl[(S, S)-p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH 2 ](η 6 -mesitylene)(chloro-((S, S)-N-p-toluenesulfonyl-1,2-diphenylethylenediamine) (η 6 -mesitylene)ruthenium) synthesized as in the Reference Example 2 was used, and by the same procedures as in the Example 71-b, the catalyst in purple crystal was recovered. The yield is 90%. Example 73-a Synthesis of Ru[(S, S)-N-p-Ts-1,2-Cyclohexanediamine](η 6 -p-Cymene)(((S, S)-N-p-Toluenesulfonyl-1,2-Cyclohexanediamine) (η 6 -p-Cymene)Ruthenium) Instead of (S, S)-p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH 2 ]((S, S)-N-p-toluenesulfonyl-1,2-diphenylethylenediamine), (S, S)-N-p-Ts-1,2-cyclohexanediamine((1S, 2S)-N-p-toluenesulfonyl-1,2-cyclohexanediamine) was used, and by the same procedures as in the Example 71-a, the catalyst in purple crystal as No.14 in Table 10 was recovered. The yield is 58%. Example 73-b Alternative Synthesis of Ru[(S, S)-N-p-Ts-1,2-Cyclohexanediamine](η 6 -p-Cymene) (((S, S)-N-p-Toluenesulfonyl-1,2-Cyclohexanediamine)(η 6 -p-Cymene)Ruthenium) Instead of RuCl[(S, S)-p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH 2 ])(η 6 -p-cymene)(chloro-((S, S)-N-p-toluenesulfonyl-1,2-diphenylethylenediamine)(η 6 -p-cymene)ruthenium), RuCl[(S, S)-N-p-Ts-cyclohexane-1,2-diamine synthesized in the Reference Example 3 was used, and by the same procedures as in the Example 71-b, the catalyst in purple crystal was recovered. The yield is 62%. Example 74-a Synthesis of Ru[(S, S)-N-p-TS-1,2-Cyclohexanediamine](η 6 -Mesitylene)((S, S)-N-p-Toluenesulfonyl-1,2-Cyclohexanediamine)(η 6 -Mesitylene)Ruthenium) Instead of (S, S)-p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH 2 ((S, S)-N-p-toluenesulfonyl-1,2-diphenylethylenediamine), (S, S)-N-p-Ts-cyclohexane-1,2-diamine ((S, S)-N-p-toluenesulfonyl-1,2-cyclohexanediamine) was used, and by the same procedures as in the Example 71-a, the catalyst as No.15 shown in Table 10 was recovered as purple crystal. The yield is 60%. Example 74-b Alternative Synthesis of Ru[(S, S)-N-p-Ts-1,2-Cyclohexanediamine](η 6 -Mesitylene) ((S, S)-N-p-Toluenesulfonyl-1,2-Cyclohexanediamine)(η 6 -Mesitylene)Ruthenium) Instead of RuCl[(S, S)-p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH 2 ](η 6 -p-cymene)(chloro-(S, S)-N-p-toluenesulfonyl-1,2-diphenylethylenediamine)(η 6 -p-cymene)ruthenium), RuCl[(S, S)-N-p-TS-1,2-cyclohexanediamine](η 6 -mesitylene)(chloro-(1S, 2S)-N-p-toluenesulfonyl-1,2-cyclohexanediamine)(η 6 -mesitylene)ruthenium) synthesized in the Reference Example 4 was used, and by the same procedures as in the Example 71-b, the aforementioned catalyst was recovered as purple crystal. The yield is 62%. Example 75-a Synthesis of RuH[(S, S)-p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH 2 ](η 6 -p-Cymene)(Hydride-(S, S)-N-p-Toluenesulfonyl-1,2-Diphenylethylenediamine)(η 6 -p-Cymene)Ruthenium) Ru[(S, S)-p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH](η 6 -p-cymene)((S, S)-N-p-toluenesulfonyl-1,2-diphenylethylenediamine)(η 6 -p-cymene)ruthenium) (600 mg; 1.0 mmol) is dissolved in 2-propanol (10 ml) in a Shlenk's reactor which is preliminarily vacuum dried and of which the inside is substituted with argon. The reaction solution was agitated at room temperature for 15 minutes. The solvent was recovered under reduced pressure at room temperature, to recover a compound in brown yellow. After rinsing the compound in cool pentane and recrystallizing the compound in methanol, the catalyst No.12 in Table 10 was recovered as orange crystal. The yield is 85%. m.p. >60° C. (decomposed) IR(KBr)[cm −1 ]:3335, 3317, 3228, 3153, 3060, 3025, 2960, 2917, 2867 1 H-NMR (400 MHz, 2 H-chloroform, δ):ppm −5.47 (s, 1H), 1.53 (d, 3H), 1.59 (d, 3H), 2.29 (d, 3H), 2.45 (s, 3H), 2.79 (m, 1H), 2.93 (m, 1H), 3.80 (d, 1H), 4.02 (m, 1H), 5.15 (d, 1H), 5.19 (d, 1H), 5.29 (m, 1H), 5.43 (d, 1H), 5.58 (d, 1H), 6.49 (d, 2H), 6.9-7.3 (m, 10H), 7.59 (d, 2H) Elemental Analysis (C 31 H 36 N 2 O 2 RuS) C H N Ru Theoretical values (%) 61.88 6.02 4.66 16.80 Experimental values (%) 61.79 5.94 4.70 16.56 The X-ray crystallography shows that the complex was of a structure satisfying the analytical results. Example 75-b Alternative synthesis of RuH[(S, S)-p-TsNCH(C 6 H 5 )CH(C 4 H 5 )NH 2 (η 6 -p-Cymene) (Hydride-((S, S)-N-p-Toluenesulfonyl-1,2-Diphenylethylenediamine) (η 6 -p-Cymene)Ruthenium) Toluene (7 ml) was added into the Ru[(S, S)-p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH](η 6 -p-cymene)((S, S)-N-p-toluenesulfonyl-1,2-diphenylethylenediamine)(η 6 -p-cymene)ruthenium) (306.2 mg; 0.5 mmol) synthesized in the Example 72 in an autoclave which was preliminarily vacuum dried and of which the inside was substituted with argon, for reaction at room temperature and a hydrogen pressure of 80 atm. After elimination of the solvent and rinsing in cool pentane and subsequent recrystallization in methanol, crystal in orange (420 mg) was recovered. The yield is 70%. Example 76-a Synthesis of RuH (S, S)-p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH 2 ](η 6 -Mesitylene) (Hydride-((S, S)-N-p-Toluenesulfonyl-1,2-Diphenylethylenediamine) (η 6 -Mesitylene)Ruthenium) Instead of Ru[(S, S)-p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH 2 ](η 6 -p-cymene)(((S, S)-N-p-toluenesulfonyl-1,2-diphenylethylenediamine) (η 6 -p-cymene)ruthenium), Ru[(S, S)-p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH](η 6 -mesitylene)(((S, S)-N-p-toluenesulfonyl-1,2-diphenylethylenediamine)(η 6 -mesitylene)ruthenium) synthesized in the Example 72 was used, and by the same procedures as in the Example 75-a, the aforementioned catalyst No.13 in Table 10 was recovered. The yield was 60%. Example 76-b Alternative Synthesis of RuH[(S, S)-p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH 2 ](η 6 -Mesitylene)(Hydride-((S, S)-N-p-Toluenesulfonyl-1,2-Diphenylethylenediamine)(η 6 -Mesitylene)Ruthenium) Instead of Ru((S, S)-p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH](η 6 -p-cymene)(((S, S)-N-p-toluenesulfonyl-1,2-diphenylethylenediamine) (η 6 -p-cymene)ruthenium), Ru[(S, S)-p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH](η 6 -mesitylene)(((S, S)-N-p-toluenesulfonyl-1,2-diphenylethylenediamine)(η 6 -mesitylene)ruthenium) synthesized in the Example 72 was used, and by the same procedures as in the Example 75-b, the aforementioned catalyst was recovered. The yield is 60%. Example 77-a Synthesis of RuH[(S, S)-N-p-Ts-1,2-Cyclohexanediamine](η 6 -p-Cymene)(Hydride-(S, S)-N-p-Toluenesulfonyl-1,2-Cyclohexanediamine)(η 6 -p-Cymene)Ruthenium) Instead of Ru[(S, S)-p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH](η 6 -p-cymene)((S, S)-N-p-toluenesulfonyl-1,2-diphenylethylenediamine) (η 6 -p-cymene)ruthenium), Ru[(S, S)-N-p-Ts-1,2-cyclohexanediamine](η 6 -p-cymene) ((S, S)-N-p-toluenesulfonyl-1,2-cyclohexanediamine)(η 6 -p-cymene)ruthenium) synthesized in the Example 73 was used, and by the same procedures as in the Example 75-a, the catalyst No.16 in Table 10 was recovered. The yield is 54%. Example 77-b Alternative Synthesis of RUH[(S, S)-N-p-Ts-1,2-Cyclohexanediamine](η 6 -p-Cymene)(Hydride-(S, S)-N-p-Toluenesulfonyl-1,2-Cyclohexanediamine)(η 6 -p-Cymene)Ruthenium) Instead of Ru[(S, S)-p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH](η 6 -p-cymene)(chloro-(S, S)-N-p-toluenesulfonyl-1,2-diphenylethylenediamine) (η 6 -p-cymene)ruthenium), Ru[(S, S)-N-p-Ts-1,2-cyclohexanediamine](η 6 -p-cymene)((S, S)-N-p-toluenesulfonyl-1,2-cyclohexanediamine)(η 6 -p-cymene)ruthenium) synthesized in the Example 73 was used, and by the same procedures as in the Example 75-b, the catalyst was recovered. The yield is 55%. Example 78-a Synthesis of RuH[(S, S)-N-p-Ts-1,2-Cyclohexanediamine](η 6 -Mesitylene)(Hydride(S, S)-N-p-Toluenesulfonyl-1,2-Cyclohexanediamine)(η 6 -Mesitylene)Ruthenium) Instead of Ru[(S, S)-p-TsNcH(C 6 H 5 )CH(C 6 H 5 )NH](η 6 -p-cymene)((S, S)-N-p-toluenesulfonyl-1,2-diphenylethylenediamine)(η 60 -p-cymene)ruthenium), Ru[(S, S)-N-p-Ts-1,2-cyclohexanediamine](η 6 -mesitylene) ((S, S)-N-p-toluenesulfonyl-1,2-cyclohexanediamine)(η 6 -mesitylene)ruthenium) synthesized in the Example 74 was used, and by the same procedures as in the Example 75-a, the catalyst No.17 in Table 10 was recovered. The yield is 52%. Example 78-b Alternative Synthesis of RuH[(S, S)-N-p-Ts-1,2-Cyclohexanediamine](η 6 -Mesitylene)(Hydride((S, S)-N-p-Toluenesulfonyl-1,2-Cyclohexanediamine)(η 6 -Mesitylene)Ruthenium) Instead of Ru[(S, S)-p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH](η 6 -p-cymene)((S, S)-N-p-toluenesulfonyl-1,2-diphenylethylenediamine) (η 6 -p-cymene)ruthenium), Ru[(S, S)-N-p-Ts-1,2-cyclohexanediamine](η 6 -mesitylene) ((S, S)-N-p-toluenesulfonyl-1,2-cyclohexanediamine)(η 6 -mesitylene)ruthenium) synthesized in the Example 74 was used, and by the same procedures as in the Example 75-b, the aforementioned catalyst was recovered. The yield is 48%. Example 79 Synthesis of (R)-1-Indanol Ru[(S, S)-p-TsNCH(C 6 H 5 )CH(C 6 H 5 )NH](η 6 -p-cymene)((S, S)-N-p-toluenesulfonyl-1,2-diphenylethylenediamine) (ruthenium-η 6 -p-cymene mesitylene (6.0 mg; 10 μmmol) synthesized in the Example 71 and 1-indanol (671 mg; 5 mmol) were weighed in a Shlenk's reactor which was preliminarily vacuum dried and of which the inside was substituted with argon, and acetone (2.5 ml) was then added to the resulting mixture for agitation at 28° C. for 6 hours. The solvent was distilled off under reduced pressure, prior to separation by silica gel chromatography (eluent; ethyl acetate:hexane=1:3), to recover (R)-indanol (286 mg) in colorless crystal. The yield is 84%. m.p. 71-72° C. [α] 24 D =−30.1° (c=1.96, chloroform) The resulting (R)-1-indanol was analyzed by HPLC (high-performance liquid chromatography), and the objective (R)-1-indanol was at an optical purity of 97% ee. <HPLC Analytical Conditions> Column: Chiralcel OB (manufactured by Daicell Chemical Industry, Co.) Developing solution: isopropanol: hexane=10:90 Flow rate: 0.5 ml/min Retention time: (S)-1-indanol 18.6 minutes (R)-1-indanol 12.9 minutes. Examples 80 to 93 According to the method described in Example 79, the optically active ruthenium-diamine complexes for racemic secondary alcohols and meso-type diols as reaction substrates as shown in Table 9 were used for reaction under reaction conditions of reaction time, to recover the individually corresponding optically active secondary alcohols at high yields. The results are collectively shown in Table 11. TABLE 11 Reaction Exam- Sub- time % % Prod- ples strates Catalysts s/c (hr) (yield) ee ucts 80 1a (S,S)-10 500 36 50 92 1a(R) 81 1a (S,S)-11 500 30 51 94 1a(R) 82 1a (S,S)-10 500 22 47 92 1b(R) 83 1b (S,S)-11 500 30 44 98 1c(R) 84 1c (S,S)-11 500 36 47 97 2a(R) 85 2a (S,S)-11 500 24 47 97 2b(R) 79 2b (S,S)-10 500 6 46 97 3a(R) 86 3a (S,S)-10 500 6 49 99 3b(R) 87 3b (S,S)-11 500 36 51 98 4(R) 88 4 (S,S)-10 500 4.5 43 93 5a(R) 89 5a (S,S)-10 500 5 46 95 5b(R) 90 5b (S,S)-11 200 3 70 96 7 91 5 (S,S)-10 200 3 56 87 9 92 1a (S,S)-14 500 36 48 82 1a(R) 93 1a (S,S)-15 500 36 48 86 1a(R) (In the table, s/c means the molar ratio of substrate/ruthenium-optically active diamine complex.) INDUSTRIAL APPLICABILITY In accordance with the present invention, optically active alcohols and optically active amines are provided, which are useful in various fields of pharmaceutical products, synthetic intermediates thereof, food, flavor, cosmetics, liquid crystal materials and the like. The ruthenium-diamine complex of the present invention is industrially useful as a chiral catalyst providing higher selectivity and activity in that the complex can be used for organic synthesis such as asymmetric synthetic reactions. If the complex is used as a hydrogen transfer-type asymmetric reduction catalyst of racemic secondary alcohols or meso-type diols, optically active secondary alcohols useful as production intermediates of drugs can be produced highly efficiently.
A method for producing optically active compounds is disclosed. The method is highly practical for producing optically active compounds useful for various utilities such as intermediates for synthesizing pharmaceutical agents, liquid crystal materials and agents for optical resolution.
2
FIELD OF THE INVENTION The buoyancy of natural gas makes transport of the gas in a dirigible an economically attractive project. In such a craft, the cargo would provide the necessary lifting force for the dirigible. The use of such a dirigible offers many advantages over transporting gas through a pipeline or in ships in its liquid state. Construction of a fleet of dirigibles is a smaller capital investment than a major pipeline. Because the dirigible would transport the gas in its natural state, no expensive conversion plants would be required as in transport in the liquid state. However, to be economically feasible, the dirigible must be large. The large size of such a craft presents problems in making a docking device for the craft. The device for docking should secure the dirigible and also allow for loading and unloading the natural gas cargo. When docked, for loading and unloading purposes, the large size of the dirigible makes it susceptible to large wind forces. Such a docking device must minimize such large wind forces to prevent damage to the aircraft and to the docking device. A dirigible must also have a haven in severe storms. Its large size would make a hanger impractical. If docked on the ground, the exposure to wind forces and possible wind damage still presents a problem. Therefore, any practical docking device must minimize wind damage. A docking device that would allow the dirigible to weathervane to offer the least wind resistance is one way to minimize damage to the dirigible. SUMMARY OF THE INVENTION The invention relates to a docking device for a dirigible. The device includes a cradle member for supporting a docked dirigible, the cradle securing the dirigible while docked and having structural components to support the dirigible in a horizontal position. The cradle is rotatably mounted to allow the docked dirigible and cradle to rotate around a pivot point to align the dirigible with the prevailing wind direction. As mentioned above, there are many problems associated in docking a dirigible to be used in transporting natural gas. The size of the aircraft would present considerable problems in the wind when docked on the ground for loading or storage. This invention overcomes the problems of high wind forces because the docking device is rotatably mounted around a central point. This allows the docked dirigible to freely weathervane in the wind so as to minimize its wind profile and corresponding wind forces. Such a docking device would provide an earthbound haven in a storm that would expose the dirigible to minimal wind damage. Other features and advantages of the present invention will be set forth in or apparent from the detailed description of preferred embodiments of the invention found hereinbelow. DESCRIPTION OF THE DRAWINGS FIG. 1 is a perspective view of the docking device as seen looking down from above. FIG. 2 is a side elevational view of the docking device with a dirigible docked in place. FIG. 3 is a front elevational view of the docking device with a dirigible docked in place. DESCRIPTION OF THE INVENTION The embodiment of the invention chosen for purposes of illustration is seen in FIG. 1. The docking is denoted as 100. The docking device 100 has two horizontal, and at least generally parallel dirigible support members 110. These support members 110 are positioned to be received by mating straight docking support structures 11 on the dirigible 10 as seen in FIGS. 2 and 3. The docking device 100 must accomodate a docked dirigible 10 having a substantially transverse circular cross section as seen in FIG. 3. Docking cradle 100 docks and secures dirigible 10. Dirigible 10 has an elongated body with a transverse circular cross section, as seen in FIGS. 2-3 and transports a cargo of natural gas. The dirigible 10 has horizontal, parallel docking structures 11 symmetrically located on the outside surface of the dirigible in a horizontal plane below the central longitudinal axis of the dirigible. A gas unloading-loading main 12 protrudes from the bottom surface of the dirigible at its lowermost point intermediate the ends of the dirigible and has a gas coupling 12A on its end. For further details on the dirigible 10, see copending application Ser. No. 545,319 filed Jan. 29, 1975 herein incorporated by reference. Dirigible support means 110 on cradle 100 are positioned to be received by mating horizontal, straight, and parallel docking structures 11 on the dirigible 10 as seen in FIGS. 2 and 3. While the embodiment chosen for the purposes of illustration has two parallel supporting means, the invention encompasses any support means that will maintain the dirigible 10 in a substantially horizontal plane. The docking cradle 11 is substantially square in plan view, having parallel, straight sides 111 and parallel, straight front and back structures 112 which are perpendicular to sides 111. Four structural members, 113, 114, 115, 116 extend inward from each corner and are joined to the geometrical centerpiece of the structure 117. The centerpiece 117 contains a vertical hollow cylinder 117A. Sides 111 are rectangular in shape in the side elevational view, having a bottom horizontal member 111A, vertical sides 111B, the docking support means 110 on top, and structural reinforcement 111C filling in the interior of the rectangle. The front and back panels 112 are also rectangular in shape, having a horizontal bottom member 112A, a horizontal top member 112B, a reinforcing web 112C between them, and sides formed by portions of the vertical sides 111B of sides 111. The bottom members 111A and 112A are in a horizontal plane. Sides 111B support the docking means 110 in a horizontal plane at an elevation to cradle a dirigible 10 of circular cross section and allow clearance for the dirigible gas filling main 12 above front and back structure bars 112B. On each corner of the horizontal square formed by members 111A and 112A are wheels 118. A vertical gas unloading main 130 protrudes through cylindrical passage 117A in the centerpiece 117 of docking cradle 100. The gas main 130 is connected to a underground distribution system (not shown). The gas main 130 has a rotating coupling 131 which mates with the gas main coupling 12A on dirigible 10. The seal between couplings 131 and 12A allows 360° of rotation without leaking. Gas main 130 is used to load and unload the cargo gas into and out of dirigible 10. Referring to FIG. 1, there is a horizontal circular track 160 located under the docking device 100. The circular track 160 has a diameter equal to the combined length of members 114 and 115. The circular track 160 is oriented to be horizontal with the vertical gas main 130 located at its center. Wheels 118 secured at the corners of the docking cradle 100 ride on the track 160 and support the docking cradle 100. This allows the docking cradle 100 to rotate around the gas loading-unloading main 130. Wheels 118 in this embodiment are spaced 90° apart along track 160. Alternatively, the docking cradle can be rotatably mounted on a central vertical axle. The axle could be mounted on a large bearing to allow the docking cradle to rotate 360°. The gas main could protrude through the center of the annular axle to load and unload gas from the docked dirigible. The docking device 100 allows a dirigible 10, to dock by nesting between docking support bars 110 and mating them with dirigible docking supports 11. Once the support means 110 and docking supports 11 are properly mated and secured as desired, the dirigible will be situated with its longitudinal centerline substantially parallel to the docking supporting means 110. When docked, the dirigible will be in a position to connect the unloading-loading gas main 12 to the unloading-loading gas main 130 which protrudes through the docking cradle centerpiece 117. Once connected, the dirigible 10 can be loaded or unloaded with gas. While docked, the dirigible will present a considerable wind resistance. The least wind resistance will exist with the dirigible oriented with its front into the wind. The rotatable gas main connection 131 and the docking cradle 100 rotatably mounted on circular track 160 allows the docked dirigible to rotate about the gas main 130. This ability to rotate allows the docked dirigible to weathervane in the wind so as to always present the profile of least resistance to the wind. In this manner, wind damage to the dirigible is minimized and the docking device is subjected to minimum stress. Although the invention has been described in detail with respect to exemplary embodiments thereof, it will be understood by those of ordinary skill in the art that variations and modifications may be effected within the scope and spirit of the invention.
A docking device for a dirigible. A supporting and securing structure is rotatably mounted on a circular track, the structure rotating about a centrally located member which may include a gas conduit for conveying gas into or out of a dirigible docked on the device. The docking device will allow the dirigible to dock and freely weathervane in the wind, even when unloading or loading a gas.
1
FIELD OF THE INVENTION This invention relates to an improved process for the manufacture of paper, and, specifically to the use of a combination of a cationic aluminum compound and an anionic aluminum compound in conjunction with a cationic polymer and anionic colloidal microparticles in a paper furnish containing cellulose fibers. BACKGROUND OF THE INVENTION Paper production involves the formation and dewatering of a web of cellulose fibers and optional fillers, and is generally performed in the presence of additives which can improve drainage and fines retention. The use of aluminum compounds in papermaking is well known. Aluminum sulfate, alum, or papermaker's alum, Al 2 (SO 4 ) 3 ·14H 2 O, is frequently used in paper sizing which provides water resistance in the finished paper and as precipitating or fixing agents to complex added dyes. Sodium aluminate is also widely used in papermaking to permit addition of extra aluminum for sizing and to increase pH. U.S. Pat. Nos. 4,385,961 (issued May 31, 1983), 4,388,150 (issued Jun. 14, 1983), 4,755,259 (issued Jul. 5, 1988), 4,961,825 (issued Oct. 9, 1990), and 4,980,025 (issued Dec. 25, 1990) disclose papermaking processes which involve use of a binder comprising a colloidal silica and a cationic polymer (starch or polyacrylamide). These patents caution against the use of other paper chemicals such as alum that can interfere with formation of the silica-cationic agglomerate. It is recommended to wait to add such agents until after the agglomerate is formed. U.S. Pat. No. 4,643,801 (issued Feb. 17, 1987) discloses a papermaking process using a binder comprising a cationic starch and a combination of ( 1 ) an anionic water soluble high molecular weight vinylic polymer of molecular weight at least 500,000 and (2) dispersed silica of particle size ranging from 1-50 nanometers, optionally in the presence of active alumina such as alum, sodium aluminate, or polyaluminum hydroxychloride. There is no suggestion to combine cationic and anionic aluminum compounds to afford additional improvement to the process. U.S. Pat. No. 4,902,382 (issued Feb. 20, 1990) discloses a process for producing a neutral paper at pH 6-9 which comprises adding to a paper stock slurry of filler and high yield pulp in order, a water soluble cationic aluminum salt, a cationic starch, and bentonite ultrafine clay, and after addition of the bentonite, or preferably, simultaneously with the bentonite, colloidal silica. U.S. Pat. No. 4,964,954 (issued Oct. 23, 1990) discloses a process for the preparation of paper by forming and dewatering papermaking fibers on a wire at pH >5 in the presence of a synthetic organic cationic polymeric retention agent, polyacrylamide or polyethyleneimine, an anionic inorganic colloid, especially silica sols containing aluminum, and a basic polyaluminum compound with at least 4 aluminum atoms per ion, preferably 10, with a ratio of polyaluminum compound to inorganic colloid of 0.01 to 3: 1. U.S. Pat. No. 5,127,994 (issued Jul. 7, 1992) discloses a process for the production of paper by forming and dewatering a suspension of cellulose containing fibers and optional fillers on a wire in the presence of an aluminum compound, such as alum, polyaluminum compounds, aluminates, aluminum chloride and aluminum nitrate, a cationic polymeric retention agent, preferably cationic starch or cationic polyacrylamide, and a polymeric silicic acid prepared by the acidification of alkali metal silicate having a specific surface area of at least 1050m 2 /g. European Patent 0 357574 (published Jul. 3, 1990) discloses a process for the production of paper by forming and dewatering a suspension of cellulose containing fibers on a wire in the presence of an anionic inorganic colloid, a cationic synthetic polymer and an aluminate. While cationic and anionic aluminum compounds have been used individually to improve various aspects of the papermaking process, the combination of these has not been recognized as providing an improvement in drainage and fines retention that is greater than the individual contribution of either aluminum compound. SUMMARY OF THE INVENTION The present invention is a process for the manufacture of paper comprising the steps of: (A) adding to an aqueous paper furnish containing cellulosic fibers (i) cationic aluminum compound in a proportional amount X; (ii) anionic aluminum compound in a proportional amount 1-X, wherein the combined weight of said aluminum compounds (as Al 2 O 3 ) is 0.005-2 weight % based on the dry weight of the furnish; (iii) cationic or amphoteric polymer in an amount of 0.05-6 weight % based on the dry weight of the furnish; and (iv) anionic colloidal microparticles in an amount of 0.001-2 weight % (as SiO 2 or, for bentonite, as solids) based on the dry weight of the furnish; and (B) forming and dewatering the aqueous suspension formed in step (A); wherein as X is varied from 0 to 1, a plot of Canadian Standard Freehess versus X has a maximum at some amount X, where O<X<1 and a plot of turbidity versus X has a minimum at some amount X where O<X<1. Optionally, the paper furnish can contain fillers and one or both of the following high molecular weight anionic polymer (flocculent) or low molecular weight cationic polymer (coagulant). DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for the manufacture of paper which provides rapid water drainage and good retention of fines by forming and dewatering paper furnish, an aqueous suspension of cellulose containing fibers and optional fillers, in the presence of a cationic aluminum compound, an anionic aluminum compound, a cationic polymer, an anionic colloidal microparticle. Optionally, the paper furnish can also contain a high molecular weight anionic polymer (flocculent) and a low molecular weight cationic polymer (coagulant). While addition of cationic aluminum compounds such as alum, and anionic aluminum compounds such as sodium aluminate alone to paper stock are known, it has been found surprisingly that the combination of a cationic aluminum compound and an anionic aluminum compound, when added to the paper stock containing known papermaking additives, provides an unexpected improvement in drainage and fines retention during the forming and dewatering steps of the papermaking process. Cationic aluminum compounds useful in the process of this invention can include alum (aluminum sulfate), aluminum chloride, polyaluminum chlorides, and other cationic aluminum salts and basic aluminum salts. Alum is preferred due to its availability and low cost. Anionic aluminum compounds useful in the process of this invention can include sodium aluminate and other anionic aluminum salts such as metal aluminates. Sodium aluminate is preferred due to its availability and low cost. The combined total alumina content (as Al 2 O 3 ) from the cationic and anionic aluminum compounds can range from about 0.005% to about 2% (0.1-40 lb/ton or 0.05-20 kg/mt) based on the dry weight of the paper furnish. It is preferable to add from about 0.02% to about 0.5%. In the process of this invention, the cationic aluminum compound and the anionic aluminum compound are added in such relative amounts that a plot of Canadian Standard Freeness versus X has a maximum value at some amount X where O<X<1, and a plot of turbidity versus X has a minimum value at some amount X, where O<X<1; X being a proportional amount of cationic aluminum compound and 1-X being a proportional amount of anionic aluminum compound which are added to the furnish. By proportional amount is meant that the anionic and cationic aluminum compound concentrations (as Al 2 O 3 ) are expressed as proportions of the combined aluminum compounds (as Al 2 O 3 ) as X and 1-X, respectively. Freeness is a measure of drainage rate of the furnish and is measured by the Canadian Standard Freeness test. Turbidity is an indirect measure of solids retention from the furnish and is measured by the turbidity of the white water drained from the Freeness test. Cationic polymers useful in the process of this invention can include cationic starch, cationic guar gum and high molecular weight synthetic cationic polymers such as cationic polyacrylamide. Cationic starches include those formed by reacting starch with a tertiary or quaternary amine to provide cationic products with a degree of substitution of from 0.01 to 1.0, containing from about 0.01 to 1.0 wt % nitrogen. Suitable starches include potato, corn, waxy maize, wheat, rice and oat. Cationic polymers can be present in amounts ranging from about 0.05% to 6% (or 1 to 120 lb/ton or 0.5-60 kg/mt) based on the dry weight of the paper furnish. The preferred range is from about 0.25% to 2% (5 to 40 lb/ton or 2.5-20 kg/mt). Amphoteric starch, guar gum and synthetic amphoteric high molecular weight polymers can also be used together with or in place of the cationic polymer. Anionic colloidal microparticles useful in the process of this invention can include polysilicic acid, colloidal silica, aluminum-modified colloidal silica, colloidal bentonite clay, polysilicate microgels and polyaluminosilicate microgels and mixtures thereof. The microgels are distinct from colloidal silica conventionally used in papermaking in that the microgel particles usually have surface areas of 1000 m 2 /g or higher and the microgels are small 1-2 nm diameter silica particles linked together into chains and three-dimensional networks. Polysilicate microgels, also known as active silicas, have SiO 2 :Na 2 O ratios of 4:1 to about 25: 1, and are discussed on pages 174-176 and 25-234 of "The Chemistry of Silica" by Ralph K. Iler, published by John Wiley and Sons, N.Y., 1979. Polysilicic acid generally refers to those silicic acids that have been formed and partially polymerized in the pH range 1-4 and comprise silica particles generally smaller than 3-4 nm diameter, which thereafter polymerize into chains and three-dimensional networks. Polysilicic acid can be prepared in accordance with the methods disclosed in U.S. Pat. No. 5,127,994, incorporated herein by reference. Polyaluminosilicates are polysilicate or polysilicic acid microgels in which aluminum has been incorporated within the particles, on the surface of the particles or both. The polysilicate microgels and polyaluminosilicate microgels useful in this invention are commonly formed by the activation of an alkali metal silicate under conditions described in U.S. Pat. Nos. 4,954,220 (issued Sep. 4, 1990) and 4,927,498 (issued May 22, 1990), incorporated herein by reference. However, other methods can also be employed. These include polyaluminosilicates formed by the acidification of silicate with mineral acids containing dissolved aluminum salts as described in U.S. patent application Ser. No. 08/212,744, filed Mar. 14, 1994, and alumina/silica microgels produced by the acidification of silicate with an excess of alum, as described in U.S. Pat. No. 2,234,285, incorporated herein by reference. The anionic colloidal microparticles used in this invention can be in the form of a colloidal silica sol containing about 2 to 60% by weight of SiO 2 , preferably about 4 to 30% by weight of SiO 2 . Alternatively, the colloid can have particles with at least a surface layer of aluminum silicate or it can be an aluminum modified silica sol. The colloidal silica particles in the sols commonly have a specific surface area of 50-1000 m 2 /g, more preferably about 200-1000 m 2 /g, and most preferably a specific surface area of about 300-700 m 2 /g. The silica sol can be stabilized with alkali in a molar ratio of SiO 2 :M 2 O of from 10:1 to 300: 1, preferably 15:1 to 100:1 (M is Na, K, Li, and NH 4 ). The colloidal particles have a particle size of less than 60 nm, with an average particle size less than 20 nm, and most preferably with an average particle size of from about 1 nm to 10nm. In addition to silica microgels and conventional silica sols, silica sols such as those described in European patents EP 491879 and EP 502089, incorporated herein by reference, can also be used for the anionic colloidal microparticle in this invention. The anionic colloidal microparticles are present in amounts ranging from about 0.001% to 2% (0.02 to 40 lb/ton or 0.01 to 20 kg/mt) on a SiO 2 basis, based on the dry weight of the paper furnish. The preferred range of addition is from about 0.005% to 0.4% (0.1 to 8 lb/ton or 0.05 to 4 kg/mt). Anionic high molecular weight polymers (flocculents) which can be optionally used in the process of this invention have number average molecular weights of at least 500,000 and a degree of anionic substitution of at least 1 mol %. Anionic flocculents with molecular weights of greater than 1,000,000 are more preferred, while best results are obtained when the molecular weight is between 5,000,000 and 30,000,000. Preferably the degree of anionic substitution is 10-70 mol %. The flocculents are preferably water soluble vinylic polymers containing acrylamide, acrylic acid, acrylamido-2-methyl propyl sulfonate and/or mixtures thereof and can also be either hydrolyzed acrylamide polymers or copolymers of acrylamide or its homolog, such as methacrylamide, with acrylic acid or its homolog, such as methacrylic acid, or perhaps even with monomers such as maleic acid, itaconic acid, vinyl sulfonic acid, acrylamido-2-methylpropylsulfonate, and other sulfonate containing monomers. Anionic flocculents have been described, for example, in U.S. Pat. Nos. 4,643,801, 4,795,531, and 5,126,014. Other anionic polymers which can be used as flocculents include anionic starch, anionic guar and anionic polyvinyl acetate. The anionic flocculent is preferably added to the paper furnish in an amount from about 0.001% to 0.8% (0.02 to 16 lb/ton or 0.01 to 8 kg/mt) and more preferably from about 0.005% to 0.25% (0.1 to 5 lb/ton or 0.05 to 2.5 kg/mt) based on the dry weight of the furnish. Cationic low molecular weight polymers (coagulants) which can be optionally used in the process of this invention have a number average molecular weight in the range between about 2,000 to about 500,000, preferably between 10,000 and 500,000. The coagulant can be polyethylene imine, polyamines, polycyandiamide formaldehyde polymers, amphoteric polymers, diallyl dimethyl ammonium chloride polymers, diallylaminoalkyl (meth)acrylate polymers and dialkylaminoalkyl (meth)acrylamide polymers, a copolymer of acrylamide and diallyl dimethyl ammonium chloride, a copolymer of acrylamide and diallylaminoalkyl (meth)acrylates, a copolymer of acrylamide and dialkylaminoalkyl (meth)acrylamides, and a polymer of dimethylamine and epichlorohydrin. These have been described in U.S. Pat. Nos. 4,795,531 and 5,126,014. The cationic coagulant is preferably added to the paper furnish in an amount from about 0.00005% to 1.25% (0.001 to about 25 lb/ton or 0.0005 to 12.5 kg/mt) preferably from about 0.001% to 0.5% (0.02 to 10 lb/ton or 0.01 to 5 kg/mt) based on the dry weight of the furnish. Papermaking furnishes useful in the process of this invention are suspensions of cellulosic materials in water and optionally contain inorganic fillers. The cellulosic materials are most commonly wood pulps derived from various sources such as bleached kraft pulp, thermochemical pulp and groundwood. Mixtures of pulps, including recycled pulp or broke with mixtures of fillers are frequently used. Inorganic fillers include clay, precipitated calcium carbonate, and titanium dioxide. The cellulosic materials generally comprise at least 50% of the total solids, and more usually, at least 70%. The pH of the furnish is within the range of pH 3-10. The components of the suspension prepared in the process of this invention can be added to the paper furnish as dilute solutions containing from about 0.01-1 wt % of dissolved solids. The order of addition is not critical and the components can be added separately or premixed when compatible. Thus anionic colloidal microparticles can be premixed with an anionic flocculent. Cationic starch can be premixed with a polyamine or other cationic polymers. Some of the cationic or anionic aluminum compound can be mixed with the anionic colloidal microparticles prior to addition to the furnish. Best results in the process of this invention are achieved when the following order of addition to the furnish is followed: first cationic aluminum compound and anionic aluminum compound, separately but substantially simultaneously, then cationic low molecular weight coagulant polymer, followed by cationic high molecular weight polymer, then anionic colloidal microparticles, and, finally anionic high molecular weight flocculent polymer. The following Examples illustrate the process of this invention. Drainage measurements were carried out using the Canadian Standard Freeness Test. Turbidity measurements of the white water from the freeness test provided an accompanying measure of degree of retention of pulp fines and filler. Mixing was conducted in a Britt Jar at an agitator speed of 750 rpm. In all Examples, the same conditions of mixing and order of addition of components were maintained. All weights are based on the dry weight of the furnish. EXAMPLE 1 Preparation of Paper using Cationic Alum/Anionic Sodium Aluminate Combination and Polysilicic Acid Microgel in Groundwood Paper Furnish An unbleached groundwood paper furnish of 0.3 wt % consistency (solids content) at pH 8 was used, wherein the solids contained 80% pulp and 20% clay filler. The following ingredients were added to the furnish in all runs: alum, sodium aluminate (both in amounts given in Table 1 ), cationic potato starch with a degree of substitution of 0.03, BMB-40 (40 lb/ton), available from Akzo Nobel, and polysilicic acid microgel, 4 lb (SiO 2 basis)/ton. Polysilicic acid microgel was prepared following a similar procedure to that described in U.S. Pat. No. 4,954,220. Dowex®50W-XS(H+), a strong sulfonic acid polystyrene ion exchange resin in the acid form, 200 g, was added batch-wise to 292 g of a well stirred dilute sodium silicate solution containing 5 wt % SiO 2 . About 3 minutes after the pH of the mixture reached 3.0, the resin was removed by filtration. The filtrate, 5% SiO 2 solution, was allowed to stand for 1 hour and then diluted to 1.0 wt % SiO 2 for stabilization. Water was added to dilute the 1.0 wt % solution to 0.125 wt % for use in preparing the suspensions. The ingredients were added as follows for all of the runs in this Example; quantities are shown in Table 1: (1) furnish was added to Britt jar and stirred for 15 seconds; (2) both aluminum compounds were addedseparately and simultaneously and stirred for 15 seconds; (3) cationic potato starch, 40 lb per ton, based on the dry weight of the pulp, was added and stirred for 15 seconds; (4) polysilicic acid microgel, 4 lb (on an SiO 2 basis) per ton, based on the dry weight of the furnish, as added and stirred for 15 seconds. The flocculated furnish contained in the Britt Jar was then transferred to the Canadian Standard Freeness tester and the freeness was determined. The turbidity of the water drained from the Freeness tester (white water) was measured on a Hach Ratio Turbidity Meter as an indication of fines retention. Results are presented in Table 1. TABLE 1______________________________________Alum (lb/ton) Sodium Aluminate (lb/ton)as Al.sub.2 O.sub.3 as Al.sub.2 O.sub.3 Freeness Turbidity______________________________________0.0 0.0 240 641.0 0.0 400 180.6 0.4 430 130.0 1.0 345 602.0 0.0 410 140.8 1.2 500 60.0 2.0 375 583.0 0.0 310 430.9 2.1 550 50.0 3.0 330 50______________________________________ The results in Table 1 grouped by threes based on total weight of aluminum reagent, show that the combination of cationic alum and anionic sodium aluminate (line 2 in each triad) unexpectedly gives improved freeness and turbidity when compared to either aluminum source alone. EXAMPLE 2 Preparation of Paper using Cationic Alum/Anionic Sodium Aluminate Combination and Polysilicate Microgel in Groundwood Paper Furnish The process of Example 1 was repeated with the same furnish, alum, sodium aluminate, and starch, but using a polysilicate microgel. Quantities of Al compounds are given in Table 2; starch added was 40 lb/ton and microgel added was 4 lb (SiO 2 basis)/ton. The polysilicate microgel was prepared by the following procedure: 295 g of a dilute sodium silicate solution containing 2.0 wt % SiO 2 with a pH of about 11.6 was mixed with sufficient sulfuric acid to reduce the pH to 9.0. The resulting solution was aged for 5 minutes and water was added to dilute to 0.125 wt % SiO 2 . Table 2 presents the results from the Canadian Standard Freeness test and turbidity measurements at a total alumina content (anionic plus cationic) of 2 lb/ton. The first and last data lines show controls where either only anionic or cationic Al compound was used outside of this invention. TABLE 2______________________________________Alum (lb/ton) Sodium Aluminate (lb/ton)as Al.sub.2 O.sub.3 as Al.sub.2 O.sub.3 Freeness Turbidity______________________________________2.0 0.0 380 281.6 0.4 420 151.2 0.8 455 110.8 1.2 490 70.4 1.6 430 220.0 2.0 340 49______________________________________ As can be seen from Table 2, combinations of cationic alum and anionic sodium aluminate give improved freeness and turbidity when compared to either aluminum source alone. EXAMPLE 3 Preparation of Paper using Cationic Alum/Anionic Sodium Aluminate Combination and Colloidal Silica in Groundwood Paper Furnish The process of Example 1 was repeated utilizing the same quantities of furnish, alum, sodium aluminate and starch (at 40 lb/ton) and as the anionic colloidal microparticles a commercial colloidal silica, BMA-0, having an average surface area of 550 m 2 /g (available from Akzo Nobel) at a loading of 8 lb (on an SiO 2 basis) per ton. Table 3 presents the results from the Canadian Standard Freeness tester and turbidity measurements at a total alumina content (anionic and cationic) of 2 lb/ton. The first and last data lines show controls where either only artionic or cationic aluminum compound was used outside of this invention. TABLE 3______________________________________Alum (lb/ton) Sodium Aluminate (lb/ton)as Al.sub.2 O.sub.3 as Al.sub.2 O.sub.3 Freeness Turbidity______________________________________2.0 0.0 420 311.6 0.4 475 161.2 0.8 520 100.8 1.2 565 40.4 1.6 540 130.0 2.0 420 36______________________________________ As can be seen in Table 3, combinations of cationic alum and anionic sodium aluminate give improved freeness and turbidity when compared to either aluminum source alone. EXAMPLE 4 Preparation of Paper using Cationic Alum/Anionic Sodium Aluminate Combination and Polyaluminosilicate Microgel in Groundwood Paper Furnish The process of Example 1 was repeated with the same furnish, alum, sodium aluminate, and starch (40 lb/ton), but using a polyaluminosilicate microgel at two different levels, 4 lb/ton and 6 lb/ton, respectively, on SiO 2 basis. Polyaluminosilicate microgel was prepared by mixing 100 g of polysilicic acid prepared as described in Example 1, containing 1.0 wt % SiO 2 , with dilute sodium aluminate containing 1.0 wt % Al 2 O 3 to yield an Al 2 O 3 :SiO 2 weight ratio of 1:30. The resulting solution was mixed for 20 minutes and then water was added to dilute to 0.125 wt % on a polyaluminosilicate basis. Tables 4A and 4B present the results from the Canadian Standard Freeness test and turbidity measurements at total alumina contents (anionic and cationic) of 1, 2, and 3 lb/ton. The first and last lines of each grouping of six show controls where either only anionic or cationic aluminum compound was used outside of this invention. TABLE 4A______________________________________4 lb/ton polyaluminosilicate microgelAlum (lb/ton) Sodium Aluminate (lb/ton)as Al.sub.2 O.sub.3 as Al.sub.2 O.sub.3 Freeness Turbidity______________________________________0.0 0.0 300 571.0 0.0 455 190.8 0.2 460 150.6 0.4 475 50.4 0.6 420 260.2 0.8 390 370.0 1.0 360 452.0 0.0 450 71.6 0.4 500 61.2 0.8 520 60.8 1.2 515 50.4 1.6 430 230.0 2.0 370 433.0 0.0 375 282.4 0.6 410 141.8 1.2 470 111.2 1.8 525 50.6 2.4 480 70.0 3.0 370 45______________________________________ TABLE 4B______________________________________6 lb/ton polyaluminosilicate microgelAlum (lb/ton) Sodium Aluminate (lb/ton)as Al.sub.2 O.sub.3 as Al.sub.2 O.sub.3 Freeness Turbidity______________________________________0.0 0.0 305 591.0 0.0 480 190.8 0.2 480 170.6 0.4 465 170.4 0.6 445 240.2 0.8 410 360.0 1.0 370 532.0 0.0 535 71.6 0.4 545 51.2 0.8 550 50.8 1.2 530 50.4 1.6 420 350.0 2.0 380 593.0 0.0 460 112.4 0.6 490 81.8 1.2 550 51.2 1.8 560 30.6 2.4 485 200.0 3.0 400 41______________________________________ As can be seen in Tables 4A and 4B, improvements in freeness and turbidity result when combinations of cationic and anionic aluminum compounds are used with polyaluminosilicate microgel. In comparison to the use of a single aluminum compound, there is a least one (and usually several) weight combinations of anionic and cationic aluminum compounds which provide improved properties and, therefore, afford freeness maxima and turbidity minima when plotted against fractional aluminum content. EXAMPLE 5 Preparation of Paper using Cationic Alum/Anionic Sodium Aluminate Combination and Aluminum Modified Colloidal Silica in Groundwood Paper Furnish The process of Example 1 was repeated utilizing the same quantities of furnish, alum, sodium aluminate and starch (at 40 lb/ton) and as the anionic colloidal microparticles a commercial aluminum modified colloidal silica, BMA-9, having an average surface area of 500 m 2 /g (available from Akzo Nobel) at a loading of 8 lb (on an SiO 2 basis) per ton, based on the dry weight of the pulp. Table 5 presents the results from the Canadian Standard Freeness test and turbidity measurements at a total alumina content (anionic and cationic) of 3 lb/ton. The first and last data lines show controls where either only anionic or cationic aluminum compound was used outside of this invention. TABLE 5______________________________________Alum (lb/ton) Sodium Aluminate (lb/ton)as Al.sub.2 O.sub.3 as Al.sub.2 O.sub.3 Freeness Turbidity______________________________________3.0 0.0 370 312.4 0.6 415 71.8 1.2 440 141.2 1.8 470 140.6 2.4 400 330.0 3.0 300 68______________________________________ As can be seen in Table 5, combinations of cationic alum and anionic sodium aluminate give improved freeness and turbidity when compared to either aluminum source alone. In this example, the best results (maximum freeness and minimum turbidity) do not occur at the same weight ratio of alum and sodium aluminate, showing that freeness and turbidity do not always track each other. EXAMPLE 6 Preparation of Paper using Cationic Alum/Anionic Sodium Aluminate Combination and Aluminum Modified Silica Sol Microgel in Groundwood Paper Furnish The process of Example 1 was repeated utilizing the same quantities of furnish, alum, sodium aluminate and starch (at 40 lb/ton) and as the anionic colloidal microparticle an aluminum modified silica sol microgel, prepared according to the procedure described in EP 491879, Example 1 C, 4 lb/ton (SiO 2 basis). Table 6 presents the results from the Canadian Standard Freeness test and turbidity measurements at a total alumina content (anionic and cationic) of 3 lb/ton. The first, second and last data lines show controls where no aluminum compound or either only anionic or cationic aluminum compound was used outside of this invention. TABLE 6______________________________________Alum (lb/ton) Sodium Aluminate (lb/ton)as Al.sub.2 O.sub.3 as Al.sub.2 O.sub.3 Freeness Turbidity______________________________________0.0 0.0 220 923.0 0.0 340 352.4 0.6 390 331.8 1.2 450 161.2 1.8 520 70.6 2.4 420 390.0 3.0 340 72______________________________________ As can be seen in Table 6, combinations of cationic alum and anionic sodium aluminate give improved freeness and turbidity when compared to either aluminum source alone. EXAMPLE 7 Preparation of Paper using Cationic Alum/Anionic Sodium Aluminate Combination and Alkaline Silica Sol in Groundwood Paver Furnish The process of Example 1 was repeated utilizing the same quantities of furnish, alum, sodium aluminate and starch (at 40 lb/ton) and as the anionic colloidal microparticles a silica sol prepared according to the procedure described in EP 502089, Example 1B, 4 lb/ton (SiO 2 basis). Table 7 presents the results from the Canadian Standard Freeness test and turbidity measurements at a total alumina content (anionic and cationic) of 3 lb/ton. The first, second and last data lines show controls where no aluminum compound or either only anionic or cationic aluminum compound was used outside of this invention. TABLE 7______________________________________Alum (lb/ton) Sodium Aluminate (lb/ton)as Al.sub.2 O.sub.3 as Al.sub.2 O.sub.3 Freeness Turbidity______________________________________0.0 0.0 210 1183.0 0.0 350 302.4 0.6 430 161.8 1.2 480 101.2 1.8 535 60.6 2.4 440 420.0 3.0 350 87______________________________________ As can be seen in Table 7, combinations of cationic alum and anionic sodium aluminate give improved freeness and turbidity when compared to either aluminum source alone. EXAMPLE 8 Preparation of Paper using Cationic Aluminum Chloride/Anionic Sodium Aluminate Combination and Polysilicic Acid Microgel in Groundwood Paper Furnish The process of Example 1 was repeated with the same furnish, sodium aluminate, starch (40 lb/ton), and polysilicic acid (4 lb/ton, SiO 2 basis) but using aluminum chloride as the cationic aluminum source. Table 8 presents the results from the Canadian Standard Freeness test and turbidity measurements at a total alumina content (anionic plus cationic) of 3 lb/ton based on dry furnish weight. The first and last data lines show controls where either only anionic or cationic aluminum compound was used outside of this invention. TABLE 8______________________________________AlCl.sub.3 (lb/ton) Sodium Aluminate (lb/ton)as Al.sub.2 O.sub.3 as Al.sub.2 O.sub.3 Freeness Turbidity______________________________________3.0 0.0 460 142.4 0.6 480 91.8 1.2 510 111.2 1.8 505 180.6 2.4 450 410.0 0.0 375 68______________________________________ As can be seen in Table 8, combinations of cationic aluminum chloride and anionic sodium aluminate give improved freeness and turbidity when compared to either aluminum source alone. The best results (maximum freeness and minimum turbidity) do not occur at the same combination of aluminum chloride and sodium aluminate, showing that freeness and turbidity do not always track each other. EXAMPLE 9 Preparation of Paper using Cationic Alum/Anionic Sodium Aluminate Combination and Polysilicic Acid in Kraft Paper Furnish The process of Example 1 was repeated using a bleached kraft furnish containing a 50/50 blend of bleached kraft hardwood and softwood and 30% clay. The furnish consistency was 0.3% solids. Alum, sodium aluminate, BMB-40 starch (40 lb/ton) and polysilicic acid (4 lb/ton, SiO 2 basis)were added to the furnish following the procedure of Example 1. Table 9 presents the results from the Canadian Standard Freeness test and turbidity measurements at 3 lb/ton of total alumina to dry weight of furnish and at 4 lb polysilicic acid per ton of dry furnish weight. TABLE 9______________________________________Alum (lb/ton) Sodium Aluminate (lb/ton)as Al.sub.2 O.sub.3 as Al.sub.2 O.sub.3 Freeness Turbidity______________________________________3.0 0.0 630 82.4 0.6 630 81.8 1.2 660 61.2 1.8 685 40.6 2.4 710 20.3 2.7 725 30.15 2.85 750 40.0 3.0 730 5______________________________________ As can be seen in Table 9, combinations of cationic alum and anionic sodium aluminate give improved freeness and turbidity when compared to either aluminum source alone. EXAMPLE 10 Preparation of Paper using Cationic Alum/Anionic Sodium Aluminate Combination and Polysilicic Acid and Cationic Coagulant in Groundwood Paper Furnish The process of Example 1 was repeated with the same quantities of furnish, alum, sodium aluminate, and polysilicic acid but using 20 lb/ton of starch and, additionally, 2.67 lb/ton of diallyldimethylammonium chloride polymer (polydadmac), a low molecular weight cationic polymer (coagulant). The ingredients were added as follows: (1) furnish was added to Britt Jar and stirred for 15 seconds; (2) polydadmac, 2.67 lb/ton, based on the dry weight of the pulp, was added to furnish and stirred for 15 seconds; (3) both aluminum compounds were added separately and simultaneously and stirred for 15 seconds; (4) cationic potato starch, 20 lb per ton, based on the dry weight of the pulp, was added and stirred for 15 seconds; (5) polysilicic acid microgel, 4 lb (on an SiO 2 basis) per ton, based on the dry weight of the pulp, was added and stirred for 15 seconds. The flocculated furnish contained in the Britt Jar was then transferred to the Canadian Standard Freeness tester and the freeness and turbidity of the white water were determined. Results are presented in Table 10. The first and last data lines show controls where either only anionic or cationic aluminum compound was used. TABLE 10______________________________________Alum (lb/ton) Sodium Aluminate (lb/ton)as Al.sub.2 O.sub.3 as Al.sub.2 O.sub.3 Freeness Turbidity______________________________________3.0 0.0 335 252.4 0.6 330 251.8 1.2 370 211.2 1.8 390 180.6 2.4 360 210.0 3.0 350 32______________________________________ As can be seen in Table 10, combinations of cationic alum and anionic sodium aluminate give improved freeness and turbidity when compared to either aluminum source alone. EXAMPLE 11 Preparation of Paper using Cationic Alum/Anionic Sodium Aluminate Combination and Aluminum Modified Colloidal Silica in Acidic Groundwood Paper Furnish The process of Example 1 was repeated, using alum, sodium aluminate, and cationic potato starch, BMB-40, available from Akzo Nobel. An unbleached groundwood paper furnish of 0.3 wt % consistency at pH 4 was used with suspended solids comprised of 80% pulp and 20% clay. An aluminum modified colloidal silica, BMA-9 (available from Akzo Nobel) was utilized as the anionic colloidal microparticles. The same mixing and addition sequence were followed as in Example 1. The amounts of cationic starch and colloidal silica were 20 lb/ton and 8 lb/ton, respectively, based on the dry weight of the furnish. Table 11 presents the results from the Canadian Standard Freeness tester and turbidity measurements at a total alumina content of 5 lb/ton. TABLE 11______________________________________Alum (lb/ton) Sodium Aluminate (lb/ton)as Al.sub.2 O.sub.3 as Al.sub.2 O.sub.3 Freeness Turbidity______________________________________5 0 280 364 1 250 513 2 240 522 3 310 291 4 375 180 5 280 43______________________________________ As can be seen in Table 11, some combinations of cationic alum and anionic sodium aluminate give improved freeness and turbidity when compared to either aluminum source alone. COMPARATIVE EXAMPLE Preparation of Paper using Two Cationic Aluminum Compounds and Polysilicic Acid in Groundwood Paper Furnish As a control, the process of Example 1 was repeated with the same furnish, starch (40 lb/ton), and polysilicic acid (4 lb/ton, SiO 2 basis)but using two cationic aluminum compounds, alum and aluminum chloride. No anionic aluminum compound was used. Table 12 presents the results from the Canadian Standard Freeness test and turbidity measurements at 3 lb/ton of total alumina per ton of dry furnish weight. TABLE 12______________________________________Alum (lb/ton) Sodium Aluminate (lb/ton)as Al.sub.2 O.sub.3 as Al.sub.2 O.sub.3 Freeness Turbidity______________________________________3.0 0.0 470 102.4 0.6 420 201.8 1.2 400 231.2 1.8 410 270.6 2.4 380 300.0 3.0 370 35______________________________________ As can be seen from Table 12, no synergistic improvement in freeness and turbidity occurs when combinations of two cationic aluminum compounds are used outside the scope of this invention and there is no maximum freeness or minimum turbidity in the plots versus aluminum content.
A process for producing paper, utilizing a combination of anionic and cationic aluminum compound additives and providing superior freeness and diminished turbidity, is provided.
3
FIELD OF THE INVENTION This invention relates to a system for teleconferencing, and in particular to such a system that permits a participant of the teleconference to collaborate separately with another party. BACKGROUND OF THE INVENTION Current teleconferencing systems cannot easily facilitate private conversations among teleconference participants who wish to communicate with each other (or with third parties) during a teleconference without being overheard by the remaining teleconference participants but while still being able to monitor the teleconference. In conventional teleconferencing systems, a teleconference participant desiring to collaborate with another teleconference participant or third party (the "collaborator") would be required to place the teleconference on "hold" and place a second call to the collaborator. However, there would no means for the first conferee to continue to monitor the teleconference while communicating with the collaborator. Of course, direct communication with the collaborator on the teleconference line is not feasible since that would disrupt the teleconference. In Eppe U.S. Pat. No. 5,034,947, there is described a "whisper circuit" for a conference call that permits two parties in a conference call to conduct a whisper conference between each other without being heard by the other parties on the conference call. At the same time, the two parties to the whisper conference can still hear the entire conversation being carried on by all of the other parties to the conference call, without the other parties being aware that the two parties are engaged in a whisper conference. Teleconference participants are interconnected to a digitized conference bridge over PCM telephone carrier lines, which are connected to a cross-point switch for interchanging the PCM speech data occurring in time slots for the two whisper conferees so that the PCM speech data for the first of the two whisper conferees is placed in the time slot for the second of the two whisper conferees and vice versa. A summation circuit is utilized to sum the telephone conversations of all remaining conferees and the two interchanged telephone conversations of the whisper conferees are then selectively added to the summed signals. Intelligibility is hampered somewhat because there is no acoustic isolation of the whisper conference. This is because a whisper conferee must extract the collaborator's voice out of the summed signals. This prior art teleconferencing circuit, which requires special system based hardware and resources, does not allow a teleconference participant to initiate a whisper conference with a third party who is not a member of the teleconference. It is beneficial to allow for whisper conferencing (or collaborative conferencing) without the need for the teleconference bridge and digital signalling processing techniques set out in this prior art patent which are typically difficult and expensive to implement. Furthermore, since a conference bridge is a shared resource concentrated at the network, there is an upper limit on the number of teleconferences that can be accommodated with whisper circuit functionality. The whisper circuit of the prior art patent will not function unless a digital voice switch hosts the teleconferencing bridge that is essential to the operation of that invention. Finally, the whisper circuit of the prior art patent restricts the number of whisper conferees to two since multiple collaborations cannot be accommodated. SUMMARY OF THE INVENTION The present invention provides a circuit and method for enabling a telephone having two lines (analog, digital, radio, etc.) to be connected to one call and have the capability of conducting a second simultaneous call while maintaining a monitoring function on the first call. In a teleconference initiated in accordance with the present invention, a user will be able to collaborate with a fellow conferee or third party (hereinafter referred to as a "collaborator"), while keeping track of the proceedings of the teleconference. With the use of the router of the present invention, the outbound audio signal of the user can easily be switched between the teleconference and the collaborator. The present invention provides a telephone collaborative conferencing circuit comprising a router having a first state and a second state and a microprocessor for selectively switching the router between the first and second state, and for selectively routing voice channels through said router; the router having first and second receive channel inputs, first and second transmit channel outputs, first and second acoustic outputs and at least one acoustic input, said acoustic input and outputs being connected to transducer devices for respectively receiving and producing sounds; wherein when the router is in the first state a first receive path is defined by a first receive voice channel appearing at the first receive channel input being routed to the first acoustic output and a first transmit path is defined by a first transmit voice channel appearing at the acoustic input being routed to the first transmit channel output, and when the router is in the second state, in addition to the first receive path, a second receive path is defined by a second receive voice channel appearing at the second receive channel input being routed to the second acoustic output and a second transmit path instead of the first transmit path is defined by a second transmit voice channel appearing at the acoustic input being routed to the second transmit channel output. In operation, the user first makes or receives the teleconference call in the normal manner on any available line. To initiate the call to the collaborator, the user presses the collaborative call key on the teleconferencing telephone set. The receive path on the teleconference line remains active, and, at the discretion of the user, may or may not be routed to another receive transducer on the teleconferencing telephone set (such as the speaker). The collaborative call is connected (both transmit and receive) to the active transducers, and is initiated in the normal fashion on the collaborative line. Once the collaborative call is established, the user's audio transmit path may be toggled between the two calls. At all times, the non-active line has its transmit path muted to ensure privacy of the collaborative call. When the collaborative call is completed, it is released using the standard call release mechanism on the teleconferencing telephone set. The teleconferencing line would then be automatically returned to the normal, non-collaborative state, with both its transmit and receive paths active. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a block diagram of the collaborative conferencing circuit of the present invention showing the line interfaces, router, microprocessor, and handset, headset, and speakerphone interfaces; FIG. 2 is a block diagram of the router showing the transmit and receive paths for the first stage of a collaborative conference call initiated in accordance with the present invention; FIG. 3 is a block diagram of the router showing the transmit and receive paths for the second stage of a collaborative conference call initiated in accordance with the present invention; FIG. 4 is a block diagram of the router showing the transmit and receive paths for the third stage of a collaborative conference call initiated in accordance with the present invention; FIG. 5 is a block diagram of the CODEC selector, two CODECS and router showing the transmit and receive paths for the second stage of a collaborative conference call initiated in accordance with the present invention; FIG. 6 is a schematic diagram of the router circuit of the present invention; and FIG. 7 is a top view of a teleconferencing telephone set that may be used in accordance with the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT The collaborative conferencing circuit 10 of the present invention consists of two line interfaces 12, 14 connected to a router 15, under the control of a microprocessor 22 as shown in FIG. 1. The router 15 also controls three acoustic outputs, labelled SPKR 16 (for the speakerphone interface), HDO 18 (for the headset interface), and HSO 20 (for the handset interface). Lines 1 and 2 (the transmit and receive channels of lines 1 and 2 are denoted by Tx 1 , Rx 1 , and Tx 2 , Rx 2 respectively) are shown being connected to line 1 interface 12, and line 2 interface 14 respectively. An example of the implementation of this collaborative conference circuit 10 would be Nortel's Digital Terminal Interface Chip, assigned the design code of AB06, that works in conjunction with a microprocessor running firmware code stored in read-only memory. On the basis of the firmware code, the microprocessor instructs the router 15 built into the AB06 chip to route receive voice channels and transmit voice channels in accordance with the present invention. The AB06 chip and microprocessor are designed to be a complete subsystem with which a teleconferencing telephone set can be built around. While the AB06 chip is designed to work in association with two incoming digital lines in an ISDN-like 2B+D format, it is expressly understood that the present invention works equally well in association with analog lines, as well as radio and wireless transmissions to the circuit 10. Collaborative conferencing is an application that makes use of channels Tx 1 , Rx 1 , and Tx 2 , Rx 2 of lines 1 and 2 and is useful in situations where a telephone conference participant wishes to initiate a private conversation with a fellow teleconference participant or third party without disrupting the original teleconference. After initiating the collaborative conference, a user will be able to monitor the teleconference in receive only mode (for example on the teleconferencing telephone set's speakerphone), while using the handset or headset to conduct a side conversation with the collaborator. Thus, there can be "collaboration" with another party while participating in the "conference". Of course, the collaborative conference call does not have to be with a single called party. Instead, the collaborative conference may itself be a separate conference call with a plurality of called parties. Typically, the user would initiate a collaborative conference call by depressing a collaborative conference key on the teleconferencing telephone set (see FIG. 7) which is used to initiate the conference call. The microprocessor 22 is programmed to detect when a particular key is depressed. When the microprocessor 22 detects that the collaborative conference key has been depressed, the collaborative conference setup stage described in detail below will be initiated. The teleconferencing telephone set may also include a toggle key to switch active transmission between the conference call and the collaborator. FIGS. 2, 3 and 4 illustrate the three stages of operation of the present invention, namely teleconference setup, collaborative conference setup, and toggle. In FIG. 2, the transmit and receive paths for lines 1 and 2 for the teleconference setup stage are shown. The acoustic inputs for the router circuit are handset microphone interface HSI, headset microphone interface HDI, and speakerphone microphone interface MIC. The acoustic outputs for the router circuit are speakerphone interface SPKR, headset interface HDO, and handset interface HSO. In the teleconference stage, the user initiates or receives the teleconference call in the normal manner on channels Tx 1 , Rx 1 . The means of setting up this initial teleconference (such as by means of a teleconference bridge, which are well known in the art) does not form part of this invention. Router 15 routes the receive path from Rx 1 to speakerphone interface SPKR, and the transmit path from speakerphone microphone interface MIC to channel Tx 1 . Of course, the teleconference call could have been routed to either the headset interface HDO, or the handset interface HSO. In this state, channels Tx 2 , Rx 2 are idle, and are not handling any traffic. In FIG. 3, the transmit and receive paths for lines 1 and 2 for the collaborative conference call setup stage are shown. Typically, the user would initiate the collaborative call by depressing the collaborative call key located on the teleconferencing telephone set. Once the key is depressed, router 15 will initiate a collaborative conference call by muting the transmit portion of the conference call on channel Tx 1 , assigning the transmit path to the collaborative conference call from handset microphone interface HSI to channel Tx 2 , and also switching on a second receive path from channel Rx 2 to handset interface HSO. The collaborator may either be a fellow teleconference participant, or third party. In this state, the user continues to hear the teleconference carried on channel Rx 1 on the speakerphone, while being able to carry on a bi-directional collaborative conference call on channels Tx 2 , Rx 2 . Since channel Tx 1 is muted, the other members of the teleconference cannot hear the communication between the user and the collaborator, and will be totally unaware that this communication is taking place. Though router 15 is shown routing the collaborative conference call to handset interface HSO, the collaborative conference call could have been routed to headset interface HDO. Headset interface HDO, and headset microphone interface HDI are not essential to the operation of the invention, and are shown for illustration purposes only. At least one microphone (located in the headset, handset, telephone unit or some other location) and two speakers (located in the speakerphone, headset, headset, or some other location) are the minimum requirement for the operation of the present invention. With reference to FIG. 3, this means that the transmit path for line 2 may be assigned by router 15 from speakerphone microphone interface MIC to channel Tx 2 . Since only one transmit path is active at any given moment, there would only be a need to have one microphone. In the circumstances of this scenario, handset microphone interface HSI would be optional to the operation of the present invention. At any time, the user may toggle the audio transmit path between the teleconference call and the collaborative call. This stage is illustrated in FIG. 4. By depressing a toggle key that would typically be located on the teleconferencing telephone set, router 15 would mute the transmit path from HSO to channel Tx 2 , and re-initiate the transmit path from MIC to channel Tx 1 . Unless the collaborator were a member of the teleconference, the collaborator would hear silence while the user actively participated in the teleconference. To toggle back to the collaborator, the user would depress the toggle key and router 15 would mute the transmit path from MIC to channel Tx 1 , and re-initiate the transmit path from HSO to channel Tx 2 . Once the collaborative call has been concluded, it is released using the standard release mechanism for the teleconferencing telephone set. The teleconference call on line 1 would be returned to its non-collaborative state, with both channels Tx 1 , Rx 1 paths active. Line 2 (ie. Tx 2 , Rx 2 ) would be idle. Persons skilled in the art will appreciate that while the router 15 shown in FIG. 2, 3 and 4 handles only analog lines, it can be modified to accommodate connections to digital lines. Where connections to digital lines are required, the router must be connected to two CODECS (analog to digital encoder/digital to analog decoder), and one codec selector. FIG. 5 illustrates the transmit and receive paths for lines 1 and 2 for the collaborative conference call setup stage, where channels Tx 1 , Rx 1 , Tx 2 and Rx 2 are digital, rather than analog as they are shown in FIG. 3. CODEC selector 60 is used to select which channel will be encoded/decoded by which CODEC. In this case, channel Rx 1 is being decoded by CODEC1, channel Tx 2 is being encoded by CODEC2, and channel Rx 2 is being decoded by CODEC2. FIG. 6 is a schematic diagram of the router circuit of the present invention. All gates A, B, C, D, E, F, G, H, I, J and K are under the control of microprocessor 22 shown in FIG. 1. Microprocessor 22 runs firmware code stored in read-only memory to set the open/closed status of the gates in response to the three stages of operation of the invention shown in FIGS. 2, 3 and 4. Receive path Rx 1 is shown being connected to speakerphone interface SPKR through gate D, to headset interface HDO through gate E, and to handset interface HSO through gate F. Signal adders 54 are used to sum signals Rx 1 and Rx 2 . Receive path Rx 2 is shown being connected to speakerphone interface SPKR through gate G, to headset interface HDO through gate H, and to handset interface HSO through gate I. Transmit path Tx 1 is shown being connected to handset microphone interface HSI through amplifier 56, signal adder 55, and gates A & J; to headset microphone interface HDO through amplifier 56, signal adder 55, and gates B & J; and to speakerphone microphone interface MIC through amplifier 56, signal adder 55, and gates C & J. Transmit path Tx 2 is shown being connected to handset microphone interface HSI through amplifier 56, signal adder 55, and gates A & K; to headset microphone interface HDO through amplifier 56, signal adder 55, and gates B & K; and to speakerphone microphone interface MIC through amplifier 56, signal adder 55, and gates C & K. Amplifiers 56 are used to amplify voice signals either to or from the router as required. In Tables 1, 2 and 3 below, the open/closed status of gates A, B, C, D, E, F, G, H, I, J and K are set out for the three stages of collaborative conferencing (teleconference setup, collaborative conference setup, and toggle) shown in FIGS. 2, 3 and 4 respectively. It is expressly understood that with the exception of gates J and K, the open/closed status of the remaining gates in Tables 1, 2 and 3 can be altered somewhat without affecting the operation of the invention. For example, in Table 1 Rx 1 is routed only to speakerphone interface SPKR through gate D. However, Rx 1 could have been routed to either the handset interface HSO, or the headset interface HSO. Similarly, in Table 1 handset microphone interface HSI and/or headset microphone interface HDI could be enabled through gates A and B respectively, in addition to or in replace of speakerphone microphone interface MIC through gate C. As will be explained in further detail below, it is not even essential to the operation of this invention that Rx 1 and Rx 2 be routed to separate acoustic transducers. However, it is essential that only one of gates J and K (and therefore only one of Tx 1 and Tx 2 ) can be open at any given time while a collaborative conference is being held. TABLE 1______________________________________Open/Closed Status of Gates During Teleconference SetupGate Open/Closed Status______________________________________A openB openC closedD closedE openF openG openH openI openJ closedK open______________________________________ TABLE 2______________________________________Open/Closed Status of Gates During Collaborative Conference SetupGate Open/Closed Status______________________________________A closedB openC openD closedE openF openG openH openI closedJ openK closed______________________________________ TABLE 3______________________________________Open/Closed Status of Gates During Toggle BetweenTeleconference and Collaborative ConferenceGate Open/Closed Status______________________________________A closedB openC openD closedE openF openG openH openI closedJ closedK open______________________________________ Following the release of the collaborative conference, channels Tx 1 , Rx 1 , Tx 2 and Rx 2 return to their pre-collaborative state, as set out in Table 1 above. Of course, the above table postulates a teleconference being initiated via speaker microphone interface MIC through gate C, and a collaborative conference being initiated via handset interface HSI through gate A. This selection of interfaces is arbitrary, and was chosen for the purpose of illustration only. For example, a teleconference could be initiated via handset interface HSI through gate A, and a collaborative conference could be initiated via headset microphone interface HDI through gate B without affecting the operability of the present invention. The selection of routing for Rx 1 and Rx 2 in the above tables was also arbitrary, and could be changed without affecting the operability of the present invention. The router circuit shown in FIG. 6 has other applications apart from merely enabling a collaborative conference. For example, in a paging application, an outside third party could initiate a call to Rx 2 and communicate a message to the user without the other members of the teleconference overhearing that message. Assuming the status of the gates shown in FIG. 6 is as set out in Table 1 above, a call received on channel Rx 2 would be connected to acoustic transducer interface HDO or HSO through gates I or H respectively. As such, the user could be "paged" without interfering with the teleconference. Alternatively, gate G could be closed to allow the paging call to be communicated through acoustic transducer SPKR, after having been added to channel Rx 1 through signal adder 54. A variable amplifier could be added to the receive path followed by Rx 2 to vary the volume of the paging signal, as compared to the teleconference signal. FIG. 7 is a top view of a teleconferencing telephone set 80 that may be used in accordance with the present invention. Telephone set 80 does not have to be exactly as depicted in FIG. 7. Any telephone containing the collaborative conferencing circuit of FIG. 1 would work in accordance with the present invention. The collaborative conferencing circuit, including router and microprocessor (shown in FIG. 1) would be self-contained within teleconferencing telephone set 80. Handset interface HSO, and handset microphone interface HSI would be connected to handset device 82. Speakerphone interface SPKR and speakerphone microphone interface MIC would be connected to speakerphone 84. Speakerphone 84 is comprised of a microphone (for receiving acoustic input) and a speaker (for transmitting acoustic output). Headset interface HDO and headset microphone interface HDI would not be operable in teleconferencing telephone set 80, because an optional headset is not depicted. To initiate a call to a collaborator, the user presses the collaborative call key 86 on telephone set 80. A toggle key 88 is also provided to switch active transmission between the conference call and the collaborator. It is understood that handset interface HSO, and handset microphone interface HSI can be connected to other handset devices beyond that shown in FIG. 6. For example, handset device 82 could be a mobile cordless handset that transmits and receives radio signals from telephone set 80. The above description of a preferred embodiment should not be interpreted in any limiting manner since variations and refinements can be made without departing from the spirit of the invention. The scope of the invention is defined by the appended claims and their equivalents.
A circuit and method is described enabling a telephone having two or more lines to have the capability of initiating two simultaneous calls, where there is two-way communication on one of the calls (the collaborating call"), and active monitoring of the second call (the "teleconference"). A router is used so that the outbound audio signal of the user can easily be switched between the teleconference and the collaborating call. At all times, the transmit path of one of the calls is muted to ensure privacy of the other call.
7
CROSS-REFERENCE TO RELATED APPLICATION This Application a Continuation of U.S. application Ser. No. 11/643,844 filed on Dec. 22, 2006 which is a Continuation of U.S. application Ser. No. 11/082,988 filed on Mar. 18, 2005, now issued U.S. Pat. No. 7,175,256, which is a Continuation of U.S. application Ser. No. 10/893,385, filed on Jul. 19, 2004, now issued U.S. Pat. No. 6,905,194, which is a Continuation of U.S. application Ser. No. 10/291,706, filed on Nov. 12, 2002, now issued U.S. Pat. No. 7,125,106, which is a Continuation of U.S. application Ser. No. 09/609,140, filed on Jun. 30, 2000, now issued U.S. Pat. No. 6,755,513, all of which are herein incorporated by reference. FIELD OF THE INVENTION This invention relates to the field of ink jet printing systems, and more specifically to a printhead support assembly and ink supply arrangement for a printhead assembly and such printhead assemblies for ink jet printing systems. DESCRIPTION OF THE PRIOR ART Micro-electromechanical systems (“MEMS”), fabricated using standard VLSI semi-conductor chip fabrication techniques, are becoming increasingly popular as new applications are developed. Such devices are becoming widely used for sensing (for example accelerometers for automotive airbags), inkjet printing, micro-fluidics, and other applications. The use of semi-conductor fabrication techniques allows MEMS to be interfaced very readily with microelectronics. A broad survey of the field and of prior art in relation thereto is provided in an article entitled “The Broad Sweep of Integrated Micro-Systems”, by S. Tom Picraux and Paul McWhorter, in IEEE Spectrum, December 1998, pp 24-33. In PCT Application No. PCT/AU98/00550, the entire contents of which is incorporated herein by reference, an inkjet printing device has been described which utilizes MEMS processing techniques in the construction of a thermal-bend-actuator-type device for the ejection of a fluid, such as an ink, from a nozzle chamber. Such ink ejector devices will be referred to hereinafter as MEMJETs. The technology described in the reference is intended as an alternative to existing technologies for inkjet printing, such as Thermal Ink Jet (TIJ) or “Bubble Jet” technology developed mainly by the manufacturers Canon and Hewlett Packard, and Piezoelectric Ink Jet (PIJ) devices, as used for example by the manufacturers Epson and Tektronix. While TIJ and PIJ technologies have been developed to very high levels of performance since their introduction, MEMJET technology is able to offer significant advantages over these technologies. Potential advantages include higher speeds of operation and the ability to provide higher resolution than obtainable with other technologies. Similarly, MEMJET Technology provides the ability to manufacture monolithic printhead devices incorporating a large number of nozzles and of such size as to span all or a large part of a page (or other print surface), so that pagewidth printing can be achieved without any need to mechanically traverse a small printhead across the width of a page, as in typical existing inkjet printers. It has been found difficult to manufacture a long TIJ printhead for full-pagewidth printing. This is mainly because of the high power consumption of TIJ devices and the problem associated therewith of providing an adequate power supply for the printhead. Similarly, waste heat removal from the printhead to prevent boiling of the ink provides a challenge to the layout of such printhead. Also, differential thermal expansion over the length of a long TIJ-printhead may lead to severe nozzle alignment difficulties. Different problems have been found to attend the manufacture of long PIJ printheads for large- or full-page-width printing. These include acoustic crosstalk between nozzles due to similar time scales of drop ejection and reflection of acoustic pulses within the printhead. Further, silicon is not a piezoelectric material, and is very difficult to integrate with CMOS chips, so that separate external connections are required for every nozzle. Accordingly, manufacturing costs are very high compared to technologies such as MEMJET in which a monolithic device may be fabricated using established techniques, yet incorporate very large numbers of individual nozzles. Reference should be made to the aforementioned PCT application for detailed information on the manufacture of MEMJET inkjet printhead chips; individual MEMJET printhead chips will here be referred to simply as printhead segments. A printhead assembly will usually incorporate a number of such printhead segments. While MEMJET technology has the advantage of allowing the cost effective manufacture of long monolithic printheads, it has nevertheless been found desirable to use a number of individual printhead segments (CMOS chips) placed substantially end-to-end where large widths of printing are to be provided. This is because chip production yields decrease substantially as chip lengths increase, so that costs increase. Of course, some printing applications, such as plan printing and other commercial printing, require printing widths that are beyond the maximum length that is practical for successful printhead chip manufacture. SUMMARY OF THE INVENTION The present invention is broadly directed to the provision of a suitable printhead segment support structure and ink supply arrangement for an inkjet printhead assembly capable of single-pass, full-page-width printing as well as to such printhead assemblies. While the invention was conceived in the context of MEMJET printhead segments (chips), and thus the following summary and description of the invention is provided with particular reference to printhead assemblies incorporating MEMJET printhead segments, it is believed that the invention also has the potential to be employed with other ink jet printhead technologies. Accordingly, it is one object of the present invention to provide a printhead segment support structure that is capable of accommodating a series of printhead segments as described in PCT/AU98/00550 in an array that permits single-pass pagewidth printing across the width of a surface passing under the printhead assembly. The term “single-pass pagewidth printing” should here be understood as referring to a printing operation during which the printhead assembly is moved in only one direction along or across the entire width or length of any print surface, as compared to a superimposed, generally orthogonal printhead carriage movement as employed in conventional ink jet printers. (Of course, printhead assembly movement may be relative, with the surface moving past a stationary printhead assembly.) It will be also understood that there are many possible page widths and the inkjet printhead segment support structure of the invention would be suitable for adaptation to a range of widths. A printhead assembly in accordance with the invention should in particular be useful where a plurality of generally elongate, but relatively small printhead segments are to be used to print across substantially the entire width of a sizable surface without the need for mechanically moving the printhead assembly or any printhead segment across as well as along the print surface. The invention has also been conceived in light of potential problems related to the relatively small size of individual printhead segments, their fragility and the required highly accurate alignment or registration of individual printhead segments with each other on the support structure and with external components in order to provide a printhead assembly capable of single-pass, full pagewidth printing. Multiple ink supply channels are required to supply ink in reliable manner to all printhead segments. Because of the small size of the segments, this in general would require high quality micro-machined parts. An ink supply conduit, on the other hand, is most economically made if it can be formed at a much coarser scale. Accordingly, another object of the invention is to provide a printhead segment support structure with a print fluid supply arrangement that ensures adequate print fluid (e.g. ink) supply to individual printhead segments mounted to the support structure, at an affordable manufacturing cost. Typical MEMJET printhead segments have a dimension of 2 cm length by 0.5 mm width, and will include (in a layout for 4-color printing) four lengthwise-oriented rows of ink ejection nozzles, the segment being of monolithic fabrication. Longer segments could be made and used, but the size mentioned gives very satisfactory fabrication yields. Each printhead segment has ink inlet holes arrayed on one surface and corresponding nozzle outlets arrayed on an opposite surface. Each of the four rows will then require connection to an appropriate ink supply, such that an inkjet printhead assembly can be provided for operation with (for example) cyan, magenta, yellow and black inks for color printing. Accordingly, yet a further object is to provide an ink supply arrangement thereby to enable supply of a number of differently colored inks (or other printing fluids) to selected ink inlets of individual printhead segments carried on a support structure for full pagewidth color printing. Another related object of the invention is to provide a print fluid supply arrangement that is simple in layout and thus easy to incorporate in a printhead support structure. It should ensure even and reliable distribution of print fluids in a pagewidth inkjet printhead assembly. In a first aspect, the invention provides a support for a plurality of inkjet printhead segments, said support including: a hollow elongate member having at least one ink supply channel formed therein, the, or each, ink supply channel being in fluid communication with an elongate slot in and extending at least partly along the elongate member; and a plurality of printhead segment carriers received and secured in neighbouring arrangement within the slot, each printhead segment carrier being adapted for mounting thereto of at least one printhead segment. Each printhead segment carrier may include at least one ink gallery that is in fluid communication with said, or an associated one of said, ink supply channels when mounted to that printhead segment carrier. The printhead segment carriers may be configured so that when the printhead segments are mounted in the printhead segment carriers they define a series of printing ranges in a direction lengthwise along the elongate member that overlap to define a combined printing range of greater lengthwise extent than any of the printing ranges of the respective printhead segments. The printhead segment carriers may be substantially identical to one another and may have stepped terminal ends thereby to enable neighbouring pairs of printhead carriers to be mounted within the slot in a staggered manner. Each printhead segment carrier may have an elongate recess in an external surface of the carrier within which at least one printhead segment is mountable and wherein recesses of neighbouring pairs of carriers overlap in a direction along the elongate member. Each printhead segment carrier may define an elongate ink delivery slot that opens into said recess of each printhead segment carrier. Each ink delivery slot may be in fluid communication with a respective ink supply channel via said ink gallery that extends from said at least one ink slot to an opening in a rear face of the printhead segment carrier. A plurality of said ink galleries and said openings may be in fluid communication with the, or each, ink delivery slot. Said openings associated with the, or each, said ink delivery slot may be arranged in a row extending in a direction along the elongate member. Each printhead segment carrier may have a plurality of ink supply channels and a plurality of said rows of openings. Each row of openings may be aligned along its length with one said ink channel for passage of ink from said ink channel through said row of openings. The ink galleries may be defined by a plurality of parallel walls extending transversely in each printhead segment carrier and intersecting with a plurality of converging walls extending from the rear face to shaped inner edges that at least partially define the ink delivery slots. The assembly may include a shim that is shaped to be received in the slot in the elongate member and to lie between the elongate member and said printhead segment carriers, said shim having at least one aperture therein to permit flow of ink between the or an associated one of said ink supply channels and a corresponding one ink gallery of the respective printhead segment carrier. The shim and the slot may be substantially semi-circular in cross-sectional shape. The shim and/or the elongate member may comprise means for snap-fittingly mounting said shim at said slot. In another example, the shim may be adhesively bonded to mating surfaces of the elongate member. In yet another example, the printhead segment carriers may be adhesively bonded to the shim. Webs, which abut external surfaces of the elongate member, may be attached to edges extending in a direction along the shim. Each printhead segment carrier may have a recess formed in an external surface thereof within which at least one printhead segment is received when mounted to the printhead segment carrier. Said external surface may have a second recess formed therein and adapted to receive at least a part of a power or signal conductor terminating on the or one said printhead segment mounted to the printhead segment carrier. Said conductor may comprise a tape automated bonded (TAB) film. Said tape automated bonded film (TAB) may be wrapped around an external surface of the elongate member and terminated on a printed circuit board secured to a side of the elongate member opposite to the printhead segment to which it is connected. The support assembly may include a first cap secured to a first terminal end of the elongate member and may have an ink inlet port in fluid communication with the or an associated one of said ink supply channels. The support assembly may further include a second cap secured to a second terminal end of the elongate member and having an opening for bleeding of air from the or an associated one of said ink supply channels. Means for sealing off said opening after such bleeding may be provided. Said second cap may include an outer face with a tortuous channel formed therein. Said tortuous channel may be in fluid communication with said opening and said sealing means may include a film removable at least in part from the outer face and adapted to adhere to the outer face thereby to cover the tortuous channel and seal off the opening. The support assembly may further include an external protective shield plate covering the printhead segment carriers and having openings arranged to permit unimpeded passage of ink ejected from nozzles of printhead segments mounted to the carriers towards a surface passing beneath the support assembly. The elongate member may have three, four or six of said ink supply channels, one each for differently colored ink. Each printhead segment carrier may be mounted within the slot at a longitudinal position within a predetermined distance of a designated longitudinal position of the carrier corresponding to a designated longitudinal position within the slot of a printhead segment when mounted to said printhead segment carrier. The elongate member may be of substantially constant cross-sectional shape along its entire length. In cross-section, the elongate member may include a peripheral structured wall including a base wall section, and side wall sections standing out from opposite edges of said base wall section, and wherein said slot lies between free edges of said side wall sections. Said elongate member may further include at least one internal web extending from the base wall section and along said elongate member. Said elongate member may have a plurality of said internal webs. In cross-section, said free edges of the side wall sections and free edges of said internal webs may lie on a semicircle and may define boundaries of said slot so that said slot is of semicircular cross-section. In a second aspect, the invention provides an inkjet printhead assembly including: a hollow elongate member having at least one ink supply channel formed therein, the or each ink supply channel being in fluid communication with an elongate slot in and extending at least partly along the elongate member; and a plurality of printhead segment carriers received and secured in neighbouring arrangement within the slot; and at least one printhead segment mounted to each printhead segment carrier. Thus, the second aspect of the invention is directed to a printhead assembly that includes the support assembly of the first aspect of the invention. It is preferred that the at least one printhead segment on each printhead segment carrier has a defined printing range in a direction lengthwise along the elongate member, and that the printing ranges of the printhead segments mounted to a plurality of adjoining printhead segment carriers overlap, so that the printhead segments mounted to said plurality of adjoining printhead segment carriers have a combined printing range of greater lengthwise extent than any of the printing ranges comprised therein. This is a suitable way in which printing may be accomplished on a surface without the presence of gaps corresponding to lengthwise gaps between individual printhead segments. In a further aspect, the invention provides a method for assembling the inkjet printhead assembly wherein the step of mounting to each printhead segment carrier its respective at least one printhead segment precedes the step of securing that printhead segment carrier within the slot. It is then preferred that the printhead segment carriers are secured within the slot sequentially, and that the at least one printhead segment in each printhead segment carrier installed after the first is positioned longitudinally relative to the at least one printhead segment in the printhead segment carrier last installed before being finally secured and immobilized within the slot. Thus, accurate relative positioning of successive printhead segments lengthwise along the elongate member can be achieved. Other aspects, objects and advantages of the invention, in its different embodiments, will also become apparent from the description given below of preferred embodiments and from the appended claims. BRIEF DESCRIPTION OF THE FIGURES FIG. 1 is a perspective view of one embodiment of an inkjet printhead assembly according to the invention; FIG. 2 is a perspective view of the inkjet printhead assembly shown in FIG. 1 , with a cover component (shield plate) removed; FIG. 3 is an exploded perspective view of a part only of the inkjet printhead assembly shown in FIG. 1 ; FIG. 4 is a perspective partial view of a support extrusion forming part of the inkjet printhead assembly shown in FIG. 3 ; FIG. 5 is a perspective view of a sealing shim forming part of the inkjet printhead assembly shown in FIG. 3 ; FIG. 6 is a perspective view of a printhead segment carrier shown in FIG. 3 ; FIG. 7 is a further perspective view of the printhead segment carrier shown in FIG. 6 ; FIG. 8 is a bottom elevation of the printhead carrier shown in FIGS. 6 and 7 (as viewed in the direction of arrow “X” in FIG. 6 ); FIG. 9 is a top elevation of the printhead carrier shown in FIGS. 6 and 7 (as viewed in the direction of arrow “Y” in FIG. 6 ); FIG. 10 is a cross-sectional view of the printhead carrier of FIGS. 6 and 7 taken at station “B-B” in FIG. 8 ; FIG. 11 is a cross-sectional view of the printhead carrier of FIGS. 6 and 7 taken at station “A-A” in FIG. 8 ; FIG. 11 a is an enlarged cross-sectional view of the seating arrangement of a printhead segment at the print carrier as per detail “E” in FIG. 11 ; FIG. 12 is a cross-sectional view of the printhead carrier of FIGS. 6 and 7 taken at station “D-D” in FIG. 8 ; FIG. 13 is an external perspective view of an end cap of the inkjet printhead assembly shown in FIG. 1 ; FIG. 14 is an internal perspective view of the end cap shown in FIG. 13 FIG. 15 is an external perspective view of a further end cap of the inkjet printhead assembly shown in FIG. 1 ; FIG. 16 is an internal perspective view of the end cap shown in FIG. 15 ; FIG. 17 is a perspective view (from the bottom) of the printhead assembly shown in FIG. 1 ; FIG. 18 is a perspective view of a part assembly of a support profile and modified sealing shim which are alternatives to those shown in FIGS. 4 and 5 ; FIG. 19 is a perspective view showing a molding tool and illustrating the basic arrangement of die components for injection molding of the printhead carrier shown in FIGS. 6 and 7 ; FIG. 20 is a schematic cross-section of the injection molding tool shown in FIG. 19 , in an open position; and FIG. 21 is a schematic transverse cross-section of the injection-molding tool shown in FIG. 19 , in a closed position, taken at a station corresponding to the station “A-A” in FIG. 8 . DESCRIPTION OF THE PREFERRED EMBODIMENT FIG. 1 shows in perspective view an inkjet printhead assembly 1 according to one aspect of the invention and, in phantom outline, a surface 2 on which printing is to be affected. In use, the surface 2 moves relative to the assembly 1 in a direction indicated by arrow 3 and transverse to the main extension of assembly 1 (this direction is hereinafter also referred to as the transverse direction of the assembly 1 ), so that elongate printhead segments 4 , in particular MEMJET printhead segments such as described in the above-mentioned PCT/AU98/00550, placed in stepped overlapping sequence along the lengthwise extension of assembly 1 can print simultaneously across substantially the entire width of the surface. The assembly 1 includes a shield plate 5 with which the surface 2 may come into sliding contact during such printing. Shield plate 5 has slots 6 , each corresponding to one of the printhead segments 4 , and through which ink ejected by that printhead segment 4 can reach surface 2 . The particular assembly 1 shown in FIG. 1 has eleven printhead segments 4 , each capable of printing along a 2 cm printing length (or, in other words, within a printing range extending 2 cm) in a direction parallel to arrow 7 (hereinafter also called the lengthwise direction of the assembly 1 ) and is suitable for single-pass printing of a portrait A4-letter size page. However, this number of printhead segments 4 and their length are in no way limiting, the invention being applicable to printhead assemblies of varying lengths and incorporating other required numbers of printhead segments 4 . The slots 6 and the printhead segments 4 are arranged along two parallel lines in the lengthwise direction, with the printing length of each segment 4 (other than the endmost segments 4 ) slightly overlapping that of its two neighboring segments 4 in the other line. The printing length of each of the two endmost segments 4 overlaps the printing length of its nearest neighbor in the other row at one end only. Thus printing across the surface 2 is possible without gaps in the lengthwise direction of the assembly. In the particular assembly shown, the overlap is approximately 1 mm at each end of the 2 cm printing length, but this figure is by no means limiting. FIG. 2 shows assembly 1 with the shield plate 5 removed. Each printhead segment 4 is secured to an associated one printhead segment carrier 8 that will be described below in more detail. Also secured to each printhead segment 4 is a tape automated bonded (TAB) film 9 , which carries signal and power connections (not individually shown) to the associated printhead segment 4 . Each TAB film 9 is closely wrapped around an extruded support profile 10 (whose function will be explained below) that houses and supports carriers 8 , and they each terminate onto a printed circuit board (PCB) 11 secured to the profile 10 on a side thereof opposite to that where the printhead segments 4 are mounted, see also FIG. 3 . FIG. 3 shows an exploded perspective view of a part only of assembly 1 . In this view, three only of the printhead segment carriers 8 are shown numbered 8 a , 8 b and 8 c , and only the printhead segment 4 associated with printhead segment carrier 8 a is shown and numbered 4 a . The TAB film 9 associated therewith is terminated at one end on an outer face of the printhead segment 4 and is otherwise shown (for clarity purposes) in the unwound, flat state it has before being wound around profile 10 and connected to PCB 11 . As can be seen in FIG. 3 , printhead segment carriers 8 are received (and secured), together with an interposed sealing shim 25 , in a slot 21 of half-circular cross-sectional shape in profile member 10 as will be explained in more detail below. FIG. 4 illustrates a cross-section of the profile member 10 (which is preferably an aluminum alloy extrusion). This component serves as a frame and/or support structure for the printhead segment carriers 8 (with their associated printhead segments 4 and TAB films 9 ), the PCB 11 and shield plate 5 . It also serves as an integral ink supply arrangement for the printhead segments 4 , as will become clearer later. Profile member 10 is of semi-open cross-section, with a peripheral, structured wall 12 of uniform thickness. Free, opposing, lengthwise running edges 16 ′, 17 ′ of side wall sections 16 and 17 respectively of wall 12 border or delineate a gap 13 in wall 12 extending along the entire length of profile member 10 . Profile member 10 has three internal webs 14 a , 14 b , 14 c that stand out from a base wall section 15 of peripheral wall 12 into the interior of member 10 , so as to define together with side wall sections 16 and 17 a total of four (4) ink supply channels 20 a , 20 b , 20 c and 20 d which are open towards the gap 13 . The shapes, proportions and relative arrangement of the webs and wall sections 14 a - c , 16 , 17 are such that their respective free edges 14 a ′, 14 b ′, 14 c ′ and 16 ′, 17 ′, as viewed in the lengthwise direction and cross-section of profile member 10 , define points on a semi-circle (indicated by a dotted line at “a” in FIG. 4 ). In other words, an open slot 21 of semicircular cross-sectional shape is defined along one side of profile member 10 that runs along its extension, with each of the ink supply channels 20 a - d opening into common slot 21 . Base wall section 15 of profile member 10 also includes a serrated channel 22 opening towards the exterior of member 10 , which, as best seen in FIG. 3 , serves to receive fastening screws 23 to fixedly secure PCB 11 onto profile member 10 in a form-fitting manner between free edges 24 (see FIG. 4 ) of longitudinally extending curved webs 107 extending from the base wall section 15 of profile member 10 . Referring again to FIG. 3 , sealing shim 25 is received (and secured) within the half-circular open slot 21 . As best seen in FIGS. 3 and 5 , shim 25 includes four lengthwise extending rows of rectangular openings 26 that are equidistantly spaced in peripheral (widthwise) direction of shim 25 , so that three lengthwise-extending web sections 27 between the aperture rows (of which two are visible in FIG. 5 ) are located so as to be brought into abutting engagement against the free edges 14 a ′, 14 b ′ and 14 c ′ of webs 14 a , 14 b , 14 c of profile member 10 when shim 25 is received in slot 21 . As can be gleaned from FIG. 4 , the free edges 16 ′ and 17 ′ of side wall sections 16 , 17 of profile member 10 are shaped such as to provide a form-lock for retaining the lengthwise extending edges 28 of shim member 25 as a snap fit. In other words, once shim 25 is mounted in profile member 10 , it provides a perforated bottom for slot 21 , which allows passage of inks from the ink supply channels 20 a - d through apertures 26 in shim 25 into slot 21 . A glue or sealant is provided where shim webs 27 and edges 28 mate with the free edges 14 a ′, 14 b ′, 14 c ′, 16 ′ and 17 ′ of profile member 10 , thereby preventing cross-leakage between ink supply channels 20 a - d along the abutting interfaces between shim 25 and profile member 10 . It will be noted from FIG. 5 that not all apertures 26 have the same opening size. Reference numerals 26 ′ indicate two such smaller apertures, the significance of which is described below, which are present in each aperture row at predetermined aperture intervals. A typical size for the full-sized apertures 26 is 2 mm×2 mm. The shim is preferably of stainless steel, but a plastics sheet material may also be used. Turning next to FIGS. 6-12 , these illustrate in different views and sections a typical printhead segment carrier 8 . Carrier 8 is preferably a single microinjection molded part made of a suitable temperature and abrasion resistant and form-holding plastics material. (A further manufacturing operation is carried out subsequent to molding, as described below.) As best seen in FIGS. 6 and 7 , the overall external shape of carrier 8 can be described illustratively as a diametrically slit half cylinder, with a half-circular back face 91 , a partly planar front face 82 and stepped end faces 83 . FIG. 8 shows a plan view of back face 91 and FIG. 9 shows a plan view of front face 82 . Carrier 8 has a plane of symmetry halfway along, and perpendicular to, its length, that is, as indicated by lines marked “b” in FIGS. 8 and 10 which lie in the plane. Line “b” as shown in FIG. 8 extends in a direction that will hereinafter be described as transverse to the carrier 8 . (When the carrier 8 is installed in the assembly 1 , this direction is the same as the transverse direction of the assembly 1 .) Lines marked “c” in FIGS. 8 , 9 , 11 and 12 together similarly indicate the position of an imaginary plane which lies between two sections of the carrier 8 of different length and whose overall cross-sectional shapes are quarter circles. Line “c” as shown in FIG. 9 extends in a direction that will hereinafter be described as lengthwise in the carrier 8 . (When the carrier 8 is installed in the assembly 1 this direction is the same as the lengthwise direction of the assembly 1 .) These sections will hereinafter be referred to as the shorter and longer “quarter cylinder” sections 8 ′ and 8 ″, respectively, to allow referenced description of features of the carrier 8 . Each stepped end face 83 includes respective outer faces 84 ′ and 85 ′ of quarter-circular-sector shaped end walls 84 and 85 and an outer face 86 ′ of an intermediate step wall 86 between and perpendicular to end walls 84 , 85 . This configuration enables carriers 8 to be placed in the slot 21 of profile 10 in such a way that adjoining carriers 8 overlap in the lengthwise direction with the step walls 86 of pairs of neighbouring carriers 8 facing each and overlapping. Such an “interlocking” arrangement is shown in FIG. 2 , wherein it is apparent that every one of the eleven (11) carriers 8 has an orientation, relative to its neighbouring carrier or carriers 8 , such that faces 84 ′ and 85 ′ of each carrier lie adjacent to faces 85 ′ and 84 ′, respectively, of its neighbouring carrier(s) 8 . In other words, each carrier 8 is so oriented in relation to its neighbouring carrier(s) as to be rotated relatively by 180° about an axis perpendicular to the face 82 . In essence, neighbouring carriers 8 will align along a common lengthwise-oriented plane defined between the step walls 86 of adjoining carriers 8 , shorter and longer quarter cylinder sections 8 ′ and 8 ″ of adjoining carriers 8 alternating with one another along the extension of slot 21 . Turning now in particular to FIGS. 7 , 9 , 11 and 11 a , front face 82 of carrier 8 includes on the shorter quarter cylinder section 8 ′ a planar surface 81 . Formed in surface 81 are two handling (i.e. pick-up) slots 87 whose purpose is described below. On the longer quarter cylinder section 8 ″, front face 82 incorporates a mounting or support surface 88 recessed with respect to edges 89 of sector-shaped end walls 84 that are co-planar with the surface 81 . As best seen in FIG. 11 , mounting surface 88 recedes in slanting fashion from a point on the back face 91 of the longer quarter cylinder section 8 ″ towards an elongate recess 90 extending lengthwise between walls 84 . Recess 90 is of constant transverse cross-section along its length and is shaped to receive in form-fitting manner one printhead segment 4 . FIG. 11 a shows, schematically only, printhead segment 4 in position in recess 90 . Mounting surface 88 is provided to accommodate in flush manner with respect to the surface 81 the terminal end of TAB film 9 connected to printhead segment 4 , as is best seen in FIG. 3 . Due to the opposing orientations of neighbouring carriers 8 along the extension of assembly 1 , the TAB films 9 associated with any two neighbouring carriers 8 lead away from their respective segments 4 in opposite transverse directions, as can be seen in FIG. 2 . Referring now to FIGS. 6 , 7 , 8 , 10 and 11 in particular, four rows of ink galleries or ink supply passages 92 a to 92 d of generally quadrilateral cross-section are formed within the printhead segment carrier 8 . The ink galleries 92 a to 92 d act as conduits for ink to pass from the ink supply passages 20 a to 20 d , respectively, via openings 26 in the shim 25 , to the printhead segment 4 mounted in recess 90 of the printhead segment carrier 8 . Galleries 92 a - 92 d extend in quasi-radial arrangement between the half-cylindrical back face 91 of carrier 8 and recess 90 located in the longer quarter cylinder section 8 ″ at front face 82 . The expression “quasi-radial” is used here because recess 90 is not located at a transversely central position across carrier 8 , but is offset into the longer quarter cylinder section 8 ″, so that the inner ends of galleries 92 a - 92 d are similarly off-set, as further described below. Each gallery 92 has a rectangular opening 93 at back face 91 . All rectangular openings 93 have the same dimension in a peripheral direction of face 91 and are equidistantly spaced around the periphery of back face 91 . Moreover, the openings 93 are symmetrically located on opposing sides of the boundary between shorter quarter cylinder section 8 ′ and longer quarter cylinder section 8 ″, as represented in FIG. 11 by the line marked “c”. All openings 93 in the shorter quarter cylinder section 8 ′ are of the same dimension, and equispaced, in the lengthwise direction. This also applies to the openings 93 in the longer quarter cylinder section 8 ″, except that openings 93 ′ in the longer quarter cylinder section 8 ″ which correspond to endmost galleries 92 a ′ and 92 b ′ are of smaller dimension in the lengthwise direction than the other galleries 92 a and 92 b , respectively. By way of further description of how the galleries 92 a to 92 d are formed, printhead segment carrier 8 includes a set of five (5) quasi-radially converging walls 95 which converge from back face 91 towards recess 90 at front face 82 and two of which define the faces 81 and 88 . The walls 95 perpendicularly intersect seven (7) generally semi-circular and mutually parallel walls 97 that are equidistantly spaced apart in lengthwise extension of carrier 8 . Of walls 97 , the two endmost ones extending into the shorter quarter cylinder section 8 ′ provide the endwalls 85 of stepped end faces 83 , thereby defining twenty-four (24) quasi-radially extending ink galleries 92 a to 92 d , of quadrilateral cross-section, in four lengthwise-extending rows each of six galleries. The walls 97 are parallel to and lie between endwalls 84 . FIG. 12 shows a cross-section through one of the lengthwise end portions of longer quarter cylinder section 8 ″ of carrier 8 . By comparison with FIG. 11 (which shows a cross-section through the main body of carrier 8 ), it will be seen that the quasi-radially extending walls 95 bordering end gallery 92 a ′ have the same shape as walls 95 which border galleries 92 a , whereas gallery 92 b ′ is bounded on one side by intermediate step wall 86 and by a wall 108 . FIG. 12 also shows a wall 111 and a wall formation 112 on the wall 86 , the purpose of which is explained below. Converging walls 95 are so shaped at their radially inner ends as to define four ink delivery slots 96 a to 96 d which extend lengthwise in the carrier 8 and which open into the recess 90 , as best seen in FIGS. 11 and 11 a . The slots 96 a to 96 d extend between the opposite end walls 84 of longer quarter cylinder section 8 ″ and pierce through the inner parallel walls 97 , including the endwise opposite walls 97 which form the end walls 85 of the shorter cylinder section 8 ′. FIG. 12 shows how slots 96 a to 96 d extend and are formed within the end portions of the longer quarter cylinder section 8 ″, where the slots 96 a to 96 d are defined by the terminal ends of two of walls 95 , walls 108 , 111 and wall formation 112 , wall formation 112 in effect being a perpendicular lip of intermediate step wall 86 . The widths and transverse positioning of the ink delivery slots 96 a to 96 d are such that when a printhead segment 4 is received in recess 90 , a respective one of the slots 96 a - 96 d will be in fluid communication with one only of four lengthwise oriented rows of ink supply holes 41 on rear face 42 of printhead segment 4 , compare FIG. 11 a . Each row of ink supply holes 41 corresponds to a row of printhead nozzles 43 running lengthwise along the front face 44 of printhead segment 4 . In the schematic representation of segment 4 in FIG. 11 a , the positions of holes 41 and nozzles are indicated by dots, with no attempt made to show their actual construction. Reference to PCT Application No. PCT/AU98/00550 will provide further details of the make-up of segment 4 . Accordingly, each of the ink galleries of a specific gallery row 92 a to 92 d is in fluid communication with one only of the rows of ink supply holes 41 . Once a printhead segment 4 is form fittingly received in recess 90 and sealingly secured with its rear face 42 against the terminal inner ends of walls 95 , and wall formations 108 , 111 and 112 (using a suitable sealant or adhesive), cross-communication and ink bleeding between slots 96 a - 96 d via recess 90 is not possible. When a carrier 8 is installed in its correct position lengthwise in the slot 21 of profile 10 , compare FIG. 3 , each opening 93 in its back face 91 aligns with one of the openings 26 in the shim 25 . Smaller openings 26 ′ in the shim 25 correspond to openings 93 ′ of the smaller galleries 92 a ′ and 92 b ′ of carrier 8 . Therefore, each one of the ink supply channels 20 a to 20 d is in fluid communication with one only of the rows of ink galleries 92 a to 92 d , respectively, and so with one only of the slots 96 a to 96 d respectively and only one of the rows of ink supply holes 41 . A suitable glue or sealant is provided at mating surfaces of the shim 25 and the carrier 8 to prevent leakage of ink from any of the channels 20 a to 20 d to an incorrect one of the galleries 92 , as described further below. The symmetrical location (mentioned above) of openings 93 on back face 91 of carrier 8 , which is matched by the openings 26 in shim 25 , enables the carrier 8 to be received in the slot 21 in either of the two orientations shown in FIG. 3 , with in both cases each row of ink galleries 92 a to 92 d aligning with one only of the ink supply channels 20 a to 20 d. As mentioned above, the longer quarter cylinder section 8 ″ of carrier 8 has two galleries 92 a ′ and 92 b ′ at each lengthwise end that have no counterpart in the shorter section 8 ′. These galleries 92 a ′ and 92 b ′ provide direct ink supply paths to that part of their associated ink delivery slots 96 a and 96 b located in the longer quarter cylinder section 8 ″, and thus to the ink supply holes 41 of the printhead segment 4 that are located near the lengthwise terminal ends of segment 4 when secured within recess 90 . There are no corresponding quasi-radial galleries to supply ink to the end regions of the slots 96 c and 96 d . However, it is desirable to provide direct ink supply to the end portions of the other two slots 96 c and 96 d as well, without reliance on lengthwise flow within the slots 96 c and 96 d of ink that has passed through galleries 92 c and 92 d respectively. This is ensured by provision of ink supply chambers 99 c and 99 d which are shown in FIG. 12 and which supply ink to the slots 96 c and 96 d , respectively. Chambers 99 c and 99 d are bounded by the walls 84 , 86 , and wall formations 108 , 111 and 112 , are open towards slots 96 c and 96 d , respectively, and are in fluid communication through holes 113 and 114 in an endmost wall 97 with endmost ones of ink galleries 92 c and 92 d , respectively. The holes 113 and 114 have outlines shaped to match the transverse cross-sectional shapes of the chambers 99 c and 99 d , respectively, as shown in FIG. 12 , and the means whereby holes 113 and 114 are formed is described below. FIGS. 13 and 14 show a first end cap 50 , which is sealingly secured to an open terminal longitudinal end of profile member 10 , as may be seen in FIGS. 1 and 2 . Cap 50 is molded from a plastics material and it incorporates a generally planar wall portion 51 that extends perpendicularly to a lengthwise axis of profile member 10 . Four tubular stubs 55 a - 55 d are integrally molded with planar wall portion 51 on side 52 of wall portion 51 which will face away from support profile 10 when end cap 50 is secured thereto. On the planar wall side 53 which will face the longitudinal terminal end of support profile 10 (see FIG. 14 ), four hollow-shaped stubs 57 a - 57 d are integrally molded with planar wall portion 51 . As best seen in FIG. 14 , ink supply conduits 56 a to 56 d are defined within tubular stubs 55 a to 55 d respectively, extend through planar wall portion 51 , and open within shaped stubs 57 a to 57 d , respectively, located on the other sides of cap 50 . The shape of each one of the insert stubs 57 a to 57 d , as seen in transverse cross-section, corresponds respectively to one of the ink supply channels 20 a to 20 d of support profile so that, when cap 50 is secured to the terminal axial end of support profile 10 , the walls of stubs 57 a - 57 d are received form-fittingly in ink supply channels 20 a - 20 d to prevent cross-migration of ink therebetween. The face 53 abuts a terminal end face of the profile 10 . Preferably, glue or a sealant can be applied to the mating surfaces of profile 10 and cap 50 to enhance the sealing function. The tubular stubs 55 a - 55 d serve as female connectors for pliable/flexible ink supply hoses (not illustrated) that can be connected thereto sealingly, thereby to supply ink to the integral ink supply channels 20 a - 20 d of support profile 10 . A further stub 58 , D-shaped in transverse cross-section, is integrally molded to planar wall portion 51 at side 53 . In completed assembly 1 , the curved wall 71 , semi-circular in transverse cross-section, of retaining stub 58 seals against the inside surface of shim 25 , with the terminal edge of shim 25 abutting a peripheral ridge 72 around the stub 58 . Preferably, to avoid cross-migration of ink among channels 20 a to 20 d , an adhesive or sealant is provided between the shim 25 and wall 71 . The stub 58 assists in retaining the shim 25 in slot 21 . A second end cap 60 , which is shown in FIGS. 15 and 16 , is mounted to the other end of the profile 10 opposite to cap 50 . Cap 60 has insert stubs 67 a to 67 d and a retaining stub 68 identical in arrangement and shape to stubs 57 a to 57 d and stub 58 , respectively, of end cap 50 . Insert stubs 67 a to 67 d and retention stub 68 are integrally molded with a planar wall portion 61 , and in the completed assembly 1 seal off the individual ink supply channels 20 a - 20 d from one another, to prevent cross-migration of ink among them. Wall 77 of the retention stub 68 abuts the shim 25 in the same way as described above. A sealant or adhesive is preferably used with end cap 60 in the same way (and for the same purpose) as described above in respect of end cap 50 . Whereas end cap 50 enables connection of ink supply hoses to the printhead assembly 1 , end cap 60 has no tubular stubs on exterior face 62 of planar wall portion 61 . Instead, four tortuous grooves 65 a to 65 d are formed on exterior face 62 , and terminate at holes 66 a to 66 d , respectively, extending through wall portion 61 . Each one of holes 66 a to 66 d opens into a respective one of the channels 20 a to 20 d so that when the cap 60 is in place on the profile 10 , each one of the grooves 65 a to 65 d is in fluid communication with a respective one of the channels 20 a to 20 d . The grooves 65 a - 65 d permit bleeding-off of air during priming of the printhead assembly 1 with ink, as holes 66 a - 66 d permit air expulsion from the ink supply channels 20 a - 20 d of support profile 10 via grooves 65 a - 65 d . Grooves 65 a - 65 d are capped under a translucent plastic film 69 bonded to outer face 62 . Translucent plastic film 69 thus also serves the purpose of allowing visual confirmation that the ink supply channels 20 a - 20 d of profile 10 are properly primed. For charging the ink supply channels 20 a - 20 d with ink, film 69 is folded back (as shown in FIG. 15 ) to partially uncover grooves 65 a - 65 d , so that displaced air may bleed out as ink enters the grooves 65 a - 65 d through holes 66 a - 66 d . When ink is visible behind film 69 in each groove 65 a - 65 d , film 69 is folded towards face 62 and bonded against face 62 to sealingly cover face 62 and so cap-off grooves 65 a - 65 d and isolate them from one another. Referring to FIG. 17 (and see also FIGS. 3 and 4 ), the printed circuit board (PCB) 11 locates between edges 24 formed on profile 10 , and is secured by screw fasteners 23 which engage with the serrations in elongate channel 22 of support profile 10 . The PCB 11 contains three surface mounted halftoning chips 73 , a data connector 74 , printhead power and ground busbars 75 and decoupling capacitors 76 . Side walls 16 , 17 of support profile 10 are rounded near the edges 24 to avoid damage to the TAB films 9 when these are wound about profile 10 . The electronic components 73 and 76 are specific to the use of MEMJET chips as the printhead segments 4 , and would of course, if other another printhead technology were to be used, be substituted with other components as necessitated by that technology. The shield plate 5 illustrated in FIG. 1 , which is a thin sheet of stainless steel, is bonded with sealant such as a silicon sealant onto the printhead segment carriers 8 . The shield plate 5 shields the TAB films 9 and the printhead segments 4 from physical damage and also serves to provide an airtight seal around the printhead segments 4 when the assembly 1 is capped during idle periods. The multi-part layout of the printhead assembly 1 that has been described in detail above has the advantage that the printhead segment carriers 8 , which interface directly with the printhead segments 4 and which must therefore be manufactured with very small tolerances, are separate from other parts, including particularly the main support frame (profile 10 ) which may therefore be less tightly toleranced. As noted above, the printhead segment carriers 8 are precision injection micro-moldings. Moldings of the required size and complexity are obtainable using existing micromolding technology and plastics materials such as ABS, for example. Tolerances of +/−10 microns on specified dimensions are achievable including the ink supply grooves 96 a - 96 d , and their relative location with respect to the recess 90 in which the printhead segments 4 are received. Such tolerances are suitable for this application. Other material selection criteria are thermal stability and compatibility with other materials to be used in the assembly 1 , such as inks and sealants. The profile 10 is preferably an aluminum alloy extrusion. Tolerances specified at +/−100 microns have been found suitable for such extrusions, and are achievable as well. FIGS. 19 , 20 and 21 are schematic representations only, intended to provide an understanding of the construction of an injection-molding die used in the manufacture of a printhead segment carrier 8 . A multi-part die 100 is used, having a fixed base die part 104 , which in use defines the face 82 , recess 90 and slots 96 a to 96 d of the carrier 8 , and a multi-part upper die part 102 . The upper die part 102 is closed against the base part 104 for molding, and includes a part 101 with multiple fingers 101 a , which in use form the galleries 92 b (including galleries 92 b ′) and parts 106 which are fixed relative to part 101 . Also included in the upper part 102 are die parts 103 which are movable relative to the part 101 and which have fingers 103 a to form the remaining galleries 92 a , 92 c and 92 d . Parts 103 seat against parts 106 when molding is underway. Spaces between the fingers 101 a and 103 a correspond to the walls 97 . In use of the die 100 , terminal tips of the fingers 101 a and 103 a close against blades 105 which in use form the ink supply slots 96 a - 96 d of carrier 8 and which are mounted to male base 104 to be detachable and replaceable when necessary. Base die part 104 also has inserts 104 a , which in use form the pickup slots 87 . Because zero draft is preferred on the stepped end faces 83 in this application, the die 100 also has two movable end pieces (not shown, for clarity) which in use of the die 100 are movable generally axially to close against the upper die part 102 and which are shaped to define the end faces 84 ′, 85 ′ and 86 ′ of carrier 8 . FIG. 21 shows a schematic transverse cross-section of the mold 100 when closed, with areas in black corresponding to the carrier 8 being molded. As was mentioned above, the two opposite end portions of the larger quarter cylinder section of carrier 8 incorporate two ink supply chambers 99 c and 99 d (see FIG. 12 ) to provide ink to the ink supply slots 96 c and 96 d in that region of the carrier 8 . These chambers 99 c and 99 d and associated communication holes 113 and 114 in parallel walls 97 that lead into the neighbouring galleries 92 c and 92 d , are formed in an operation subsequent to molding, by laser cutting openings of the required shape in the end walls 84 and the neighbouring inner parallel walls 97 from each end. The openings cut in end walls 84 are only necessary so as to access the inner walls 97 , and are therefore subsequently permanently plugged using appropriately shaped plugs 115 as shown in FIG. 6 . Extrusions usable for profile 10 can be produced in continuous lengths and precision cut to the length required. The particular support profile 10 illustrated is 15.4 mm×25.4 mm in section and about 240 mm in length. These dimensions, together with the layout and arrangement of the walls 16 and 17 and internal webs 14 a to 14 c , have been found suitable to ensure adequate ink supply to eleven (11) MEMJET printhead segments 4 carried in the support profile to achieve four-color printing at 120 pages per minute (ppm). Support profiles with larger cross-sectional dimensions can be employed for very long printhead assemblies and/or for extremely high-speed printing where greater volumes of ink are required. Longer support profiles may of course be used, but are likely to require cross-bracing and location into a more rigid chassis to avoid alignment problems of individual printhead segments, for example in the case of a wide format printer of 54″ (1372 mm) or more. An important step in manufacturing (and assembling) the assembly 1 is achieving the necessary, very high level of precision in relative positioning of the printhead segments 4 , and here too the construction of the assembly 1 as described above is advantageous. A suitable manufacturing sequence that ensures such high relative positioning of printheads on the support profile will now be described. After manufacture and successful testing of an individual printhead segment 4 , its associated TAB film 9 is bumped and then bonded to bond pads along an edge of the printhead segment 4 . That is, the TAB film is physically secured to segment 4 and the necessary electrical connections are made. The terms “bumped” and “bonded” will be familiar to persons skilled in the arts where TAB films are used. The printhead carrier 8 is then primed with adhesive on all those surfaces facing into recess 90 that mate and must seal with the printhead segment 4 , see FIG. 11 a , i.e. along the length of the radially-inner edges of walls 95 , 108 and 111 , the face of formation 112 and on inner faces of walls 84 . The printhead segment 4 is then secured in place in recess 90 with its TAB film 9 attached. Extremely accurate alignment of the printhead segment 4 within recess 90 of printhead segment carrier 8 is not necessarily required (but is preferred), because relative alignment of all segments 4 at the support profile 10 is carried out later, as is described below. The assembly of the printhead segment 4 , printhead segment carrier 8 and TAB film 9 is preferably tested at this point for correct operation using ink or water, before being positioned for placement in the slot 21 of support profile 10 . The support profile 10 is accurately cut to length (where it has been manufactured in a length longer than that required, for example by extrusion), faced and cleaned to enable good mating with the end caps 50 and 60 . A glue wheel is run the entire length of semi-circular slot 21 , priming the terminal edges 14 a ′, 14 b ′, 14 c ′ of webs 14 a - 14 c and edges 16 ′, 17 ′ of profile side walls 16 , 17 with adhesive that will bond the sealing shim 25 into place in slot 21 once sealing shim 25 is placed into it with preset distance from its terminal ends (+/−10 microns). The shim 25 is snap-fitted into place at edges 16 ′, 17 ′ and the glue is allowed to set. Next, end caps 50 and 60 are bonded into place whereby (ink channel sealing) insert stubs 57 a - 57 d and 67 a - 67 d are received in ink channels 20 a - 20 d of profile 10 , and faces 71 and 77 of retention stubs 58 and 68 , respectively, lie on shim 25 . This sub-assembly provides a chassis in which to successively place, align and secure further sub-assemblies (hereinafter called “carrier subassemblies”) each consisting of a printhead segment carrier 8 with its respective printhead segment 4 and TAB film 9 already secured in place thereon. A first carrier sub-assembly is primed with glue on the back face 91 of its printhead segment carrier 8 . At least the edges of walls 95 and 86 are primed. A glue wheel, running lengthwise, is preferably used in this operation. After priming with glue, the carrier sub-assembly is picked up by a manipulator arm engaging into pick-up slots 87 on front face 82 of carrier 8 and placed next to the stub 58 of end cap 50 (or the stub 68 of cap 60 ) at one end of slot 21 in profile 10 . The glue employed is of slow-setting or heat-activatable type, thereby to allow a small level of positional manipulation of each carrier subassembly, lengthwise in the slot 21 , before final setting of the glue. With the first carrier subassembly finally secured to the shim 25 within the slot 21 , a second carrier sub-assembly is then picked up, primed with glue as above, and placed in a 180-degree-rotated position (as described above, and as may be seen in FIG. 3 ) next to the first carrier sub-assembly onto shim 25 and within the slot 21 . The second carrier sub-assembly is then positioned lengthwise so that there is correct lengthwise relative positioning of its printhead segment 4 and the segment 4 of the previously placed segment 4 , as determined using suitable fiducial marks (not shown) on the exposed front surface 44 of each of the printhead segments 4 . That is, lengthwise alignment is carried out between successive printhead segments 4 , even though it is the printhead segment carrier 8 that is actually manipulated. This relative alignment is carried out to such (sub-micron) accuracy as is required to match the printing resolution capability of the printhead segments 4 . Finally, the bonding of the second carrier sub-assembly to shim 25 is completed. The above process is then repeated with further carrier sub-assemblies being successively positioned, aligned, and bonded into place, until all carrier subassemblies are in position within the slot 21 and bonded in their correct positions. The shield plate 5 has a thin film of silicon sealant applied to its underside and is mated to the printhead segment carriers 8 and TAB films 9 along the entire length of the printhead assembly 1 . By suitable choice of adhesive properties of the silicon sealant, the shield plate 5 can be made removable to enable access to the printhead segment carriers 8 , printhead segments 4 and TAB films 9 for servicing and/or exchange. A sub-assembly of PCB 11 and printhead control and ancillary components 73 to 76 is secured to profile 10 using four screws 23 . The TAB films 9 are wrapped around the exterior walls 16 , 17 of profile 10 and are bumped and bonded (i.e. physically and electrically connected) to the PCB 11 . See FIG. 17 . Finally, the completed assembly 1 is connected at the ink inlet stubs 55 a - d of end cap 50 to suitable ink supplies, primed as described above and sealed using sealing film 69 of end cap 60 . Power and signal connections are completed and the inkjet printhead assembly 1 is ready for final testing and subsequent use. It will be apparent to persons skilled in the art that many variations of the above-described assembly and components are possible. For example, FIG. 18 shows a shim 125 that is substantially the same as shim 25 , including having openings 126 and 126 ′ corresponding to the openings 26 and 26 ′ in shim 25 , save for longitudinally extending rim webs 128 which, when the shim 125 is mounted to a support profile 110 , abut in surface-engaging manner against the outside of the terminal ends of side walls 116 , 117 of profile 110 instead of being snap-fittingly received between them as is the case with shim 25 . This arrangement permits wider tolerances to be used in the manufacture of the support profile 110 without compromising the mating capability of the shim 125 and the profile 110 . In yet another possible arrangement, the shim 25 could be eliminated entirely, with the printhead segment carriers 8 then bearing and sealing directly on the edges 14 a ′- 14 c ′ and 16 ′, 17 ′ of the webs 14 a - 14 c and side walls 16 , 17 at slot 21 of support profile 10 . It will be appreciated by persons skilled in the art that still further variations and modifications may be made without departing from the scope of the invention. The embodiments of the present invention as described above are in no sense intended to be restrictive.
A printhead assembly comprises an elongate support structure; a series of side wall sections extending a length of the support structure and defining ink supply channels, edges of the walls delineating a gap; a plurality of carriers positioned end-to-end in the gap and supported by said edges of the walls, the carriers defining a recess and ink supply passages in fluid communication with the recess and the ink supply channels; and a printhead integrated circuit mounted in each recess to receive ink from the ink supply channels. The elongate support structure is configured to permit a printed circuit board (PCB) to be fastened to an outside of the support structure so that the PCB can be connected to the printhead integrated circuits.
1
BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to new solutions or dispersions of cationically and optionally non-ionically hydrophilically modified polyisocyanate addition products with built-in acyl urea groups, a process for their preparation and their use as coating compounds for flexible or rigid substrates or as sizes for paper. 2. Description of the Prior Art Processes for the preparation of ionically modified polyurethanes are known and have been described, for example, in the following literature: DE-PS No. 880,485, DE-AS No. 1,044,404, U.S. Pat. No. 3,036,998, DE-PS No. 1,178,586, DE-PS No. 1,184,946, DE-AS No. 1,237,306, DE-AS No. 1,495,745, DE-OS No. 1,595,602, DE-OS No. 1,770,068, DE-OS NO. 2,019,324, DE-OS No. 2,035,732, DE-OS No. 2,446,440, DE-OS No. 2,345,256, DE-OS No. 2,345,245, DE-OS No. 2,427,274, U.S. Pat. No. 3,479,310 and Angewandte Chemie 82, 53 (1970) and Angew. Makromol. Chem. 26, 85 et seq. (1972). The aqueous dispersions of the above mentioned polyurethanes may be used for a wide range of purposes, e.g. as adhesives or for coating various flexible or non-flexible substrates. In spite of the large number of known processes and the products obtained from them, however, the demand persists for aqueous dispersions which have quite specific properties. The process described below provides the possibility of a simple method of altering the properties of the products in the desired direction over a wide range by suitable choice of an organic substituent attached by way of acyl urea group. The preparation of isocyanate polyaddition products containing acyl urea groups is known per se and has been described, for example, in DE-OS No. 2,436,740 and DE-OS No. 2,714,293. In these known processes, the products are either prepared in the form of solutions and converted into films to form coatings, lacquer coverings or foils (DE-OS No. 2,436,740) or the polyhydroxyl compounds containing acyl urea groups are first prepared and then converted into foams containing acyl urea groups, (DE-OS No. 2,714,293). It was not foreseeable, however, that this principle would also be applicable to the chemistry of aqueous polyurethane dispersions and in particular that the dispersions according to the invention described below of polyurethanes containing hydrophobic side chains attached by way of acyl urea groups would be at least equal in quality as paper sizes, for example to the high quality products disclosed in DE-OS No. 2,400,490. In particular, the dispersions and solutions of polyurethanes containing cationic groups and hydrophobic side chains described below are superior to the paper sizes disclosed in the last mentioned prior publication due to their improved sizing action both in alum-free paper and in alum-containing or pre-sized paper or paper containing wood. SUMMARY OF THE INVENTION The present invention relates to aqueous solutions or dispersions of polyisocyanate addition products which contain about 2 to 300 milliequivalents per 100 g of solids of chemically incorporated ternary or quaternary ammonium groups and up to about 25% by weight, based on solids, of chemically incorporated ethylene oxide units, --CH 2 --CH 2 --0--, present within a polyether chain, the ternary or quaternary ammonium groups and the ethylene oxide units being present in an amount sufficient to guarantee the solubility or dispersibility of the polyisocyanate addition products in water, characterized in that the polyisocyanate addition products contain segments built into the polymer chain corresponding to the general formula ##STR2## wherein R represents a saturated or unsaturated aliphatic hydrocarbon group having 1 to 35 carbon atoms, preferably 9 to 22 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms or an araliphatic hydrocarbon group having from 7 to 10 carbon atoms or, where several groups R are present in the same molecule, they may constitute different groups conforming to the above definition for R, the total quantity of structural units of the above mentioned formula corresponding to an acylated urea group content of the formula ##STR3## in the polyisocyanate addition product of about 0.1 to 20% by weight, based on the solids content. The present invention also relates to a process for the preparation of these solutions or dispersions by the reaction of (a) organic polyisocyanates and optionally organic monoisocyanates, with (b) compounds containing isocyanate reactive groups. In this process, the starting components (b) include components containing ternary or quaternary ammonium groups or groups capable of being converted into ternary or quaternary ammonium groups, the at least partial conversion into salt groups of this kind taking place during or after the polyaddition reaction. Components (a) and/or (b) may include compounds containing ethylene oxide units present within a polyether chain, the total quantity of such hydrophilic components being calculated to provide sufficient ternary or quaternary ammonium groups in the polyisocyanate polyaddition product to enable it to be dissolved or dispersed in water, that is about 2 to 300 milliequivalents per 100 g of solid substance and optionally 0 to about 25% weight of ethylene oxide units of the type mentioned above. The process according to the invention further includes conversion of the polyisocyanate addition product prepared as described above into an aqueous solution or dispersion during or after the addition reaction, and the process is characterized in that the starting components (a) and/or (b) contain starting components containing acyl urea groups corresponding to the formula ##STR4## the quantity of these starting components being so calculated that the polyisocyanate addition product contains about 0.1 to 20% by weight, based on the solids content, of structural units corresponding to the formula ##STR5## Lastly, the present invention relates to the use of the solutions or dispersions according to the invention as coating compounds for flexible or non-flexible substrates and as sizes for paper or for the preparation of sizes for paper. DETAILED DESCRIPTION OF THE INVENTION The dispersions according to the invention are prepared from (a) organic polyisocyanates, optionally together with monofunctional isocyanates,° (b) compounds containing at least 2 isocyanate reactive groups, optionally together with corresponding, monofunctional compounds, and optionally (c) further auxiliary agents and additives. The following are examples of suitable starting components (a): (a1) diisocyanates of the formula Q(NCO) 2 , wherein Q denotes an aliphatic hydrocarbon group having 4 to 12 carbon atoms, a cycloaliphatic hydrocarbon group having 6 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 15 carbon atoms or an araliphatic hydrocarbon group having 7 to 15 carbon atoms. Examples of such diisocyanates include tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl cyclohexane, 4,4'-diisocyanatodicyclohexyl methane, 4,4'-diiscoyanato-dicyclohexyl propane-(2,2), 1,4-diisocyanatobenzene, 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, 4,4'-diisocyanatodiphenyl methane, 4,4'diisocyanato diphenyl propane-(2,2), p-xylylene-diisocyanate, α, α, α', α',-tetramethyle-m-or -p-xylylene diisocyanate, and mixture of these compounds. The following are further examples of components (a) suitable for the purpose of this invention: (a2) prepolymers containing isocyanate groups of the type known in polyurethane chemistry which are obtained by the reaction of simple diisocyanates of the type exemplified under (a1) with organic polyhydroxyl compounds of the type exemplified under (b1), using an NCO/OH equivalent ratio of about 1.2:1 to 10:1, preferably about 1.5:1 to 2.5:1. It will be evident from the above mentioned equivalent ratio that the term "isocyanate prepolymers" as used in the context of this invention also includes so called "semi-prepolymers" i.e. mixtures of excess, unreacted diisocyanates with isocyanate prepolymers. Compounds suitable as starting components (a) according to the invention also include the following: (a3) polyisocyanates containing acyl urea groups of the general formula ##STR6## wherein R has the meaning indicated above. Polyisocyanates containing several acyl urea groups in which the individual groups R conform to the above definition but differ from one another may also be used as component (a3). The polyisocyanates (a3) containing acyl urea groups may be either comparatively low molecular weight or comparatively high molecular weight isocyanate prepolymers. The starting components (a3) are prepared by a method analogous to that of the teaching of DE-OS Nos. 2,436,741 by partial carbodiimidization of the isocyanate groups of organic polyisocyanates of the type exemplified under (a1) and (a2) above with subsequent chemical addition of organic carboxylic acids R--COOH to the resulting, carbodiimide-modified polyisocyanates. Typical examples of suitable starting components (a3) include diisocyanates corresponding to the following formula ##STR7## which are prepared by initially reacting the carbodiimide groups of diisocyanatocarbodiimides corresponding to the following general formula OCN--(R.sup.1 --N═C═N).sub.m --R.sup.1 --NCO either completely or partially with carboxylic acids of the general formula R--COOH, optionally in the presence of a suitable solvent at temperatures of about 25° to 100° C. In the above formulae, R denotes a group of the type already indicated in the definition for R, R 1 denotes a divalent hydrocarbon group optionally containing urethane, ester and/or ether groups, which is obtained by removal of the isocyanate end groups from a simple organic diisocyanate or from an isocyanate prepolymer containing urethane groups and optionally ether or ester groups, the groups R 1 may be either identical or different if several such groups R 1 are present in the same molecule, and m represents an integer or (as a statistical average) a fraction having a value 1 to 10, preferably 1 to 4. The method of preparation of the diisocyanatocarbodiimides is known and has been described, for example, in U.S. Pat. Nos. 2,840,589 and 2,941,966 and by P. W. Campbell and K. C. Smeltz in Journal of Organic Chemistry, 28, 2069 (1963). A particularly mild method of preparation resulting in diisocyanatocarbodiimides which are free from by-products consists of a heterogeneous catalysis according to German Offenlegungsschriften Nos. 2,504,400 and 2,552,350. The carbodiimidization of diisocyanates in the presence of very small quantities of phospholine oxide followed by blocking of the catalyst with acid chlorides has been described in DE-OS No. 2,653,120. The starting components for the diisocyanates containing carbodiimide groups are preferably aromatic diisocyanates of the type exemplified under (a1). Examples of suitable carboxylic acids corresponding to the formula R--COOH include acetic acid, propionic acid, hexane carboxylic acid, lauric acid, palmitic acid, stearic acid, benzoic acid, phenyl acetic acid, acrylic acid, methacrylic acid, crotonic acid, 10-undecenic acid, oleic acid and linoleic acid. Other monocarboxylic acids not corresponding to the definition for R indicated above could in principle also be used in the process according to the invention, e.g. chloroacetic acid, cyclohexane carboxylic acid, abietic acid and 4-dimethyl-aminobenzoic acid as well as monoesters and monoamides of dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid with monohydric alcohols or amines. The use of such special monocarboxylic acids is less preferred purely on the grounds of cost although it would constitute an entirely equivalent method of carrying out the process claimed according to the invention. Any mixtures of acids of the general formula R--COOH exemplified above could in principle also be used in the process according to the invention. The quantity of acid used is calculated to provide about 0.2 to 1.2, preferably about 0.5 to 1.2 mol of carboxyl groups per mol of carbodiimide groups in the reaction mixture. The isocyanate prepolymers containing acyl urea groups which are also suitable as component (a3) may be prepared either by a reaction of the above mentioned polyisocyanates based on low molecular weight diisocyanates and containing acyl urea groups with subequivalent quantities of polyhydroxyl compounds of the type exemplified below under (b1) and/or (b2) or by partial carbodiimidization of isocyanate prepolymers of the type exemplified above under (a2), followed by reaction of the products of carbodiimidization with carboxylic acids R--COOH as described above. The following are further examples of compounds. which may be used as starting components (a) for the process according to the invention: (a4) hydrophilically modified polyisocyanates such as diisocyanates containing ethylene oxide units built into polyether side chains according to U.S. Pat. No. 3,920,598. The inclusion of such hydrophilically modified polyisocyanates is, however, less preferred since the hydrophilic groups in the process according to the invention are preferably incorporated using starting component (b) described below. In the process according to the invention, components (a1) to (a4) exemplified above could in principle also be used in combination with higher functional low molecular weight polyisocyanates such as the reaction products of 3 mols of 2,4-diisocyanatototluene and 1 mol of trimethylol propane or in combination with mono-functional isocyanates such as phenyl isocyanate, hexyl isocyanate or n-dodecyl isocyanate. Mono-functional isocyanates containing polyether chains with built in ethylene oxide units of the type mentioned in U.S. Pat. Nos. 3,920,598 and 4,237,264 may also be used, but when such mono-functional isocyanates are used it is generally necessary to prevent premature chain breaking by simultaneously using higher than difunctional components, especially for preparing high molecular weight polyurethanes. The starting components (a) used in the process according to the invention are preferably difunctional isocyanates of the type exemplified above. The following are examples of suitable starting components (b) for the process according to the invention: (b1) polyhydroxy polyesters or polyethers having a molecular weight of 400 to about 4,000 known from polyurethane chemistry, preferably the difunctional compounds of this type. The polyesters may be obtained in known manner by the reaction of polybasic acids, in particular difunctional acids such as adipic acids, phthalic acid, tetrahydrophthalic acid and/or hexahydrophthalic acid, with excess quantities of polyhydric alcohols, preferably dihydric alcohols of the type exemplified below under (b2). The polyethers may be obtained by the alkoxylation of suitable starter molecules such as water, ammonia aniline or the polyhydric alcohols exemplified below under (b2) with alkylene oxides such as ethylene oxide and/or propylene oxide. The following are further examples of suitable starting components (b) for the process according to the invention: (b2) polyhydric alcohols, in particular dihydric alcohols having a molecular weight of 62 to 399, especially the alkane polyols such as ethylene glycol, propylene glycol, tetramethylene diol, hexamethylene diol, glycerol, trimethylol propane or trimethylol ethane, or low molecular weight alcohols containing ether groups such as diethylene glycol, triethylene glycol, dipropylene glycol or tripropylene glycol. Any mixtures of such alcohols may also be used in the process according to the invention. Further examples of suitable starting components (b) for the process according to the invention are as follows: (b3) Compounds having a molecular weight of 32 to 400 containing at least two aminic or hydrazinic amino groups such as ethylene diamine, hexamethylene diamine, isophorone diamine, 2,4-diaminotoluene, 4,4'-diaminodiphenyl methane, 4,4'-diaminodicyclohexyl methane, diethylene triamine, triethylene tetramine, hydrazine and hydrazine hydrate. Starting components of this kind may also be used in a masked form, i.e. in particular in the form of the corresponding ketimines or ketazines (reaction products with simple ketones such as acetone, methylethyl ketone or methyl isobutyl ketone). When such masked chain lengthening agents are used, the isocyanate reactive groups are not released until subjected to the hydrolytic influence of the water of dispersion. The following are further examples of compounds suitable as starting components (b): (b4) ionic starting components or potentially ionic starting components having a molecular weight of 60 to 400, preferably 89 to about 400, and containing at least one ternary or quaternary ammonium group or a group capable of being converted into such a group in addition to at least one isocyanate reactive group. These compounds include amino alcohols containing tertiary amine nitrogen in which the tertiary nitrogen atoms can be at least partially converted into ternary or quaternary ammonium groups by neutralization or quaternization during or after completion of the isocyanate polyaddition reaction. Specific examples include N-methyl-diethanolamine, N-butyl-diethanolamine, N-methyl-diisopropanolamine, N-ethyl-diethanolamine, N-ethyl-diisopropanolamine and N,N'-bis-(2-hydroxyethyl)-perhydropyrazine, and corresponding monohydric alcohols such as N,N-dimethyl-ethanolamine, 2-(2-dimethylamino-ethoxy)-ethanol, N-N-diethyl-ethanolamine, 2-(2-diethylamino-ethoxy)-ethanol, N,N-di-n-butyl-aminoethanol, N-(3-hydroxypropyl)-dimethylamine, N-(2-hydroxypropyl)-dimethylamine, 1-diethylamino-2-propanol and 1,3-bis-(dimethyl amino)-2-propanol. Also included are the analoguous starting components having at least 1 tertiary amino group, i.e. a potential ternary or quaternary ammonium group, and containing, instead of the one or more than one hydroxyl group, at least one primary or secondary aminic or hydrazinic amino group, e.g. N-methyl-bis-(3-aminopropyl)-amine, N-methyl-bis-(2-aminoethyl)-amine and N,N'N"-trimethyl-diethylene triamine as well as monofunctional compounds such as 1-amino-2-diethylamino-ethane, 1-amino-3 -dimethylamino-propane, 1-amino-3 -diethylamino-propane and N,N-dimethyl hydrazine. In the process according to the invention, incorporation of the ionic groups, i.e. the ternary or quaternary ammonium groups, is preferably carried out by the addition of starting components containing tertiary amino groups followed by conversion of the tertiary amino groups into the corresponding ammonium groups by neutralization with inorganic or organic acids such as hydrochloric acid, acetic acid, fumaric acid, maleic acid, lactic acid, tartaric acid, oxalic acid, N-methyl-N-(methyl- aminocarbonyl)-aminomethane sulphonic acid or phosphoric acid, or by quaternization with suitable quaternizing agents such as methyl chloride, methyl iodide, dimethyl sulphate, benzyl chloride, ethyl chloroacetate or bromo acetamide. Other examples of suitable neutralizing or quaternizing agents are disclosed in DE-OS No. 2,827,156. The neutralization or quaternization of the starting components containing tertiary nitrogen could in principle also be carried out before or during the isocyanate polyaddition reaction although this is less preferred. Furthermore, ternary or quaternary ammonium groups could be introduced into the polyisocyanate polyaddition products by way of polyether polyols containing tertiary amino groups used as starting components (b1) followed by neutralization or quaternization of the tertiary amino groups. This again is not a preferred method of carrying out the process according to the invention. In all the variations of the process according to the invention, the quantity of starting components containing tertiary amino groups or ammonium groups and the degree of neutralization or quaternization are chosen so that the products of the process according to the invention contain about 2 to 300, preferably about 5 to 200 and most preferably about 5 to 120 milli-equivalents of ternary or quaternary ammonium groups per 100 g of solid substance. The following are further examples of suitable starting components (b) according to the invention: (b5) monohydric and dihydric alcohols containing ethylene oxide units built into polyether chains. The alcohols include compounds corresponding to the general formula: ##STR8## wherein Q represents a divalent group such as may be obtained by removal of the isocyanate groups from a diisocyanate of the formula Q(NC0) 2 as mentioned under (a1), R" represents hydrogen or a monovalent hydrocarbon group having 1 to 8 carbon atoms, preferably hydrogen or a methyl group, R"' represents a monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably an unsubstituted alkyl group with 1 to 4 carbon atoms, X represents a group such as may be obtained by removal of the terminal oxygen atom from a polyalkylene oxide chain having about 5 to 90, preferably about 20 to 70 chain members, of which at least about 40%, preferably at least about 65% are ethylene oxide units and which in addition to the ethylene oxide units may include propylene oxide, butylene oxide or styrene oxide units, propylene oxide being preferred, and Y represents oxygen or NR iv , wherein R iv conforms to the definition given for R"'. Compounds corresponding to the last mentioned formulae may be prepared by the procedures disclosed in U.S. Pat Nos. 3,905,929 and 4,190,566. Compounds corresponding to the general formula HO--X--Y--R"' wherein X, Y and R"' have the meaning already indicated are also preferred hydrophilic starting components (b5). When such monofunctional, non-ionic, hydrophilic polyethers are used, it may often be advantageous to prevent premature chain breaking by adding starting components which are more than difunctional. The monofunctional polyethers corresponding to the last mentioned general formula are prepared by known processes such as those described in U.S. Pat. Nos. 3,905,929, 4,190,566 or 4,237,264. The following are further examples of starting components (b) suitable for the purpose of the invention: (b6) amino alcohols having a molecular weight of 61 to 300 which are free from tertiary nitrogen, e.g. ethanolamine, propanolamine, diethanolamine or dipropanolamine. Also suitable are (b7) polyhydric, preferably dihydric, alcohols containing acyl urea groups such as those obtained by a reaction of the diisocyanates containing acyl urea groups exemplified under (a3), in particular those based on low molecular weight starting diisocyanates, with the compounds exemplified under (b1) (b2) and/or (b6) using an OH/NCO equivalent ratio of about 1.2:1 to 30:1 or, when amino alcohols (b6) are used, an NH 2 /NCO ratio of about 0.6:1 to 1.2:1. Preferably these compounds are prepared by reaction of the polyisocyanates containing carbodiimide groups mentioned under the definition of component (a3), preferably diisocyanates based on low molecular weight starting isocyanates, with the above mentioned polyhydroxyl compounds using an OH/NCO equivalent ratio of about 1.2:1 to 30:1 or, when amino alcohols (b6) are used, an NH 2 /NCO equivalent ratio of about 0.6:1 to 1.2:1, followed by a reaction of the reaction products with carboxylic acids R--COOH in accordance with the particulars given above. When starting materials (b1) and/or b2 containing hydroxyl groups are used, the reaction of the polyhydroxyl component with the isocyanate component is preferably carried out at an OH/NCO equivalent ratio of about 1.5:1 to 15:1, in particular about 1.5:1 to 3:1. Preparation of the starting components (b7) containing hydroxyl groups and of their intermediate products containing carbodiimide groups used for the preparation of the hydroxyl compounds (b7) is generally carried out at a temperature of about 25 to 130° C., preferably about 50° to 120° C., optionally in the presence of an inert solvent of the type exemplified in DE-OS No. 2,714,293. Details of the preparation of such polyhydroxyl compounds containing acyl urea groups are also given in this publication. Lastly, as suitable starting component (b) for the purpose of the invention should also be mentioned (b8) water, which can serve both as continuous phase of the dispersions according to the invention and as chain lengthening agent. The starting components (b) used for the process according to the invention are preferably difunctional in isocyanate addition reactions although, as already mentioned above, monofunctional starting components (b) may also be used, in particular compounds of the type mentioned under (b4) or (b5), or higher than difunctional components (b) may be used for the purpose of obtaining chain branching of the molecule if desired. The following are examples of auxiliary agents and additives (c) which may be used in the process according to the invention: (c1) solvents optionally used for the synthesis of the polyurethanes. Examples of suitable solvents include toluene, xylene, acetone, methyl glycol acetate, ethyl glycol acetate, butyl acetate, N-methyl pyrrolidone, ethyl acetate and methyl ethyl ketone. It is preferred to use water miscible solvents such as acetone or N-methyl pyrrolidone. The following may also be used as auxiliary agents and additives (c) in the process according to the invention: (c2) compounds which react with isocyanate groups to form acylated amino groups and compounds capable of reacting with such acylated amino groups to undergo a condensation reaction. The first mentioned compounds include ammonia and urea, while the latter compounds include aldehydes, in particular formaldehyde. Auxiliary agents and additives (c2) are used when the "melt dispersion process" is carried out, as will be explained below. The following are examples of auxiliary agents and additives (c) optionally used: (c3) known accelerators for the isocyanate polyaddition reaction used in polyurethane chemistry. The use of such catalysts, however, is generally not necessary. Further examples of auxiliary agents and additives (c) optionally used are as follows: (c4) emulsifiers which are not chemically incorporated and are preferably non-ionic. These are optionally used in addition to the chemically incorporated emulsifiers but are, of course, not essential. Examples of such emulsifiers include ethoxylated nonyl phenol, polyoxyethylene-lauryl ether and polyoxyethylene-laurate, -oleate and -stearate. These additives generally contain 8 to 50 oxyethylene units per molecule. The external emulsifiers may be added to the products of the process after completion of the isocyanate addition reaction in order to improve their solubility or dispersibility in water. The additional oxyethylene units thereby introduced into the solutions or dispersions according to the invention are not taken into account when calculating the ethylene oxide unit content of the polyisocyanate addition products since the quantity of ethylene oxide units indicated refers solely to the number of such units which are chemically incorporated. The auxiliary agents and additives (c) optionally used also include the usual additives such as inert fillers, pigments, dyes, plasticizers and additives which influence the flow properties. The process according to the invention, i.e. preparation of the dispersions according to the invention, may be carried out using methods known in the art. Whatever variation of the process according to the invention is carried out, however, the following conditions should be observed: The starting components containing ionic groups or potentional ionic groups (b4 and/or when polyether polyols containing tertiary amine nitrogen atoms are used, optionally also b1) should be incorporated in such a quantity in the polyisocyanate addition product and the degree of neutralization of the potential ionic groups incorporated in the polyurethanes should be such that the polyisocyanate addition products have about 2 to 300, preferably about 5 to 200 and in particular about 5 to 120 milliequivalents of incorporated ternary or quaternary ammonium groups per 100 g of solids content. It is necessary to ensure that the ionic group content of the polyisocyanate addition products together with any non-ionic hydrophilic groups optionally present is sufficient to render the polyisocyanate addition products soluble or dispersible in water. (ii) Any starting components containing non-ionic hydrophilic groups (a4 and/or b5) should be present in such a quantity that the polyisocyanate addition products contain at most about 25% by weight, preferably at most about 20% by weight and most preferably not more than about 15% by weight of ethylene oxide units, --CH 2 --CH-- 2 --0--, within the polyether chains, based on the solids content. (iii) Finally, the quantity of starting components containing acyl urea groups (a3 and/or b7) should be such that the polyisocyanate addition products contain about 0.1 to 20% by weight, preferably about 2 to 15% by weight, of structural units of the formula ##STR9## As already mentioned above, the process according to the invention may be carried out by any of several known methods. 1. The "acetone process" is carried out in a manner analogous to the teaching of DE-OS No. 1,495,745 (=U.S. Pat. No. 3,479,310) or DE-OS No. 1,495,847 (=G.B. Pat. No. 1,076,788). A prepolymer containing isocyanate end groups is prepared either solvent free or in the presence of solvents of the type exemplified under (c3). The starting materials used in this case are in particular simple diisocyanates of the type mentioned under (a1), optionally relatively high molecular weight polyhydroxyl compounds of the type mentioned under (b1), optionally chain lengthening agents of the type exemplified under (b2) as well as under (b3), ionic starting components of the type exemplified under (b4) or the corresponding potential ionic starting components and optionally non-ionic hydrophilic starting components of the type exemplified under (b5), together with starting components containing acyl urea groups exemplified under (a3) and/or (b7). In this process, an isocyanate prepolymer is generally first prepared and this is then dissolved in a suitable solvent, whereupon chain lengthening is carried out in solution to form the polyurethane. The incorporation of ionic groups is achieved during preparation of the polymer by means of suitable ionic or potential ionic starting components (b4) and/or during chain lengthening by means of low molecular weight, difunctional ionic or potential ionic starting components of the type exemplified under (b4). The potential ionic groups are converted into ionic groups before or during dispersion in water. In this embodiment, it is preferred to use difunctional starting components of the type exemplified. The equivalent ratio of isocyanate groups to isocyanate reactive groups is preferably about 0.7:1 to 2:1. The solution of the resulting polyurethane is then mixed with water which optionally contains neutralizing agents of the type exemplified under (b4) for the purpose of neutralizing any potential ionic groups present. After mixing the polyurethane solution with water, the solvent may, if desired, be removed from the resulting aqueous polyurethane dispersion by distillation. In this embodiment, conversion of any tertiary nitrogen atoms present into quaternary nitrogen atoms may be achieved by quaternization of the polyisocyanate addition product present in solution. According to one variation of this embodiment, separately prepared isocyanate prepolymers of the type exemplified under (a2) are reacted in solution with the starting components containing acyl urea groups mentioned under (a3) and/or (b7) and preferably low molecular weight ionic starting components of the type mentioned under (b4) and optionally non-ionic hydrophilic starting components of the type mentioned under (b5) and the reaction mixture is then mixed with water after the reaction. 2. Another embodiment of the process according to the invention is similar to that disclosed in DE-OS No. 2,725,589, U.S. Pat. Nos. 4,269,748, 4,192,937 or 4,292,226, in which masked chain lengthening agents of the type mentioned under (b3) are used as chain lengthening agents. U.S. Pat. No. 4,192,937 discloses oxazolidines as chain lengthening agents or U.S. Pat. No. 4,292,226 wherein amine salts are used as chain lengthening agents. In these processes, isocyanate prepolymers which have previously been prepared solvent free or in solution from the starting materials exemplified above with the addition of starting components containing acyl urea groups exemplified under (a3) and/or (b7) and ionic starting components of the type mentioned under (b4) and optionally non-ionic hydrophilic starting components of the type mentioned under (b5) are mixed with the above mentioned masked chain lengthening agents at an equivalent ratio of isocyanate groups to isocyanate reactive groups of about 1.2:1 to 3:1. Water is then added to the resulting mixture to liberate the previously masked amine or hydrazine for reaction as a chain lengthening agent with the prepolymer. In this procedure, the water may again contain, in solution, the neutralizing agent for any potential ionic groups present. This embodiment also may include quaternization of the polyisocyanate addition product, either solvent free or in solution before addition of the masked chain lengthening agent. 3. Another embodiment of the process according to the invention corresponds to the "melt dispersion process" disclosed in U.S. Pat. No. 3,756,992, in which isocyanate end groups of hydrophilically modified prepolymers are reacted with urea, ammonia or other suitable compounds under solvent free conditions to form acylated amines which in turn are converted into methylol groups by a reaction with formaldehyde before, during or after the addition of water. The products containing methylol groups, which are dissolved or dispersed in water, may then be converted into high molecular weight polyurethanes, for example by heating to a temperature of about 50 to 150° C., whereby the reactive methylol groups undergo a condensation reaction. Here again, any tertiary nitrogen atoms present may be quaternized before the addition of water. The isocyanate prepolymers used in this embodiment are prepared, as in the second embodiment with the aid of the starting components (a3) and/or (b7) which are essential components for the invention. 4. In another method of carrying out the process according to the invention, prepolymers containing isocyanate groups and the starting components (a3) and/or (b7) which are essential to the invention, are first dispersed in water optionally containing the neutralizing agent required for neutralizing the potential ionic groups, and the resulting aqueous dispersion is then mixed with an aminic or hydrazinic chain lengthening or cross linking agent of the type mentioned under (b3) containing free amino groups, at an NCO/NH equivalent ratio of about 1:0.2 to 1:1.1, preferably about 1:0.3 to 1:0.98. Chain lengthening is then carried out at about 5 to 90° C., preferably about 20° to 80° C. Again, quaternization of the isocyanate prepolymers optionally containing tertiary nitrogen atoms could conceivably be carried out before the dispersion in water. If starting components (b4) and/or (b1) containing tertiary nitrogen atoms are used and quaternization is subsequently carried out or if the corresponding compounds already containing quaternized tertiary nitrogen atoms are used, preparation of the solutions or dispersions according to the invention could in principle be conducted by first carrying out the isocyanate addition reaction using starting materials containing carbodiimide groups corresponding to compounds (a3) and/or (b7) and then carrying out the chemical addition of the carboxylic acid with formation of acyl urea groups after the isocyanate addition reaction. Such a procedure, however, is less advantageous than the described embodiments of the process according to the invention. The properties of the polyurethanes, in particular their molecular weight can be varied within wide limits and adapted to their particular purpose by suitable choice of the starting components and of the equivalent ratios employed in the various embodiments. In the context of the present invention, the terms "polyisocyanate addition products" and "polyisocyanate polyaddition products" thus also include comparatively low molecular weight reaction products which may be prepared by the ionic modification of isocyanates containing acyl urea groups with monohydric alcohols containing tertiary amino groups, followed by neutralization or quaternization without any further chain lengthening of the molecule. Conversion of the solutions or solvent-free preparations of the polyisocyanate addition products or prepolymers obtained according to the various embodiments into an aqueous solution or dispersion may in principle be carried out by various methods. Apparatus producing high shearing gradients or non-chemical dispersing agents such as extremely high frequency sound waves may be used, but are generally not necessary since simple mixing apparatus such as stirrer vessels or so called reflux mixers are sufficient for dispersing the polyisocyanate addition products or prepolymers which are generally self dispersing. For the same reason, polyisocyanate addition products according to the invention could in principle be obtained in a solid form, i.e. in the form of powders, resins or lumps, and these materials can be dispersed or dissolved in a separate step. Furthermore, it has surprisingly been found that salt formation of the potential hydrophilic groups can initially be carried out to such an extent that only relatively coarse dispersions or suspensions are obtained and these may subsequently be converted into finely divided dispersions or solutions by the further addition of neutralizing agents. Owing to the low viscosity of the coarse intermediates, they can be prepared at higher concentrations, thereby reducing the transport costs. If desired, the dispersions according to the invention may subsequently be modified with isocyanates by a procedure analogous to that disclosed in DE-OS No. 2,708,242. In all the various embodiments of the process according to the invention, the quantity of water used is generally calculated to result in solutions or dispersions having a solids content of less than about 60% by weight, preferably about 10 to 60% by weight, most preferably about 10 to 50% by weight. The particle diameter of the dispersed solids is generally below about 1 μm, preferably about 0.001 to 0.5 μm. The average particle diameter should be below about 0.5 μm and preferably in the range of about 0.01 to 0.3 μm. If the hydrophilic group content is very low, average particle diameters of about 5μ to 50μ may be obtained. Such dispersions are of interest, for example, for the preparation of polyurethane powders. If the dissolved or dispersed polyisocyanate addition products also contain ethylene oxide units as hydrophilic groups, they are to a large extent insensitive to electrolytes in spite of containing ionic groups. The solutions or dispersions may be mixed with other dispersions, e.g. with polyvinyl acetate or dispersions of polyethylene, polystyrene, polybutadiene, polyvinyl chloride, polyacrylate and copolymer resins. Known emulsifiers which are not chemically fixed and are preferably non-ionic may also be added, as already mentioned above, but they are, of course, not essential. Finally, fillers, plasticizers, pigments, carbon black sols and silica sols, aluminum dispersions and clay and asbestos dispersions may also be incorporated in the above mentioned dispersions. The solutions and dispersions according to the invention are in most cases stable and suitable for storage and transport and may be processed at any subsequent date, e.g. for molding or otherwise shaping them. They generally dry on their own to form dimensionally stable plastic coatings although shaping of the products of the process may also be carried out in the presence of known cross linking agents. The products obtained vary in their properties according to the nature of the acyl urea groups contained in them. Thus, valuable paper sizes may be obtained by the incorporation of relatively long chained fatty acids R-COOH containing at least 10 carbon atoms. Another advantage is the problem free introduction of double bonds in side chains by the incorporation of unsaturated carboxylic acids R-COOH, which provides the possibility of subsequent cross linking. Furthermore, the hydrophilic or hydrophobic characteristics of the products can easily be controlled by suitable choice of the acyl urea groups in side chains. The products of the process are suitable for coating, covering and impregnating woven and non-woven textiles, leather, paper, wood, metal, ceramics, stone, concrete, bitumen, hard fiber, straw, glass, porcelain, a wide variety of plastics, and glass fibers. They are capable of forming anti-static and crease resistant finishes and may be used as binders for non-woven webs, adhesives, adhesifying agents, laminating compounds, hydrophobicizing agents, plasticizers and bonding agents, e.g. for cork powder or wood powder, glass fibers, asbestos, paper type materials, plastics and rubber waste and ceramic materials. They may also be used as auxiliary agents in textile printing and in the paper industry as additives for polymers and as sizing agents, for example for glass fibers, and for dressing leather. Dispersions and particularly solutions according to the invention of polyisocyanate addition products containing acyl urea groups in which the hydrophilic centers are exclusively ammonium groups and which have a molecular weight, calculated from the nature and stoichiometric proportions of the starting materials, of about 600 to 10,000, preferably about 800 to 5,000 and most preferably about 800 to 3,000, are particularly suitable for sizing paper. These low molecular weight polyisocyanate addition products are preferably prepared without the aid of the relatively high molecular weight polyhydroxyl compounds of the type exemplified under (b1) and optionally with the addition of chain breakers, e.g. monofunctional alcohols such as methanol, ethanol, n-butanol or n-octanol. An isocyanate prepolymer is first prepared from difunctional starting materials, using an excess of NCO, and this prepolymer is then reacted with the chain breaking agent. When the dispersions or solutions according to the invention, in particular the last mentioned solutions of comparatively low molecular weight polyisocyanate addition products containing cationic groups, are used as paper sizes for the preparation of paper sizes, the usual additives for paper sizes may be employed such as alum or cationic or anionic auxiliaries based on cationic starch or quaternized polyamines, quaternized polyamidamine, quaternized basic formaldehyde resins, methyl cellulose, carboxy methyl cellulose, lignin sulphonic acids, starches and polysaccharides of various origin, xanthane, pullulan, chitosan, and polymers or copolymers of (meth) acrylic acid, (meth) acrylamide, maleic, fumaric or itaconic acid or other polymers and copolymers containing carboxylic or sulphonic acid groups, optionally in salt form, or collagen, gelatine, alginates or carageenates. The effect of the sizes according to the invention is not impaired by the addition of white toners. Furthermore, the aqueous preparations can be obtained without the aid of emulsifying agents although such agents may be used if desired. The sizes, used alone or in combination with other sizes, are particularly suitable for the surface sizing of paper but may, of course, also be used for internal sizing. They may be used not only for paper containing chalk or kaolin but also for paper which is free from filter or contains a different type of filler, e.g. talcum or gypsum. The sizes are also suitable for sizing cellulose materials such as cardboard, textiles, leather, carton, woodchip board or insulating board. The invention will be described below by way of examples. The parts, proportions and percentages given refer to weight unless otherwise indicated. EXAMPLES Example 1 90.7 parts (0.52 mol) of a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate (proportions 65:35) were carbodiimidized with 0.1 ml of a solution of a commercial mixture of 1-methyl-1-phospha-2-cyclo-pentene-1-oxide and 1-methyl-1-phospha-3-cyclo- pentene-1-oxide in N-methyl-pyrrolidone (1:6) as catalyst at 60° C. When the isocyanate content reached 20.6%, the reaction was stopped with 0.1 ml of phosphorus trichloride and the mixture was stirred for 30 minutes. The isocyanate content reached a constant value of 19.8%. 32.2 parts (0.36 mol) of butane-1,4-diol and 52 parts of acetone were then added. After 30 minutes, the isocyanate content had fallen to 0%. 64.8 parts (0.228 mol) of stearic acid were added at 60° C. and the mixture was reacted for 40 minutes until an acid number of 0 was obtained. A further 82.2 parts (0.47 mol) of a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate (ratio 65:35) were then added and the mixture was reacted at 60° C. until an isocyanate value of 8.0% was obtained. 200 parts of acetone were added for dilution, and 29.9 parts (0.25 mol) of N-methyl-diethanolamine were added at 60° C., followed, after 10 minutes, by 6.4 parts (0.086 mol) of n-butanol. When the isocyanate content had fallen to 0%, salt formation was carried out by the addition of 22.6 parts (0.25 mol) of DL-lactic acid, and 731 parts of water were used to form dispersion after 30 minutes stirring. The acetone was drawn off immediately thereafter. A finely divided dispersion having a solids content of 32% by weight and containing 80 milliequivalents of quaternary ammonium groups per 100 g of solid substance and 6.2% of acylated urea groups, ##STR10## based on the solids content was obtained. Example 2 87 parts (0.5 mol) of a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate (ratio 65:35) were carbodiimidized with 0.1 ml of a solution of a commercial mixture of 1-methyl-1-phospha-2-cylclopentene-1-oxide and 1-methyl-1-phospha-3-cyclopentene-1-oxide in N-methyl-pyrrolidone (1:6) as catalyst at 60° C. The reaction was stopped at an isocyanate content of 20.6% by the addition of 0.1 ml of phosphorus trichloride and then stirred for 30 minutes. The isocyanate content reached a constant value of 20.0%. 31.1 parts (0.35 mol) of butane-1,4-diol and 50 parts of acetone were then added. After 30 minutes, the isocyanate content had fallen to 0%. 62.1 parts by weight (0.218 mol) of stearic acid were added at 60° C. and the mixture was reacted for 40 minutes to an acid number of 0. A further 49.2 parts (0.28 mol) of a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate (ratio 65:35) were then added and the reaction was continued to an isocyanate value of 3.5% at 60° C. 200 parts of acetone were added for dilution and the reaction was stopped with 19.6 parts (0.25 mol) of N,N-dimethyl-ethanolamine at 60° C. When the isocyanate content had fallen to 0%, 80.1 parts by weight (0.22 mol) of a 50% solution of N-methyl-N-(methylaminocarbonyl)-aminomethane sulphonic acid in water was added for salt formation and the reaction mixture was dispersed after 30 minutes stirring by the addition of 600 parts by weight of water. The acetone was drawn off immediately thereafter and a finely divided dispersion having a solids content of 30%, a quaternary ammonium group content of 80 milliequivalents per 100 g of solid substance and an acylated urea group content, ##STR11## of 6.8%, based on the solids content, was obtained. Example 3 87 parts (0.5 mol) of a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate (ratio 65:35) were carbodiimidized at 60° C. using 0.1 ml of a solution of a commercial mixture of 1-methyl-1-phospha-2-cyclopentene-1-oxide and 1-methyl-1-phospha-3-cyclopentene-1-oxide in N-methyl pyrrolidone (1:6) as catalyst. The reaction was stopped with 0.1 ml of phosphorus trichloride when the isocyanate content was 19.6% and stirring was then continued for 30 minutes. The isocyanate content settled at a constant value of 18.7%. The reaction product was diluted with 50 parts of acetone, and 64.5 parts (0.23 mol) of stearic acid were then added at 60° C. When the acid number was 0, a further 200 parts of acetone was added for dilution. 8.9 parts (0.12 mol) of n-butanol were then added, followed after 10 minutes by 17.8 parts (0.2 mol) of N,N-dimethyl ethanolamine. The mixture was reacted at 60° C. until the isocyanate content was reduced to 0%. Salt formation was then carried out by the addition of 72.8 parts (0.2 mol) of a 50% solution of N-methyl-N-(methyl-aminocarbonyl)-aminomethane sulphonic acid in water, and the reaction mixture was dispersed with 430 parts of water after 30 minutes. The acetone was distilled off immediately thereafter. A finely divided dispersion having a solids content of 32%, a quaternary ammonium group content of 100 milliequivalents per 100 g of solid substance and an acylated urea group content, ##STR12## of 9.0%, based on the solids content was obtained. Example 4 87 parts (0.5 mol) of a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate (ratio 65:35) were carbodiimidized at 60° C. with 0.1 ml of a solution of a commercial mixture of 1-methyl-1-phospha-2-cyclo-pentene-1-oxide and 1-methyl-1-phospha-3-cyclopentene-1-oxide in N-methyl pyrrolidone (1:6) as catalyst. The reaction was stopped with 0.1 ml of phosphorus trichloride when the isocyanate content was 21.7% and the mixture was then stirred for 30 minutes. The isocyanate content reached a constant value of 20.0%. The reaction product was diluted with 50 parts of acetone, and 62.0 parts (0.23 mol) of stearic acid were added at 60° C. 31.1 parts (0.35 mol) of butane-1,4-diol were added after 60 minutes and the reaction was continued to an isocyanate content of 0%. A further 49.2 parts (0.28 mol) of a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate (ratio 65:35) was then added and the reaction was continued at 60° C. to an isocyanate value of 3.5%. The reaction mixture was then diluted with 200 parts of acetone and the reaction was stopped at 60° C. with 19.6 parts (0.25 mol) of N,N-dimethyl ethanolamine. When the isocyanate value had fallen to 0%, salt formation was carried out with 80.1 parts (0.22 mol) of a 50% solution of N-methyl-N-(methylaminocarbonyl)-aminomethane sulphonic acid in water, and the reaction mixture was dispersed with 600 parts of water after 30 minutes stirring. The acetone was drawn off immediately thereafter. A finely divided dispersion having a solids content of 27%, a quaternary ammonium group content of 80 milliequivalents per 100 g of solid substance and an acylated urea group content, ##STR13## of 6.8%, based on the solid substance, was obtained. Example 5 87 parts (0.5 mol) of a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate (ratio 65:35) were carbodiimidized at 60° C. with 0.1 ml of a solution of a commercial mixture of 1-methyl-1-phospha-2-cyclo-pentene-1-oxide and 1-methyl-1-phospha-3-cyclopentene-1-oxide in N-methyl pyrrolidone (1:6) as catalyst. The reaction was stopped at an isocyanate content of 20.1% by the addition of 0.1 ml of phosphorus trichloride and the mixture was then stirred for 30 minutes. The isocyanate content reached a constant value of 18.5%. The reaction product was diluted with 50 parts of acetone, and 64.7 parts by weight (0.23 mol) of stearic acid were added at 60° C. When the acid number had fallen to 0, the reaction mixture was diluted with a further 200 parts of acetone 8.7 parts (0.12 mol) of n-butanol were then added, followed after 10 minutes by 17.8 parts by weight (0.2 mol) of N,N-dimethyl ethanolamine, and the reaction was continued at 60° C. to an isocyanate content of 0%. Salt formation was then carried out by the addition of 72.8 parts (0.2 mol) of a 50% solution of N-methyl-N-(methylaminocarbonyl)-aminomethane sulphonic acid in water. The acetone was distilled off immediately thereafter. A crystalline solid which could be ground down to powder form and dispersed at any convenient time thereafter was obtained. The solid substance contained 100 milliequivalents of quaternary ammonium groups per 100 g of solid and 9% of acylated urea groups, ##STR14## Example 6 174 parts (1.0 mol) of a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate (ratio 65:35) were carbodiimidized at 60° C. with 0.2 ml of a solution of a commercial mixture of 1-methyl-phospha-2-cyclo-pentene-1-oxide and 1-methyl-1-phospha-3-cyclopentene-1-oxide in N-methyl pyrrolidone (1:6) as catalyst. The reaction was stopped at an NCO content of 27.7% by the addition of 0.2 ml of phosphorus trichloride and the mixture was stirred for 30 minutes. The isocyanate content reached a constant value of 25.8%. 101.8 parts (0.36 mol) of stearic acid were added to the reaction product at 60° C. and the mixture was reacted for 2 hours. The resulting reaction product containing acylated urea groups had an isocyanate content of 16.6%. 100 parts (0.117 mol) of a polyester diol of adipic acid and hexanediol (OH number 133.6) and 12 parts by weight of a polyethylene oxide/polypropylene oxide polyether (OH number 26: 73.3% ethylene oxide) which had been started on butanol were dehydrated in a water jet vacuum for 30 minutes at 110° C. The mixture was cooled to 80° C. and 32.1 parts (0.145 mol) of isophorone diisocyanate and 78.9 parts (0.145 mol) of the above-mentioned polyisocyanate containing acylated urea groups were added and the temperature was raised to 100° C. The isocyanate content reached a constant value of 3.4%. 4.2 parts by weight of n-butanol were then added and the reaction mixture was diluted with 900 ml of acetone. The temperature fell to 50° C. 1.1 parts (0.222 mol) of hydrazine hydrate and after 5 minutes 6.37 parts (0.044 mol) of N,N-bis-(3-aminopropyl)-methylamine in 50 parts of acetone were added for chain lengthening at 50° C. After 10 minutes, salt formation was carried out by the addition of 3.95 parts (0.044 mol) of DL-lactic acid in 20 parts of water, and the reaction product was dispersed in 550 parts of water after a further 10 minutes. The acetone was drawn off under vacuum immediately thereafter. A finely divided dispersion having a solids content of 30% and containing 20 milliequivalents of quaternary ammonium groups per 100 g of solid substance, 3.8% of ethylene oxide units built into a polyether chain and 3.9% of acylated urea groups, based on the solids content, was obtained. Example 7 522 parts by weight (5.0 mol) of a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate (ratio 65:35) were carbodiimidized at 60° C. with 0.6 ml of a solution of a commercial mixture of 1-methyl-1-phospha-2-cyclopentene-1-oxide and 1-methyl-1-phospha-3-cyclopentene-1-oxide in N-methyl pyrrolidone (1:6) as catalyst. The reaction was stopped with 0.2 ml of phosphorus trichloride when the NCO content reached a value of 28.9% and the mixture was then stirred for 30 minutes. The isocyanate content reached a constant value of 26.5%. 90.2 parts (1.05 mol) of methacrylic acid were added to the reaction mixture at 60° C. and the mixture was reacted for 2 hours. The resulting reaction product containing acylated urea groups had an isocyanate content of 22.5%. 100 parts (0.117 mol) of a polyester diol of adipic acid and hexanediol (OH number: 133.6) and 12 parts of a polyethylene oxide/polypropylene oxide polyether (OH number 26: 73.3% ethylene oxide) which had been started on butanol were dehydrated in a water jet vacuum at 110° C. for 30 minutes. The mixture was cooled to 80° C., and 32.1 parts (0.145 mol) of isophorone diisocyanate and 54.0 parts by weight (0.145 mol) of the above-mentioned polyisocyanate containing acylated urea groups were added. 6.41 parts (0.071 mol) of butane-1,4-diol were added after a reaction time of 1 hour and the temperature was raised to 100° C. The isocyanate content reached a constant value of 3.9%. The reaction mixture was then diluted with 900 ml of acetone the temperature fell to 50° C. Chain lengthening was then carried out by the addition of 1.1 parts (0.022 mol) of hydrazine hydrate at 50 ° C., followed after 5 minutes by the addition of 6.44 parts (0.044 mol) of N,N-bis-(3-aminopropyl)-methylamine in 50 parts by weight of acetone. Salt formation was carried out after 10 minutes by the addition of 4.0 parts (0.044 mol) of DL-lactic acid in 20 parts of water and the reaction product was dispersed in 484 parts of water after a further 10 minutes. The acetone was drawn off under vacuum immediately thereafter. A finely divided dispersion having a solids content of 30% and containing 20 milliequivalents of quaternary ammonium groups per 100 g of solid substance, 4.4% of ethylene oxide units built into a polyether chain and 4.1% of acylated urea groups, based on the solids content, was obtained. In the following examples of practical application, the dispersion prepared according to Example 1 was investigated for its suitability as a sizing agent for paper. Examples of Practical Application These examples of practical application demonstrate the good sizing properties of the products according to the invention on various qualities of paper differing in their material composition. The Cobb value (according to DIN 53 132) was determined as a measure of the special sizing effect. The papers used had the following compositions: (a) Paper free from alum 50% pine wood cellulose, 50% hard wood cellulose, 10.5% clay ash, pH in breast box: 7.3%: wet absorption in a laboratory sizing press: about 80%: weight of paper: 80 g /m 2 . (b) Paper containing alum 50% pine wood cellulose, 50% hard wood cellulose, 1% alum, 11.8% clay ash, pH in breast box: 4.4%: water absorption about 80%: weight of paper: 80 g/m 2 . (c) Pre-sized paper 50% pine wood cellulose, 50% hard wood cellulose, 1% alum, 0.1% bewoid size, 11.9% clay ash, pH in breast box: 4.5: wet absorption about 60%; weight of paper: 80 g/m 2 . (d) Paper containing chalk 50% pine wood cellulose, 50% hard wood cellulose, 10.9% chalk ash, pH in breast box: 7.5: wet absorption: about 90%: weight of paper: 75 g/m 2 . (e) Paper containing wood 40% pine wood cellulose, 60% wood pulp, 12.0% clay ash, pH in breast box: 4.5: wet absorption: about 40%: weight of paper: 75 g/m 2 . The paper was sized in a laboratory press of Mathis, Zurich/Switzerland, type HF. The sizing liquor used was a solution of 5% by weight of commercial starch and 0.2 to 0.6% by weight of the size to be examined (calculated as 100% active substance) in water. The surface sized paper was dried on a drying cylinder at about 100° C. for 1 minute. The paper had been air conditioned at room temperature for 2 hours before the size was tested. The results obtained are given in Table 1. TABLE 1______________________________________ Quantity usedType of Paper % of liquor sizing effect*______________________________________(a) free from alum 0.36 28.2(b) containing alum 0.36 65(c) pre-sized 0.36 25.2(d) containing chalk 0.36 26.2(e) containing wood 0.36 19.5______________________________________ *The Cobb values are given in g/m.sup.2 of water absorption in 60 seconds determined according to DIN 52 132. Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
The present invention relates to aqueous solutions or dispersions of polyisocyanate addition products which contain about 2 to 300 milliequivalents per 100 g of solids of chemically incorporated ternary or quaternary ammonium groups and up to about 25% by weight, based on solids, of chemically incorporated ethylene oxide units, --CH 2 --CH 2 --O--, present within a polyether chain, the ternary or quaternary ammonium groups and the ethylene oxide units being present in an amount sufficient to guarantee the solubility or dispersibility of the polyisocyanate addition products in water, characterized in that the polyisocyanate addition products have segments incorporated in the polymer chain which correspond to the following general formula ##STR1## in an amount of about 0.1 to 20% by weight based on the above formula, but excluding the weight of R. The present invention also relates to a process for the production of polyisocyanate addition products and to their use as coating agents for flexible or inflexible substrates and as sizing agents for paper or for the production sizing agents for paper.
2
CROSS REFERENCE TO RELATED APPLICATIONS [0001] Not Applicable STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH AND DEVELOPMENT [0002] Not Applicable BACKGROUND OF THE INVENTION [0003] b 1 . Field of the Invention [0004] The present invention relates to the field of magnetic bearing or suspension systems. More specifically, the invention is directed towards a passive radial magnetic bearing system that includes damping elements and may also include a mechanism to provide increased stiffness at large rotor amplitudes. [0005] 2. Description of Related Art [0006] Passive magnetic bearings are well known in the art. Many configurations of these types of bearings are possible (e.g. U.S. Pat. Nos. 5,894,181; 5,619,083; 4,072,370; 3,958,842; and 3,614,181 among others). Each of these configurations suffers from a lack of damping. Rotors supported on these types of bearings, therefore, will be poorly damped. This condition results in large vibrational amplitudes when the rotors traverse their critical speeds, increased sensitivity to imbalance forces, and decreased resistance to rotordynamic instabilities. This combination sometimes results in failure of the machines. [0007] Many various techniques for introducing damping into passive magnetic systems have been developed (e.g. U.S. Pat. Nos. 5,910,695; 5,679,992; 5,521,448; and 5,386,166). Some of these methods have developed eddy current dampers, but these generally provide very low damping levels. An alternative method, utilized in some of the above patents, is to use a damping material, such as an elastomeric material or a woven material, to provide the damping. Many different configurations of this approach have also been disclosed. These configurations generally rely on introducing an intermediate housing between the rotor and the machine frame. In general, the stationary portion of the passive magnetic bearing is mounted in the intermediate housing. The damping material is then positioned between the intermediate housing and the machine frame. Undesired rotor vibrational forces are transmitted from the rotor magnets to the stator magnets through the magnetic field. The transmitted vibrational forces cause movement of the stator magnets, and the intermediate housing into which the magnets are mounted. The motion is resisted by the damping material, either in shear or in compression. The resistance of the damping material to the vibrations results in frictional forces, thus dissipating the vibrational energy. [0008] This approach has several limitations. First, the intermediate housing represents an additional component that must be manufactured and assembled, adding to system cost and complexity. Secondly, the intermediate housing has a finite, and usually substantial, mass that is added to the bearing mass. This results in a reduction in the resonant frequency of the combined bearing stator and intermediate housing, above which a loss of damping occurs. Finally, in this configuration, all of the forces transmitted through the bearing must pass through the damping element. This limits the designers' ability to independently adjust the stiffness and damping of the bearing system to optimize rotordynamic performance. [0009] In addition, several of these configurations rely on a single ring of magnetic material on each of the stator and rotor sections. Variations in the magnetic strength of the rotor and stator magnet materials result in variations of the magnetic forces as one ring rotates relative to the other. This results in “magnetic run-out,” or a mechanical vibration of the rotor due to unbalanced magnetic forces. This sensitivity to variations in the magnetic field strength of the bearing magnets is undesirable. BRIEF SUMMARY OF THE INVENTION [0010] It is therefore an object of the current invention to provide a passive magnetic support and damping system without the above listed drawbacks. [0011] It is therefore a further object of the present invention to provide a passive magnetic support and damping system that is made of easily manufacturable components in a readily assemblable configuration. [0012] It is therefore a still further object of the present invention to provide a passive magnetic support and damping system that provides increased stiffness in response to large amplitude vibrations. [0013] It is therefore a still further object of the present invention to provide a passive magnetic support and damping system that is minimally sensitive to variations in the magnetic properties of the permanent magnet materials used. [0014] These and other objects of the present invention, which will become apparent hereinafter, are achieved by providing a passive magnetic support and damping system in which the rotor portion of the damping system is comprised of a series of disks or annular rings of permanently magnetized material fixedly attached to the rotor of the machine. The stator portion is also comprised of a series of annular rings of permanently magnetized material, which are positioned concentrically with the rotor magnets. The stator and rotor magnets are formed and positioned such that a radial gap is present between said stator magnets and said rotor magnets. At least one, and preferably an even number, of the stator magnets are mounted in a damping material, which, in turn, is fixedly attached to the machine stator. This damping material may be an elastomeric material, a woven material, or any other type of material that exhibits primarily frictional losses in response to shear or compressive strains. The “soft mounted” stator magnet(s) provide damping to the system. The remaining stator magnets are fixedly attached to the machine stator and provide stiffness (“hard mounted”). By varying the number, size, and magnetic strength of the stator magnets mounted in these two ways, the stiffness and damping of the bearing assembly can be varied substantially independently. Further, because only a single stator magnet is interposed between the rotor and each layer of damping material, the resonant frequency of the damping mechanism is very high (i.e. the effective mass of each damper element is minimized). This results in improved damping at higher frequencies than was available in the prior art. [0015] An additional feature of the present invention is that the soft mounted stator magnets can be provided with a backing material that limits their displacement. When the soft mounted magnets come into contact with the backing material, they effectively become hard mounted, and contribute additional stiffness to the system. In this manner large excursions of the rotor, which cause large displacements of the soft mounted magnets, will result in increased bearing stiffness, tending to restore the rotor to the nominal position. BRIEF DESCRIPTION OF THE DRAWINGS [0016] [0016]FIG. 1 is a cross sectional view of a passive magnetic support and damping system configured to provide radial stiffness and damping with minimal axial forces. [0017] [0017]FIG. 2 is a cross sectional view of a passive magnetic support and damping system configured to provide radial stiffness and damping and in addition to provide an axial force. [0018] [0018]FIG. 3 is a cross sectional schematic view of an example showing a small flywheel utilizing passive magnetic support and damping systems to provide radial support and axial pre-load. [0019] [0019]FIG. 4 is a cross sectional view of a passive magnetic support and damping system configured to provide radial stiffness and damping and in addition to provide axial damping and an axial force. [0020] [0020]FIG. 5 is an axial view of the passive magnetic support and damping system displayed in FIG. 2, configured for large diameter and/or high speed systems. DETAILED DESCRIPTION OF THE INVENTION [0021] Referring now to FIG. 1 one configuration of a radial bearing 10 according to the present invention is shown. The bearing is comprised of a rotor element 20 and a stator element 30 . The rotor element is typically attached to a shaft 21 and is further comprised of at least one rigidly mounted magnet 22 . Said rotor magnet(s) may be directly mounted to the shaft, or may be mounted with a spring element 23 (e.g. a Tolerance Ring; manufactured by USA Tolerance Rings, West Trenton N.J.) with a spring constant significantly higher than the stiffness of the magnetic field between the rotor and stator magnets. Such spring elements allow some differential expansion between the shaft 21 and housing 31 and the magnets 22 and/or 34 , without generating excessive stresses in the magnets. The rigidly mounted rotor magnets may be spaced axially from each other by means of rigid spacers 25 . These spacers may be made of a magnetic material but are preferably non-magnetic. [0022] The stator element can be mounted into a housing 31 , which is attached to the non-rotating portion of the machine, not shown. Alternatively, the stator elements can be directly mounted into the machine. The stator element is further comprised of at least one magnet 32 mounted concentrically with the rotor magnet. Said magnet(s) are attached on at least one side, but preferably both sides, to a damping material 33 , such as a viscoelastic material, an elastomer, a woven or felted metal, or another material that exhibits frictional shear losses resulting in damping. The damping material is in turn attached to a structure that is rigidly mounted to the fixed portion of the stator housing. This structure may be another concentrically mounted magnet 34 , a rigid spacer element 35 , the stator housing 31 or any other element that is fixedly attached to the stationary machine. Functionally, the “soft mounted” stator magnets 32 are allowed to follow the radial vibrations of the “hard mounted” rotor magnets 22 . The motion of the soft mounted stator magnets results in shearing of the damper materials 33 . Thus, vibrational motions of the rotor magnets are transmitted through the magnetic coupling, producing vibrational motions of the soft mounted stator magnets. This motion is in turn transmitted to shear or compressive deformations of the damping material, further resulting in frictional dissipation of the vibrational energy. This frictional dissipation provides damping to the rotor through the magnetic coupling. In the illustrated example, additional magnetic coupling between the hard mounted rotor magnets 22 and the hard mounted stator magnets 34 provide bearing stiffness. [0023] Also in FIG. 1 it is seen that the soft mounted magnets are surrounded on their outside diametral surface by a radial gap 36 which allows radial displacements to occur. These radial displacements are necessary to generate the damping. The low stiffness of the damping material, however, reduces the overall stiffness of the bearing that would normally be expected of magnets of the given size and material properties. By introducing a rigid backing material 37 which limits the radial displacement of the soft mounted magnets, this stiffness can be partially restored in response to large vibrations. Alternatively, the full radial area shown as gap 36 and element 37 could be filled with additional damping material, increasing the effective damping of the system. [0024] In the preferred embodiment, more than one rigidly mounted magnet is present in the rotor portion of the bearing to reduce the effects of variations in the magnetic properties of any one magnet. In addition, in the preferred embodiment, the magnets are magnetized in the axial direction, as shown in the figure. Radially magnetized magnets in both the rotor and stator segments, arranged in opposition, would also work but are more difficult to produce. [0025] [0025]FIG. 2 illustrates a different embodiment of the present invention in which the rotor element 20 surrounds the stator element 30 . In this illustration, the rotor magnets 22 are positioned about the outside diameter of the stator magnets 32 and 34 . This arrangement results in radial pre-compression of the rotor magnets, which is advantageous for high-speed applications in which the rotational stresses may cause tensile failure of the rotating magnets. Also, an additional magnet 40 has been added to the rotor element to generate an axial force. This is beneficial in situations in which a static load, such as gravity, needs to be countered. Depending on the configuration of the machine, additional magnets generating axial forces could be added to the rotor, the stator, or both. [0026] Two possible arrangements of additional magnets 40 exist: 1) the additional magnet can generate a repulsive force between the rotor and stator as shown in the bottom bearing of FIG. 3 or 2) the additional magnet can generate an attractive force between the rotor and the stator as shown in the example of FIG. 2. [0027] In the case of FIG. 2, the attraction between the stator magnet 34 and the additional rotor magnet 40 increases the positive radial stiffness and the magnitude of the negative axial stiffness of the bearing. This increased radial stiffness is often advantageous. The attractive force on the additional magnet, however, tends to pull it out of its housing, complicating the task of assembly. [0028] In the axial repulsive force configuration (FIG. 3), the radial stiffness of the bearing assembly is reduced, but a positive axial stiffness element is introduced. The overall axial stiffness of the bearing remains negative, but the magnitude is reduced. In addition, in this case, the repulsive force tends to keep the additional magnet in the housing, reducing the required complexity of the housing. In the example fly wheel shown in FIG. 3, a motor generator, not shown, could be placed internal to the flywheel body 60 inside the cavity 50 . Electrical leads for this device could enter through a hollow shaft 51 . [0029] As seen in FIG. 4, this repulsive force between a rotor magnet 22 and the additional magnet 40 can also be utilized to introduce a layer of damping material 41 between the additional magnet and the machine, introducing axial damping. In this case, any undesired axial vibrations of the rotor assembly 20 would be transmitted through the repulsive force between magnets 22 and 40 , resulting in axial motions of the additional stator magnet 40 . This motion would be resisted by the damping material 41 resulting in frictional dissipation of the axial vibration energy, or damping. [0030] [0030]FIG. 5 represents an axial view of the assembly displayed in FIG. 2, further configured for high-speed applications. In this example the stator magnet(s) 32 (and 34 , not shown) are ring magnets mounted as described earlier. In cases in which the rotational speed is very high, or in which the rotor (outer) magnet 22 diameters are very large, it may be advantageous to manufacture those magnets from sections 22 a. These sections can be bonded to, or otherwise restrained by, the rigid spacers 25 . It is obvious that this same strategy can be used in cases in which the outer magnets are the stator magnets. In this case, the damper material could be positioned between rigid spacers that hold the magnet assemblies in place and fixed portions of the machine. [0031] A further embodiment can be illustrated by FIG. 2. In this illustration, FIG. 2 is an axial cross-section of a translational passive magnetic support and damping system that provides stiffness and damping in the horizontal axis, while allowing translation in the axis that extends perpendicular to the figure such that it extends into and out of the drawing sheet. This embodiment is configured to allow translational movements, such as those used in a linear slide or a positioning table. In this case, Stationary member 30 would consist of a base 31 a and a series of one or more bar magnets ( 32 , 34 ). The translational moving portion of the assembly 20 similarly contains bar magnets 22 rigidly mounted into a housing 21 a or the translational portion of the machine (not shown). The soft mounted magnets 32 are mounted to provide damping in the manner described earlier. The axis of movement in this example is perpendicular to the drawing page, i.e.; it extends into and out of the drawing sheet. [0032] The present disclosure should not be construed in any limited sense other than that limited by the scope of the claims having regard to the teachings herein and the prior art being apparent with the preferred form of the invention disclosed herein and which reveals details of structure of a preferred form necessary for a better understanding of the invention and may be subject to change by skilled persons within the scope of the invention without departing from the concept thereof.
A type of passive magnetic bearing that provides for both positive radial stiffness and significant levels of passive radial damping. Axial damping and axial forces can also be generated with minor modifications to the basic configuration. The bearing is comprised of a series of magnet, damping, and rigid non-magnetic elements essentially defining a laminated or composite structure. The damping material is directly mounted between the magnets and a rigid material, resulting in constrained layer damping. The range of motion of these floating, or soft mounted, magnets may also be restricted to generate higher stiffness in response to large vibrations.
5
CROSS-REFERENCE TO RELATED APPLICATIONS [0001] The present application claims the benefit of U.S. Provisional Application Nos. 61/296,551 filed on Feb. 2, 2010, which is incorporated herein by reference. STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT [0002] The present invention was not developed with the use of any Federal Funds, but was developed independently by the inventors. BACKGROUND OF THE INVENTION [0003] Conventional Power Factor Correction (PFC) uses a rectifier bridge followed by a separate boost stage. Such boost converters produce a relatively high voltage which is filtered and stored in a capacitor. A subsequent power stage reduces the voltage and regulates the output. Conventional PFC circuits operate in Discontinuous Conduction Mode (DCM), Continuous Conduction Mode (CCM), or Critical Mode. Each mode of operation has advantages and disadvantages, but changing from one mode to another is difficult or impossible for a particular controller. Further, these circuits are limited to matching input current to AC line voltage, and are not suited for applications which require more flexible control of input current. [0004] U.S. Pat. Nos. 4,974,141, Severinsky et al, and 7,202,640 B2, Morita, teach single stage power converters with both regulation and improved PFC. Those devices rely on the output capacitance to filter line frequency ripple. That filter capacitance must then be much larger than in the usual case where only the much higher switching frequency need be filtered. Very large output capacitors are bulky and expensive and limit the agility of a power converter. AC output voltage or current is not feasible for power converters requiring large output filter capacitors. BRIEF DESCRIPTION OF THE INVENTION [0005] The desirability of smaller and more efficient power converters is well understood. This invention allows a single inductor, single stage, power converter to perform PFC and agile output regulation. Size and efficiency gains result. Further, this invention allows operation in DCM, CCM or Critical Mode, and can match the input current to the phase and shape of an arbitrary waveform. [0006] As used herein a single inductor may mean a plurality of inductors in series or parallel and refers to the principal energy converting inductor of the power converter (for example, L 1 in FIG. 1 ). Obviously, the power converter may have additional inductors throughout the circuit to accomplish current or voltage smoothing and filtering or for other well know circuit design purposes. Indeed, the load may be an inductive element within the circuit. [0007] The ability to independently regulate multiple control loops using a single inductor in DCM/CCM operation is unique, and is a more generally useful ability. Devices made according to this invention can perform AC-AC conversion, act as uninterruptable power supplies, or can act as nodes in AC or DC power distribution networks. [0008] Adding two more switches to the six-switch teaching of U.S. Pat. No. 7,786,709 (the '709 patent), by the same inventors, creates a truly universal power converter. The two additional switches connect from either side of the switched inductor to a storage port. That port can access a rechargeable battery, a capacitor, an ultracapacitor, or other electrically active device. That port can be used as an additional output port, or can connect to another bidirectional power converter for networked power. Stored energy can be of either polarity. [0009] These devices can perform AC-AC, AC-DC or DC-AC conversion, and Power Factor Correction (PFC), power conditioning, and they can function as an uninterruptable power supply (UPS). As well, they can duplicate all the six-switch embodiment functions of the '709 patent. Just a few, or all, of the switches employed could need to be bipolar-blocking depending of the allowable polarities of the inputs and outputs. [0010] The input current can be matched to any profile, provided externally, or derived from an AC power input waveform, or, the input voltage can be regulated by adjusting the input current. Input voltage and current regulation can be useful for maximization of photovoltaic panel power output. Controllable AC input current profiles enable dynamic vibration damping in wind generators. With storage, output regulation becomes independent of input regulation, and, in AC applications, output frequency becomes independent of input frequency. [0011] Separate conventional converter stages can do the same jobs, but will require multiple inductors and potentially as many switches as this invention. Also, multiple conventional controllers would need to function in concert. According to this invention, much of the power converted need move only once through a single inductor from a preferred source to a preferred destination. Efficiency is thereby improved by reducing wasted energy due to inductive losses, extra gate drive energy and direct switching losses. The addition of a few extra switches allows fewer switch transitions and can enable the elimination of an entire stage of power conversion. Any extra complexity is primarily in the control intelligence, which is becoming faster, lower power, and lower cost every year. [0012] The multiplexed examples cited above have two independent regulation processes time-sliced using a single inductor. One embodiment does PFC and rectification and regulation in a single stage. This technique takes the opportunism described in the '709 patent to a new level. The development of GaN switches (which are bipolar-blocking and very fast) will facilitate diverse embodiments of this invention. For example, additional bipolar ports and regulation processes could be more easily added. With DCM/CCM regulation well managed, and with fully bipolar energy movement capability, the distinction between energize and transfer states ceases to be central. Instead, the minimum and maximum continuous current in the switched inductor become additional parameters among the multiple parameters being regulated. Depending on the continuous current, the optimum operation at a given time could be either a transfer to a port of energy stored in the inductor, or an energize sub-cycle to first increase the inductive energy. [0013] Each bidirectional, bipolar port requires four switches, one to either end of the switched inductor from either terminal of the port. With those switches, the added port can be placed in circuit with the switched inductor in either polarity. The inductor current can flow in either direction for any energize or transfer sub-cycle. In practice, many switches are redundant and need not be duplicated. For full bipolar, bidirectional flexibility with three ports sharing return paths, eight switches are needed. [0014] In some topologies, a given port can either provide or receive energy during a particular chopping cycle. In those cases, designating a port as an input port or an output port may not yield best clarity. A given port can be said to function as a donor port when used as a source for energizing the inductor, regardless of polarity. A port can be called a receptor port when energy of either polarity is delivered to it from the inductor. Ports that function sometimes as donor ports and sometimes as receptor ports can be called donor/receptor ports. [0015] The conventional means for Power Factor Correction (PFC) involves placing a boost converter stage in advance of the main regulation power stage. The main regulation stage is normally then a buck converter. All power runs through the boost stage and is stored as a relatively high voltage in a capacitor. That capacitor provides the input for the subsequent stage. There are more advanced forms of PFC referred to as bridgeless, because they do not have a separate diode bridge for rectification. “Bridgeless” PFCs do comprise bridges made of diodes and switches. The “bridgeless” form typically involves two switches and two diodes, or sometimes four switches, following two boost inductors. A Fairchild patent number 7269038 single-stage PFC and rectification describes the four-switch technique. Only a DC output is taught and claimed, and a subsequent stage is required for regulation. In essence, it is still a boost converter followed by a second stage for regulation. [0016] The prior art separation of PFC and regulation is inherently inefficient. Every energy transfer incurs loses. Ideally, energy transfers should be minimized. This invention accomplishes that minimalization. [0017] The concept of transferring energy opportunistically in an agile cycle-by-cycle controlled power converter is taught in the '709 patent. Bipolar, AC or DC energy can be transferred bidirectionaly using those teachings. The need for PFC when an input port is the AC line was not addressed. The need for local storage when performing AC to AC or AC to DC conversion was incompletely addressed. [0018] A slightly modified version of the six-switch topology described in the '709 patent embodies both efficient storage and PFC all with a single inductor in a single stage converter. Storage can be any electrically activated bidirectional energy reservoir. Storage can be sufficient to provide a regulated output voltage in the absence of a power input voltage for a fraction of a single cycle, or for many hours. [0019] In the preferred embodiment, two independent control loops are time multiplexed in one chopping cycle. One loop regulates the input current waveform, and the other regulates the output voltage. The switched inductor is first energized from the power input, VP, up to the amount required by the PFC reference signal. If a predictive energy balance calculation determines that the load will require additional energy after an energy transfer, inductor energizing is continued using the storage port as the source. In the preferred embodiment, inductive energy is then transferred to the output. Surplus energy obtained during the PFC subcycle is subsequently transferred from the inductor to storage. Alternatively, this invention may be practiced by transferring excess energy to storage before transferring the balance to the load. [0020] The PFC limit can be dynamically scaled with a non-critical, slow feedback loop to keep the stored energy within preset limits. For normal PFC function, the PFC limit would be a rectified sinusoid in phase with the power input voltage. For other purposes, any arbitrary current input waveform could be reproduced that was within the bandwidth of the converter. In some applications, like wind turbines, the ability to independently regulate the input current waveform enables dynamic vibration control. [0021] The storage port receives and supplies only energy that can not move directly from input to output. Thus, the total transferred energy and the number of energy movements are minimized. [0022] The use of consecutive transfer periods was taught in the '709 patent. The use of consecutive energizing periods without an intervening transfer period is a departure from the prior art. [0023] According to this invention, “N” ports can be served by (N−1) independent control loops, all using the same switched inductor. Thus, a multi-output converter or a node in a local power network that can move power, at will, between multiple ports can be embodied according to this invention. [0024] In general, such embodiments of this invention are easier to understand if they operate in Discontinuous Conduction Mode because the two loops are unlikely to interact. However, Continuous Conduction Mode is useful for higher power systems. If sufficient control intelligence is provided to account for inductive energy differences instead of absolute energies, multiple control loops can intermingle without cross regulation, even in the presence of continuous inductor current. The ability to accommodate CCM is valuable for the construction of capable, opportunistic power converters. BRIEF DESCRIPTION OF THE DRAWINGS [0025] FIG. 1 shows an 8-Switch Power Converter. [0026] FIG. 2 shows a flowchart for 8-Switch Power Converter. [0027] FIG. 3 shows a flowchart Subroutines for 8-Switch Power Converter. [0028] FIG. 4 shows an input Waveforms for 8-Switch Power Converter. [0029] FIG. 5 shows operational Waveforms for 8-Switch Power Converter. [0030] FIG. 6 shows a flowchart for a 6-Switch Power Converter. [0031] FIG. 7 shows a truth table for one implementation of the invention. DETAILED DESCRIPTION OF THE INVENTION [0032] FIG. 1 shows an eight-switch bipolar bidirectional power converter with a storage port. All three ports can be AC or DC, unipolar or bipolar, and unidirectional or bidirectional. For simplicity, in this embodiment, the storage port is operated as a DC port to avoid the possibility of needing energy from storage when a stored AC voltage crosses zero. The power input port is here used in unidirectional fashion to demonstrate power factor correction. This embodiment is a very limited subset of the possibilities enabled by this invention. Any port can be voltage or current driven, and the non-driven parameter can be controlled. [0033] In the preferred embodiment, the input port current is regulated to match a PFC waveform input labeled pfcRef. The output port voltage is regulated to match a reference voltage input labeled Ref. The power converter is synchronous, clocked by the signal SET, in this case, at a frequency of 400 KHz. The controls support CCM, DCM, and critical operation and can close both control loops independently with minimal interaction. [0034] For maximum efficiency, energy placed in the switched inductor for the purpose of PFC can be delivered directly to the load as needed, without a second stage of power conversion or the need of extra switching transitions. When the load requirement exceeds the PFC requirement, additional energy is obtained from storage. When PFC energy exceeds the immediate load requirement, excess energy in the switched inductor is placed in storage before or after the load is satisfied. If, instead of demand, there is excess energy at the load, that energy is moved through the inductor to storage. In this, or similar, fashion energy is moved the minimum number of times, and by the most direct path. [0035] This principle of “opportunism” was first described in the '709 patent. Here, opportunism is extended to enable handling of continuous currents in either polarity for any energy transfer. Without that ability, under rapidly changing conditions, there remains the possibility of requiring inductive energy polarity to be reversed before a useful energize or transfer function. The embodiments described in the '709 patent may lose time and energy to reverse the inductive current flow. Furthermore, in the '709 patent the energy transfer must be predicted in order to correctly polarize the inductor charging. Requiring such anticipation necessarily limits opportunism. According to this invention, the polarity of inductor current is not important. Thus, it is possible to handle continuous inductor currents with minimum additional control complexity. [0036] Typically, the PFC portion of the cycle can be controlled by a slow, noncritical auxiliary feedback path that modulates the amplitude of the PFC path to keep the storage voltage within preset limits. Note that with sufficiently deep storage, the output can be kept in regulation for extended periods with no input voltage available. This feature provides uninterruptable power supply functionality. For typical PFC applications, the input current reference signal, pfcRef, will be in phase with the AC line. According to this invention, the input current reference signal does not need to be in phase with the AC line, nor does it need to have any particular frequency or shape. The input current can track any arbitrary waveform. This ability could be particularly useful for controlling mechanical vibration in wind generators, or for variable frequency AC applications, in general. [0037] The power converter of FIG. 1 decodes the outputs of ten comparators to determine the switch settings for energizing the switched inductor, L 1 , and transferring energy from L 1 to a port. SenseiL produces a voltage proportional to the current in L 1 , iL. Block |iL| produces the absolute value of the voltage iL, absiL. Clock signal set initiates a chopping cycle and momentarily activates switch S 9 to store the present value of absil in capacitor C 3 as divided by resistors R 1 and R 2 . That voltage, ilast, represents the minimum iL for the preceding chopping cycle. [0038] Comparator CErr produces a high output at pErr if Ref is greater than the output voltage, Vout. [0039] Comparator CVP produces a high output at pVP if the Power input voltage, VP, is greater than zero. [0040] Comparator CiL produces a high output at piL if iL is positive. [0041] Comparator CRef produces a high output at pRef if Ref is greater than zero. [0042] Comparator CPFC produces a high output at pfcCk if pfcRef is greater than absiL. [0043] Comparator CPED produces a high output at ped if iLast is greater than absiL. [0044] Comparator CiLim produces a high output at iLim if absiL is greater than iMax. [0045] Comparator CSP produces a high output at nsp if iL is greater than the slightly positive threshold voltage thr 1 . [0046] Comparator CNP produces a high output at nsn if iL is less than the slightly negative threshold voltage thr 2 . [0047] The next series of circuits blocks perform the energy balance calculations described in Law 10 an 12 . Mult 1 squares iL, producing i 12 . MultK multiplies IL 2 by a scaling factor, K to produce KL, representing the inductive energy supply. Multout squares Vout to give Out 2 . MultRef squares Ref to give Ref 2 . SUM 1 subtracts Out 2 from Ref 2 , giving KdV, which is proportional to the energy demand at the load. The final comparator, CBal, produces a high output at Bal if supply, KL, is greater than demand, Kdv. [0048] Switches S 2 and S 4 connect VP to L 1 terminals 1 and 2 respectively. [0049] Switches S 3 and S 5 connect the shared return to L 1 terminals 1 and 2 respectively. [0050] Switches S 7 and S 1 connect Vstore to L 1 terminals 1 and 2 respectively. [0051] Switches S 8 and S 6 connect Vout to L 1 terminals 1 and 2 respectively. [0052] C 2 is the storage capacitor. An ultra capacitor or rechargeable battery or other storage means can be substituted. C 1 filters Vout. [0053] DtoB is a standard 8 bit decimal to binary decoder. A 1 unblocks the ith limit for positive inductor current responsive to bit B 5 of DtoB, A 2 unblocks the ith limit for negative inductor current responsive to bit B 4 of DtoB. OR gate A 3 combines the positive and negative current limits to produce the ith input signal for the SwitchDecode block. [0054] Block SwitchDecode, in combination with the control logic, StateBlock, determine which switches are ON according to the following table. [0055] E indicates Energize. T indicates Transfer. [0056] Transfers continue until the ith threshold and need polarity to be specified, N or P. P means iL flows left to right, N means iL flows right to left. [0057] At the ith threshold transfers change to state 6 , recirculation. [0058] All Energize states and Recirculation are unconditional. [0059] FIG. 7 is decoding truth table to implement the flow chart of FIGS. 2 and 3 in the invention as shown in FIG. 1 . [0060] FIG. 2 is a flowchart which describes the behavior of StateBlock. A positive clock edge from set begins the Evp subcycle, which is terminated by a positive edge on pfcCk. If, at that time, the polarity of error is different from the polarity of the reference, a Eout subcyle begins. Eout continues until the polarity of error reverses, or until iLim. The remainder of the chopping cycle is then a Tstor subcycle. If, at the end of the Evp subcycle the polarity of error is not different from the polarity of the reference, the condition of Bal determines the next subcycle. If Bal is true, a Tout subcycle follows until the polarity of error reverses, or until iLim. A Tstor subcycle then completes the chopping cycle. If the Bal test yields not true, an Estor subcycle follows until Bal or until iLim. A Tout subcycle then completes the chopping cycle. [0061] FIG. 3 flowcharts the individual energize functions, Evp, Eout and Estor, and the individual transfer functions Tstor, Tout and Tvp. The choices made in these individual functions serve the purpose of making them independent of the polarity of current in L 1 . Estor selects state 9 or 17 dependent on piL. Evp selects state 1 or 8 dependent on piL XOR pvp. Eout selects state 3 or 18 dependent on piL XOR pvp. [0062] Tstor selects state 13 or 10 dependent on piL. Tvp selects state 4 or 5 dependent on piL XOR pVP. Tout selects state 2 if piL AND pRef, state 15 if pRef AND (NOT piL), state 7 if (NOT pRef) AND (NOT piL), and state 16 if (NOT pRef) AND piL. [0063] The power converter of FIG. 1 employs predictive energy balancing for better regulation. Because an excess of inductive energy can always be transferred to storage or recirculated, it is not entirely necessary to complete the energy balancing calculations. Instead of relying on the Bal signal for control, an adaptive current limit can be used which would be determined by the recent operation history. The adaptive limit would be determined by a slow feedback loop which acted to cause a small surplus of energy to remain in L 1 at the end of a typical chopping cycle. If a substantial amount of excess energy remained, with a substantial amount of time remaining in a chopping cycle, that excess energy could, optionally, be transferred to Vstore. Minimum and maximum limits on continuous current could be regulated in this fashion. [0064] Also, the preferred embodiment power converters taught here use a sensor to detect inductor current. Inductor current can be approximated by substituting a volt-time product with little change in performance. [0065] FIG. 4 shows the simulated behavior of the power converter of FIG. 1 for the PFC input current and the power input voltage, VP. The VP is the upper trace, a sine wave with peak-to-peak amplitude of 160 volts at 6000 Hz. A frequency of 60 Hz would be typical for PFC, but the higher frequency shown here illustrates the wide bandwidth capability of the input current regulation. The lower trace is a somewhat averaged representation of the input current, seen to be matching in phase and shape with VP. The addition of a small filter on the input will remove any objectionable higher frequency components from the input current waveform. [0066] FIG. 5 shows operational waveforms for the converter of FIG. 1 . It is split into two axes with the same time scale. Above, as in FIG. 4 , is VP. Here, the time period is extended to show that VP ceases after 0.5 mS and remains at zero volts for the duration. Note that the output voltage continues to follow the reference voltage in the absence of VP, even as the load changes polarity. [0067] The power converter can continue to regulate because power is drawn from the storage port. Note that the changeover to storage is completed in a single 5 us chopping cycle with no disturbance in regulation. The lower trace on the upper axis is inductor current, iL. The inductor current can be in either polarity with either polarity of input voltage, and is seen to pass from DCM to CCM and back several times over the 1 ms period shown. [0068] The lower axis of FIG. 5 shows vRef, vOut and Load Current. The reference is a sine wave of +/−10 volt amplitude at a frequency of 2 KHz. Load Current switches between +6 amps and −6 amps with 1 us rise and fall time. The output, vOut can be seen to closely track vRef regardless of input or output polarity or of the polarity of the load. [0069] The power converter of FIG. 1 one can be usefully implemented with six switches with some limitations. The six-switch form can provide functionality for an AC input, unipolar DC output, unidirectional power converter with PFC. Switches 1 and 8 are eliminated. CCM operation is less practical in this reduced topology. [0070] FIG. 6 is a flowchart showing one alternate control method. There are two time-sliced control loops. One loop regulates the input current waveform, and the other regulates the output voltage. Energy, in either polarity, is first obtained from VP up to the amount demanded by the load, as predicted by the balance calculation, or, up to the PFC reference, whichever occurs first. That inductive energy is then transferred to the output port up to the ith current limit. If the load requires additional energy after a PFC-limited transfer, the right side of the flowchart shows the appropriate sequence for the second half-cycle. The inductor is energized from the storage port up to predicted balance, then energy is transferred to the output port. If the load did not require the full PFC reference amount, the left side of FIG. 6 applies. The second half-cycle energizes from VP until the remainder of the PFC energy has been loaded into the inductor. Then, that energy is transferred to the storage port. [0071] The performance of the 6-switch variation is equivalent to that of the power converter of FIG. 1 , given a unipolar load and unipolar output voltage.
A switched-mode power converter power converter, in one preferred embodiment with eight switches connected between three ports and an inductive element, with a donor (charging) port, a receptor port (load) and donor/receptor port (storage) operated so that energy may be switch between any of the ports regardless of the polarity and magnitude of the inductor current at the beginning of a chopping cycle. In one embodiment of the invention power conversion and power factor correction are accomplished in a single stage.
8
TECHNICAL FIELD This invention relates to arrangements for mounting apparatus, and, more specifically, for the adjustable mounting of a superstructure on a fixed base. BACKGROUND OF THE INVENTION Many types of equipment gain added versatility from a flexible mounting arrangement. The most common example is a lamp which can be arranged to shine on an appropriate surface as needed. However, the kinds of arrangements used for lamps, which have a relatively heavy base and a relatively light superstructure are of limited utility for controlling the positioning of a relatively heavy superstructure on a relatively light base. Such an arrangement is needed, for example, for adjustable orientation video display terminals used in computer and communications systems. Many arrangements have been used to allow video display terminals to be mounted so that the superstructure containing a cathode ray tube (CRT) can be tilted back and forth to minimize glare. When a superstructure is tilted so that its center of gravity is no longer directly above or below its support axis, gravity exerts a torque on the superstructure tending to change the tilt angle. A number of different arrangements are available to adjust and maintain a given tilt angle in a display terminal. For example, a display terminal sold by the Data General Corporation includes a costly high strength encompassing arm structure and a costly high strength housing to support the heavy CRT assembly from the sides. Here, the center of gravity is close to the support axis so that the forces tending to move the superstructure away from a given tilt angle are weak, and a relatively simple friction bolt will maintain a given tilt angle. In another prior art display terminal sold by Teletype Corporation, a superstructure which is supported at the base has a tilt angle that is adjustable in steps over a relatively small range, up to 15 degrees from vertical. Here, the center of gravity of the superstructure is much higher than the support axis at the base, so that a large torque tends to move the superstructure away from a given tilt angle when the superstructure is in an extreme tilt position, because the center of gravity is then substantially displaced from a position above the support axis. The support includes a costly high strength toothed arrangement for locking the superstructure into one of seven positions. Another base supported arrangement manufactured by Wyse Technology, San Jose, Calif., uses only friction to maintain a given tilt and also avoids the structural expense of the high strength support arms and the high strength superstructure housing. Here, the center of gravity is also much higher than the center of rotation of the superstructure, so that substantial forces tend to move the superstructure further from a neutral position when it is displaced substantially therefrom. However, the tilt is limited to 20 degrees from vertical, insufficient for support applications in which an operator sometimes works from a standing position. In this type of arrangement, if the friction is too great, the unit does not tilt readily; however, the friction must be great enough to maintain a superstructure position near the extreme levels of tilt adjustment. Accordingly, there is no satisfactory mounting arrangement in the prior art for conveniently adjusting a heavy superstructure, such as the CRT assembly of a video display terminal, over a large continuously adjustable tilt angle. This large angle is needed, for example, if the operator using the terminal may be standing or sitting. SUMMARY OF THE INVENTION In accordance with the present invention, apparatus for movably mounting a superstructure on a base has two matching, slidingly engaged, curved surfaces, attached to the superstructure and the base, and a spring arrangement tending to counteract gravitational forces. When the superstructure is tilted from a neutral tilt angle and the center of gravity is no longer directly above or below the tilt axis, gravity exerts a force tending to move the superstructure; the spring arrangement exerts a force tending to counterbalance this gravitational force. Friction between the two surfaces compensates for any difference between the gravitational force and the counterbalancing spring force. Advantageously, such a mounting arrangement allows a superstructure to be moved easily and to be maintained in any position within wide limits of tilt angle. Further, because the superstructure is supported from below, no arm supports are required and the side walls are not required to provide structural support. In one embodiment of the invention, the two surfaces are portions of a cylindrical surface. The spring arrangement includes two opposing helical extension springs, each attached to the base and the superstructure. One of the two slidingly engaged surfaces is composed of thermosetting plastic material; the other surface includes adhering bearing strips with a relatively smooth surface made of ultrahigh molecular weight polyethylene material. Advantageously, this provides a bearing surface arrangement having a smooth sliding action with only moderate sliding friction, giving the person adjusting the superstructure "finger tip control" over a large tilt angle range, and a good "feel" of a continuous, low resisting force as the tilt angle is adjusted. Advantageously, such an arrangement permits a large angle of tilt for a heavy superstructure, such as a video display terminal, whose center of gravity is much higher than the support axis. The large angle of backward tilt is particularly advantageous since it allows an operator to use the terminal in a standing position as well as in the customary sitting position. Advantageously, if tilt in only one direction from the neutral position is required, only one spring is needed. In an alternative embodiment of the invention, the two surfaces are portions of a spherical surface. Advantageously, such an arrangement can be used to rotationally adjust the superstructure about a vertical as well as a horizontal axis, while maintaining the advantages of easy, smooth adjustment. BRIEF DESCRIPTION OF THE DRAWING The organization and operation of the mounting apparatus designed according to this invention will be better understood from a consideration of the detailed description in conjunction with the accompanying drawing in which: FIG. 1 is a side view of a video display terminal utilizing one exemplary embodiment of the mounting apparatus of this invention; FIG. 2 is an exploded view of the mounting apparatus depicted in FIG. 1 showing the elements thereof; FIG. 3 is a vertical sectional view through the mounling apparatus depicted in FIG. 1 showing the assembly of the elements; FIG. 4 is an enlarged view of the mounting apparatus depicted in FIG. 1 showing the operating relationship of the elements; FIG. 5 is a view of the bottom of the mounting apparatus depicted in FIG. 1 showing the elements of the spring mechanism; and FIG. 6 is a vertical sectional view through the mounting apparatus of an alternative exemplary embodiment of the invention which utilizes a spring counterbalanced ball and socket arrangement. DETAILED DESCRIPTION FIG. 1 illustrates an arrangement of the adjustable mounting apparatus 10 of this invention, the details of which are shown in FIG. 2, being used to support the superstructure 11 of a video display terminal atop a base assembly 12. The base assembly 12 provides a housing 14 for electronic components and an annular support 16 upon which the adjustable mounting apparatus 10 is able to rotate about a vertical axis. The superstructure 11 has a housing 18, for a CRT or video display unit 19 and associated electronic components, which is attached to a journal 22 of the adjustable mounting apparatus 10. The journal 22 has the shape of a segment of a cylinder, in this embodiment, nearly a semicylinder, whose axis of rotation is a horizontal axis P (the end point of which is designated P in the drawing). The convex surface 23 of the journal 22 bears on a matching concave surface 27 within a socket bearing 26 enabling superstructure 11 to be tilted forward or backward about the horizontal axis of journal 22. The limits of forward and backward tilt of this exemplary embodiment of the invention, 5 degrees forward and 30 degrees backward, are shown by the phantom lines in FIG. 1. The center of gravity of this superstructure, marked CG, is much higher than horizontal axis P. The wide range of tilt, especially backward, causes a movement of the center of gravity CG far beyond the horizontal axis P of the adjustable mounting apparatus 10. Normally a substantial shift in the center of gravity CG would overcome the relatively small frictional forces between the journal 22 and socket bearing 26 causing the superstructure 11 to tilt unobstructed to one of its extreme limits. However, a spring mechanism 30 attached between the socket bearing 26 and journal 22 approximately compensates for the gravitational force tending to pull the superstructure to one of its limits, and permits a relatively small frictional force to retain the superstructure 11 in the position where it is set by an operator. Additionally the relatively small frictional force between the journal 22 and socket bearing 26 gives the operator one-handed, finger tip control with smooth operation over the entire tilting range of the adjustable mounting apparatus 10. In one constructed model, a helical extension spring 75 having a spring constant of 5.0 lb/in (0.89 kg/cm) approximately compensates for the gravitational force tending to pull a 27.2 pound (12.3 kilogram) superstructure 11 to its forward limit and a helical extension spring 76 having a spring constant of 5.0 lb/in (0.89 kg/cm) approximately compensates for the gravitational force tending to pull the superstructure 11 to its backward limit. At the extreme backward position, the center of gravity CG of the superstructure 11 exerts a clockwise torque of 49.2 in-lb (56.7 cm-kg) about the horizontal axis P and the expanded spring 76 exerts a counterclockwise or compensating torque of 37.2 in-lb (42.9 cm-kg). When changing the tilt angle, the operator applies only a relatively small force of 3 pounds (1.4 kilograms) to overcome the frictional force between the convex surface 23 and concave surface 27. This frictional force advantageously improves the "feel" of movement of the adjustable mounting apparatus 10. FIG. 2 is an exploded view of the adjustable mounting apparatus 10, which includes the journal 22 with its convex surface 23 that conforms to the matching concave surface 27 of the socket bearing 26. As previously mentioned, socket bearing 26 is mounted in an annular support 16 to permit the superstructure 11 to be rotated about its vertical axis. A washer 54 placed atop a flange 17 of the annular support 16 provides a low friction surface between the superstructure 11 and base assembly 12 when superstructure 11 is rotated to the left or right. In the constructed model of the invention the operator has to apply a force of only 1.25 lb (0.57 kg) on the right or left side of the housing 18 in order to rotate the superstructure 11 to a desirable position. A retaining ring 56 holds the mounting apparatus 10 to the annular support 16 and has four tabs 58 equally spaced apart which maintain the axial alignment of the mounting apparatus 10 within the annular support 16. The spring mechanism 30 is attached to the journal 22 by a center bracket 60 and to the socket bearing 26 by a front bracket 61 and a rear bracket 62. A square head shoulder screw 52 is held in a boss 46 of the journal 22, passes through a screw access slot 40 of the socket bearing 26 and through a hole 64 of the center bracket 60, securing the bracket 60 between a shoulder 53 of the shoulder screw 52 and a locknut 88. A screw 71 passes through a hole 65 of the front bracket 61, a hole 57 of the retaining ring 56 and is secured in one of the threaded mounting holes 41 of the socket bearing 26. The extension spring 75 links the front bracket 61 to the center bracket 60 and extension spring 76 links the rear bracket 62 to the center bracket 60. As the superstructure 11 is pushed backward, the center bracket 60 moves forward and extends spring 76 which exerts an opposite force tending to restore the superstructure 11 to its neutral position. The neutral position is that position in which the center of gravity of the superstructure is directly above the axis of rotation; in this position, the superstructure tends to move neither forward nor backward. Only spring 76 is active when the superstructure 11 is pushed substantially backward from the neutral position and likewise only spring 75 is active when superstructure 11 is pulled substantially forward from the neutral position. In FIG. 1, the superstructure 11 is shown tilted backward 6 degrees which is the neutral position of one constructed model. FIG. 2 also illustrates the construction of each of the coactive elements, socket bearing 26 and journal 22, of the adjustable mounting apparatus 10. The bearing socket 26 has molded into its circular shape a socket 32 defined by the concave surface 27 and end walls 34. The concave surface 27 has bonded near each end thereto, thin bearing strips 36 for frictionally supporting journal 22. The concave surface 27 also has formed therein cable access slots 38 which are equally spaced apart from a centrally located screw access slot 40. Four threaded mounting holes 41 are provided in the bottom surface at the periphery of the socket bearing 26. The journal 22, shown broken away from its parent housing 18, consists of side walls 42 and the convex surface 23 which conforms to the circumferential dimension presented by the bearing surface of strips 36 within the socket 32. The convex surface 23 also has formed therein cable access slots 44 whose locations conform to the cable slots 38 of the socket bearing 26. A centrally located boss 46 provides a square recess 48 and bolt access hole 50 which is used to capture the square head shoulder screw 52. FIG. 3 illustrates the assembly of the adjustable mounting apparatus 10 atop the annular support 16 of base assembly 12. The socket bearing 26 rotates upon flange 17 of the annular support 16 with washer 54 inserted therebetween. The socket bearing 26 is secured to the annular support 16 by screws 71 and 72 which are inserted from underneath the base assembly 12 and which fasten front bracket 61 and rear bracket 62 to retaining ring 56 and to an annular flange 28 on the underside of the socket bearing 26. The journal 22 rests within the socket 32 of the socket bearing 26 and atop bearing strips 36. The journal 22 is prevented from being lifted out of socket 32 by shoulder screw 52, center bracket 60, and locknut 88. The square head shoulder screw 52 is secured within the square cavity 48 of boss 46 by a plate 80 and screws 82 and protrudes through hole 50 and access slot 40 of the socket bearing 26. The shoulder 53 of shoulder screw 52 extends slightly beyond the underside of socket 32; thus when the center bracket 60 is fastened between the shoulder 53 and locknut 88 it does not come in contact with the underside of the socket 32, but does prevent the removal of the superstructure 11 from the base assembly 12. In addition, the shoulder screw 52 provides a means of fastening journal 22 to spring mechanism 30, as further illustrated in FIG. 5. A semicircular hole 64 in the center bracket 60 prevents center bracket 60 from rotating when spring 75 or 76 is extended. Two through-holes 67 and 68 are provided in the center bracket 60 to catch inner-formed spring ends or tines 77 and 78 of extension springs 75 and 76 respectively. Two "O" rings 89 and 90 cushion tines 77 and 78 against center bracket 60 to help provide smooth and quiet operation of spring mechanism 30. The outer-formed end or loop 83 of extension spring 75 is attached to front bracket 61 by screw 85. The loop 84 of extension spring 76 is similarly attached to rear bracket 62 by screw 86. The extension springs 75 and 76 are both slightly extended (not readily apparent in the drawing) when the superstructure 11 is in the neutral position to help provide smooth operation of the spring mechanism 30 as the superstructure is tilted through the neutral position. The operation of the adjustable mounting apparatus 10 is illustrated in FIG. 4. In a case where an operator may be using the video display terminal on a desktop but is working in a standing position, the operator can adjust superstructure 11 sharply backward. As the operator pushes the top of the housing 18 backward, the journal 22 rotates about its axis of rotation, horizontal axis P. The convex surface 23 of journal 22 moves over the surface of the bearing strips 36, and the center bracket 60 pulls on tine 78, expanding spring 76. As the weight of the superstructure 11 exerts a torque in the the clockwise direction, an opposite torque is exerted by the extended spring 76 about the axis of rotation, horizontal axis P. The operator can stop the video display terminal superstructure 11 at any point within its range of movement and the position of the superstructure 11 remains stable because the extended spring 76 exerts a torque that approximately compensates for the torque caused by the weight of the superstructure; the relatively small frictional force between convex surface 23 and bearing strips 36 is enough to make up the difference between the two torques. It should be noted here that as spring 76 is extended, spring 75 remains unextended because center bracket 60 moves toward extension spring 75 allowing a straight portion 79 of extension spring 75 to pass freely within through-hole 67. In a similar manner, as the superstructure 11 is tilted forward, spring 75 becomes extended and spring 76 remains unextended. However, because springs 75 and 76 are slightly expanded in the neutral position, there is a small distance in the center range of movement where one spring begins expanding while the other spring is still restoring. Thus, a feeling of spasmodic motion is eliminated that would otherwise be felt if one spring was completely restored before the other began expanding. When the superstructure 11 is moved by the operator to the extreme backward position, the shank 91 of shoulder screw 52 is butted against the front end 92 of slot 40. The extreme forward position is defined by the point where the shank 91 of shoulder screw 52 is butted against the back end 93 of slot 40. While one exemplary embodiment of this invention utilizes a 5-degree range of forward tilt, a video display terminal for use on a high shelf could have a much larger forward range of tilt by extending slot 40 backward. If no forward tilt from the neutral position is required, then the back end 93 of slot 40 can be brought further forward and spring 75 can be eliminated. Cabling between electronic components or connectors in the base assembly 12 and superstructure 11 is hidden by providing cabling access through the adjustable mounting apparatus 10. FIG. 5 shows cable access slots 44 of the journal 22 in alignment with cable access slots 38 of the socket bearing 26. As the superstructure 11 is tilted, the access slots 44 move within the range defined by the access slots 38 but never beyond the point where the cables can be pinched or deformed. The relatively narrow dimensions of the access slots 38 and 44 and their location do not harm the structural integrity of the coactive journal 22 and socket bearing 26. As previously mentioned, the adjustable mounting apparatus 10 also rotates atop annular support 16 and washer 54. In order to further protect cabling between the base assembly 12 and housing 18, the degree of rotation is limited by a stop 96 on flange 17 of annular support 16. A groove 97 in flange 28 of the socket bearing 26 and a corresponding groove 98 in retainer 58 allow the adjustable apparatus 10 to rotate freely until an end portion of the grooves 97 and 98 are butted against stop 96. In one constructed model a 60-degree range of rotation is allowed, 30 degrees to the right and 30 degrees to the left. If desired, the range of rotation can be increased by lengthening the corresponding grooves 97 and 98. As the operator rotates and tilts the video display terminal 11 to its desired position, movement about the horizontal axis or yaw is prevented by the supporting action of end walls 34 of the socket bearing 26 against side walls 42 of the journal 22. Further stability is gained due to the confinement of shank 91 of the shoulder screw 52 within slot 40. However, tolerances between walls 34 and 42 and between shank 91 and slot 40 are within limits that prevent unwanted binding. In this illustrative embodiment of the invention, the coactive elements, i.e., annular support 16, socket bearing 26 and journal 22 are molded from a thermosetting plastic structural foam which offers lightness, strength and excellent frictional properties. The strength is required in order to carry the relatively heavy superstructure 11 and the frictional properties are utilized as the journal 22 slides back and forth upon bearing strips 36 and as the socket bearing 26 rotates upon annular support 16. The relatively smooth bearing strips 36, made of an ultrahigh molecular weight polyethylene material, along with the thermosetting plastic provides sliding surfaces having a relatively low coefficient of friction thus allowing the journal 22 to tilt easily and smoothly within socket bearing 26. Together with spring mechanism 30, the frictional bearing arrangement prevents the superstructure 11 from moving to an extreme tilt position. Both the annular support 16 and journal 22 are advantageously molded into their respective housings 14 and 18. An alternative exemplary embodiment of an adjustable mounting apparatus 100 utilizing a counterbalanced ball and socket arrangement is illustrated in FIG. 6. The design of a particular video display terminal may not require a base capable of housing electronic components and/or not require cable access openings between the base assembly and superstructure. In this case, the adjustable mounting apparatus 100 which does not require a separate assembly for providing left and right rotation could be utilized to achieve the operational features of the first exemplary embodiment, i.e., to allow the superstructure to be rotated and tilted through a wide range of angles smoothly and with minimal effort by an operator. The adjustable mounting apparatus 100 consists of a ball part 122, a mating socket bearing 126 and a spring mechanism 130. The shape of the ball part 122 is that of a spherical segment upon which a supported superstructure (not shown) is tilted and rotated. A convex surface 123 of the ball part 122 has molded therein a centrally located pin access slot 140 which is used to both limit the range of tilt and to prevent yaw of the superstructure. A front boss 161 and rear boss 162 are molded within the ball part 122 to provide a mounting surface for a spring mechanism 130. The socket bearing 126 has molded therein a socket 132 whose shape conforms to that of ball part 122. A concave surface 127 of the socket 132 has bonded annularly thereto thin bearing pads 136 for frictionally supporting ball part 122. A centrally located boss 146 molded on the underside of socket 132 provides a square recess 148 and pin access hole 150 which are used to capture a shoulder pin 152. The spring mechanism 130 is attached to the socket bearing 126 by a center bracket 160 and to the ball part 122 at front boss 161 and rear boss 162. The square headed shoulder pin 152 is held in boss 146 by plate 180 and screws 182, passes through pin access slot 140 of the ball part 122 and through a hole 164 in center bracket 160. The center bracket 160 is loosely secured atop shoulder 153 of the shoulder pin 152 by a washer 155 and a split ring 156 allowing center bracket 160 to freely rotate about the neck 154 of shoulder pin 152. An extension spring 175 links the front boss 161 to the center bracket 160 and an extension spring 176 links the rear boss 162 to the center bracket 160. Two opposing through-holes 167 and 168 are provided in arms 169 and 170 of center bracket 160 to catch tines 177 and 178 of extension springs 175 and 176, respectively. Two "O" rings 187 and 188 cushion tines 177 and 178 against arms 169 and 170. The loop 183 of extension spring 175 is attached to front boss 161 by screw 185 and the loop 184 of extension spring 176 is attached to rear boss 162 by screw 186. Both springs 175 and 176 are slightly extended when the superstructure is in the neutral position. As an operator rotates and tilts a superstructure supported by the adjustable mounting apparatus 100, the convex surface 123 of ball part 122 moves over the surface of the bearing pads 136. A rotational movement of the superstructure will cause the ball part 122 to rotate about the shank 191 of shoulder pin 152 and a tilting movement allows the ball part 122 to move within the length of pin access slot 140. As the ball part 122 is rotated about the vertical axis, center bracket 160 follows the movement of ball part 122; thus, keeping extension springs 175 and 176 in their proper alignment within ball part 122. As the superstructure is tilted backward the ball part 122 pulls on loop 183 at boss 161, extending spring 175 which counters the torque exerted by the backward movement of the center of gravity of the superstructure. The operator can stop the superstructure at any point within its range of movement and its position will remain stable because of the counterbalancing effect of the extended spring 175 and the friction between surface 123 and bearing pads 136. The backward and forward limits in the range of tilt are determined by the point where the shank 191 of shoulder pin 152 is butted against the back end 192 and front end 193 of the slot 140. As spring 175 is extended, spring 176 remains unextended because a straight portion 179 of spring 176 passes freely through hole 168 in arm 170, and under arm 169. In a similar manner, as the superstructure is tilted forward, spring 175 becomes extended and spring 176 remains unextended. The slight expansion of springs 175 and 176 in the neutral position along with the cushioning effect of "O" rings 187 and 188 provide a smooth transition of the spring mechanism 130 as the superstructure is tilted through the neutral position. As the operator rotates and tilts the superstructure to its desired position, movement about the horizontal axis or yaw is prevented by the supporting action of the side walls 194 of slot 140 against the shank 191 of shoulder pin 152. The ball and socket arrangement of FIG. 6 and the journal and socket arrangement of FIGS. 1-5 represent two geometries of bearing and borne surface pairs. In general, any pair of surfaces which are defined by surfaces of revolution about a common axis can be used, since such surfaces match and are capable of moving one with respect to the other about an axis of rotation. For example, the bearing and borne surfaces could be portions of cone surfaces, the cone having as its central axis the tilt axis of the superstructure. The portions of the surfaces of revolution need not be complete segments, provided that at all angles of tilt, some portion of the bearing and borne surfaces be in frictional contact. The arrangements described in FIGS. 1-6 show a superstructure supported from a base below the superstructure. The same arrangement can be used if the base is attached to a ceiling or wall provided that the bearing surface attached to the base provides support for the bearing surface attached to the superstructure over the full range of tilt angles. In some of these configurations, gravity tends to return the superstructure to the neutral position, and spring arrangements which are appropriately mounted and constrained to provide counteracting forces tending to push the superstructure further from neutral must be used. What has been described is considered to be only two illustrative embodiments of the invention. Thus, it is to be understood that various and numerous other arrangements may be devised by one skilled in the art without departing from the spirit and scope of the invention. For example, although the spring mechanisms shown utilize two alternatively acting expansion springs, this mechanism could use a single spring or instead use one or two helical compression, spiral, or torsional springs. The adjustable mounting apparatus of this invention could then be readily correspondingly modified. The invention is thus limited only as defined in the accompanying claims.
Apparatus for mounting a movable superstructure on a fixed base is disclosed. The superstructure, a video display unit, is attached to a cylindrical segment journal which rests on a matching cylindrical segment socket. The journal rotates within the socket as the video display unit is tilted back and forth. Two helical springs are each attached to the superstructure and the base in such a way as to counteract gravitational forces and to tend to restore the superstructure to a neutral tilt angle when it is moved therefrom. The surfaces of the journal and socket have enough friction to exceed the relatively small differences between the gravitational forces tending to move the superstructure further from the neutral tilt angle and the spring forces tending to restore the superstructure thereto. As a result, the superstructure will maintain any position but can be moved (tilted) by overcoming only the relatively small frictional force. In one constructed model, a video display unit superstructure weighing 27.2 pounds (12.3 kilograms) was provided with a maximum backward tilt of 30 degrees and could be tilted to any position upon the application of a force of only three pounds (1.4 kilograms).
8
FIELD OF THE INVENTION The present invention concerns stable, concentrated aqueous suspensions of 2,2-dibromo-3-nitrilopropionamide and methods of preparing and using said suspensions in biocidal applications. BACKGROUND OF THE INVENTION 2,2-Dibromo-3-nitrilopropionamide (DBNPA) is a well-known compound useful in aqueous systems due to its biocidal activity. DBNPA has proven especially useful in controlling the fouling of cooling towers due to slime accumulation and in removing slime from wood pulp prior to processing operations in the paper industry. See, for example, U.S. Pat. Nos. 3,751,444; 4,163,796;, 4,241,080; and 4,328,171. For many antimicrobial applications, it is desirable to employ DBNPA in a liquid concentrate composition for ease of shipment, storage, and especially for dispersibility in aqueous systems. Due to its cost, availability, and safety, water would be an ideal solvent for use in preparing such concentrates. Unfortunately, since DBNPA is only slightly soluble in water and usually degrades after prolonged contact with water, its use in such concentrates has not been found to be acceptable. See for example, "Rates and Products of Decomposition of 2,2-dibromo-3-nitrilopropionamide", Exner et al., J. Agr. Food Chem., Vol. 21, No. 5, pp. 838-842. Because water has an adverse impact upon DBNPA, various types of stabilizers and non-aqueous solvents have been utilized in preparing liquid formulations of DBNPA. A recent commercial group of stabilizers for DBNPA are the polyalkylene glycols as disclosed in U.S. Pat. No. 5,070,105. Unfortunately, commercial formulations comprising DBNPA, a polyalkylene glycol such as tetraethylene glycol, and water are fairly expensive due to the cost of the polyalkylene glycol. In addition, the DBNPA still degrades significantly over the course of time. Yet another disadvantage of this formulation includes the environmental concerns associated with employing polyalkylene glycols. One such environmental concern is that increased chemical oxygen demand of the industrial waste water, e.g., cooling tower effluent, results when DBNPA is employed with organic solvents such as polyalkylene glycols. Chemical oxygen demand represents the amount of oxygen consumed in the oxidation of organic and oxidizable inorganic material contained in the waste water. See Richard J. Lewis, Hawley's Condensed Chemical Dictionary, Twelfth Edition, 1993, p. 253. A high chemical oxygen demand is undesirable for a body of water whether the body be a wastewater treatment pool or a natural body of water. A high chemical oxygen demand for a body of water is undesirable because biodegradation of microorganisms may cause oxygen depletion in said body of water. If the body of water is a wastewater treatment pool then oxygen depletion could be detrimental to the efficient operation of the wastewater treatment plant. If the body of water is a natural body of water then oxygen depletion could be detrimental to aquatic life which require oxygen for survival. Formulations comprised of DBNPA and organic solvents contribute more chemical oxygen demand than if DBNPA is employed alone or with non-organic solvents because organic solvents serve as a feeding ground for microorganisms by providing nutrients. Therefore, even though the DBNPA may destroy a majority of the microorganisms before it degrades, a few microorganisms still survive. Those few microoganisms multiply very rapidly in the presence of an organic solvent. Therefore, when DBNPA-treated waste water containing an organic solvent is released to the environment, or even if it is in a closed system, chemical oxygen demand will increase significantly over time due to the rapidly multiplying microorganisms consuming oxygen in the water. It would be desirable to discover liquid formulations of DBNPA that utilize water as a suspending medium and in which the DBNPA is protected to prevent or reduce the decomposition or degradation thereof. This type of formulation would not only reduce the chemical oxygen demand as compared to the present commercial formulations which employ polyalkylene glycols, but such a formulation would also be less expensive. It would also be advantageous if a wide range of concentrations of DBNPA could be employed in the formulations. Furthermore, it would be desirable if the formulations were insensitive to changes in temperature and electrolyte concentration. SUMMARY OF THE INVENTION Surprisingly, it has been discovered that novel formulations of DBNPA can be produced which have a lower chemical oxygen demand than previous formulations. Even more surprisingly, the novel, less expensive formulations employ water as a suspending medium and less degradation of DBNPA results than when known organic solvents are employed. A wide range of concentrations of DBNPA are useful, i.e., about three weight percent to about 70 weight percent DBNPA are possible in formulations of the invention. The formulations are substantially insensitive to changes in temperature from about 0° to about 100° C. and to changes in the electrolyte concentration. The formulation comprises a suspension of DBNPA and water in the presence of a suspending amount of a thixotrope which exhibits Ellis-Plastic behavior over a pH range of from about 1 to about 4. These thixotropes include such natural gums as xantham gum and locust bean gum, such clays as bentonites, and mixtures thereof. The present invention also includes a process of making the above formulations as well as a method of using the above formulations. The process comprises suspending from at least about 3, preferably at least about 20, more preferably at least about 50, to at most about 70 weight percent DBNPA in at least about 30, preferably at least about 40, to at most about 97 weight percent water in the presence of a suspending amount of a thixotrope which exhibits Ellis-Plastic behavior over a pH range of from about 1 to about 4. The above formulations are useful as a method for biological control in an aqueous industrial system in need of such control which comprises contacting the system with an antimicrobially effective amount of the above formulation. The term "thixotrope exhibiting Ellis-Plastic behavior" refers to compounds or mixtures of compounds which cause a formulation to exhibit the following properties. First, the formulation must form a gel which liquefies when agitated, yet returns to the gel state when it is at rest. Second, in contrast to most liquids which will flow when subjected to any shear stress, i.e., force applied to the liquid, no matter how small the stress, formulations of this invention require some minimum amount of shear stress in order to liquefy the formulation and cause it to flow. This minimum amount of shear stress is called the "yield value" and it varies as the particular thixotrope and its concentration vary. The yield value of the thixotrope must be high enough to suspend DBNPA particles in water. This means the yield value must exceed the force of gravity acting on the DBNPA particles or the DBNPA will settle to the bottom. In general, the minimum yield value necessary to suspend a spherical particle may be determined by the following equation: minimum yield value =(4/3)(C r )(ρ p -ρ m ) wherein C r represents the radius of the particles to be suspended, ρ p represents the density of the particles to be suspended, and ρ m represents the density of the suspending matrix. See, for example, Carbopol™ Bulletin DET-3 from BF Goodrich 3/93. Thus, the yield value will necessarily be higher when larger DBNPA particles are employed in the formulation. Thirdly, the thixotrope must cause the formulation to exhibit "shear thinning" behavior. This means that when the shear stress is above the yield value, the viscosity of the formulation will be reduced as the shear stress increases. The thixotrope must exhibit these properties over a pH range of from about 1 to about 4 to be effective in a formulation with DBNPA because when DBNPA is added to water, the pH normally equilibrates this level. The term "suspending amount" refers to that amount of thixotrope that provides for suspending DBNPA particles such that less than about 5, preferably less than about 3, percent of the DBNPA settles to the bottom during conventional shipment and storage for about 6-12 months, yet still allows the suspension to be pumped as a liquid upon slight agitation. The term "antimicrobial" refers to the function of DBNPA as a biocide, i.e., inhibits the growth of, or kills, microorganisms such as bacteria, molds, yeasts, algae, protozoa, etc. The term "effective amount" refers to that amount of the antimicrobial formulation of the present invention which will provide for biological control in aqueous systems. The term "biological control" or "biologically controlling" refers to prevention, reduction, or elimination of any adverse consequences such as slime formation, corrosion, odor, etc., in aqueous industrial systems that are directly, indirectly, or otherwise due to the presence and/or growth of microorganisms. The aqueous systems contemplated for application of the method of the present invention include those aqueous industrial systems susceptible to growth, accumulation, or presence of microorganisms; for example, cooling towers, pulp and paper mills, metalworking fluids, air washers, and the like. DETAILED DESCRIPTION OF THE INVENTION Suitable thixotropes for suspending DBNPA in water according to this invention include those which exhibit Ellis-Plastic behavior at a pH of from about 1 to about 4, preferably from a pH of about 2 to about 3. These thixotropes typically exhibit a yield value which exceeds the force of gravity acting on the DBNPA particles thereby allowing the DBNPA particles to be suspended in water and thus protected from the degrading effects water usually has upon DBNPA. Useful thixotropes include natural gums such as xantham gum and locust bean gum, clays such as bentonites and mixtures thereof. Other thixotropes useful in this invention may be determined by the following test. Test for Determining Suitable Thixotropes 1. In a cylindrically shaped vessel, a uniform mixture of the thixotrope to be tested is prepared by admixing a predetermined amount of the thixotrope in a predetermined amount of water to give various predetermined concentrations of the thixotrope in water. A series of mixtures ranging from 0.1 weight percent to 2 weight percent thixotrope in water are thus prepared. To each of these mixtures, a predetermined amount of solid DBNPA is then added with agitation to prepare a series of formulations containing from 3 to 70 weight percent DBNPA. Typically, a few minutes of agitation is sufficient to achieve a uniform suspended mixture in the form of a gel for each formulation. However, three hours should pass before Step 2 is undertaken in order that the formulation reaches an equilibrium at which it will exhibit its final thixotropic properties. 2. After three hours have passed, the formulations can now be tested for suitability in the invention. Gentle agitation is applied to the formulations. If little or no flow occurs upon agitation of the formulation then the thixotrope is not suitable for use in the invention. Suitable thixotropes (assuming they exhibit suitable yield value and stability as determined in step three below) should cause the formulation to liquefy and flow upon agitation and return to its gel form almost immediately upon cessation of agitation. 3. The formulation's yield value and stability are tested by storing the suspended gel mixtures at about 40° C. for four weeks. If the formulation has not settled in this time then the thixotrope is suitable for use in the invention. Non-uniformity of the formulation indicates unsuitability of the thixotrope for use in this invention. Non-uniformity is detected by the formation of an appreciably particle free upper liquid layer and/or a dense solid bottom layer. If less than about 5 percent of the solid DBNPA has settled to the bottom or if less than about 10 volume percent of a substantially particle free upper layer has formed, the thixotrope is acceptable for use in formulations of this invention. The amount of solid DBNPA at the bottom, if any, can be determined by decanting the formulation to leave only the solid DBNPA that had settled. The solid DBNPA is then dried and weighed to determine if more than 5 percent of the total DBNPA has settled. If more than 5 percent of the DBNPA is present then the thixotrope is unacceptable. If a particle free upper liquid layer exists then it can be determined if said layer is more than 10 volume percent by dividing the depth of the upper layer by the depth of the total formulation. If the ratio is more than 0.1 (10 percent) then the thixotrope is unacceptable. Once a thixotrope has been identified as useful in the invention by the above test, the suspending amount of thixotrope necessary must be determined. Typically, this amount will vary depending upon the nature of the thixotrope as well as the amount of DBNPA and water present. However, in general the amount of thixotrope should not be so much that the suspension becomes too thick to be pumped as a liquid. On the other hand, the amount should be sufficient to suspend and maintain the DBNPA in water with less than about 5, preferably less than about 3, percent of the DBNPA settling during conventional shipment and storage of the suspension for 6-12 months. Generally, the suspending amount is at least about 0.03 weight percent of the total suspension, preferably at least about 0.8, to at most about 4, preferably to at most about 2 weight percent of the total suspension. A preferred thixotrope and amount is a mixture of from about 0.05 to about 1.5 weight percent xantham gum and about 0.01 to about 0.5 weight percent locust bean gum. Advantageously, formulations of this invention may be made which utilize a wide range of DBNPA concentrations. This allows the utilization of a concentration of DBNPA that is suitable for a particular application as well as a concentration that is convenient to ship and store. Although the concentration of which the formulation is capable may vary with the particular thixotrope chosen, it is usually from at least about 3, preferably at least about 5 weight percent DBNPA to at most about 70, preferably at most about 60 weight percent DBNPA. This is due to the fact that with most thixotropes, if more than about 70 weight percent DBNPA is employed then the formulation will exhibit a clay-like consistency and not readily disperse when employed in an aqueous system. On the other hand, since about 1.5 weight percent of DBNPA dissolves in water, it is not practical to employ less than about 3 percent. Although it is not required, it is desirable to use the crystalline form of DBNPA for ease of dispersing and suspending it in the water. Smaller crystals are generally desirable. This is due to the fact that the required yield value of the thixotrope will be less, as described above, as well as the fact that the DBNPA will more rapidly disperse in the water. However, the DBNPA particles should not be so small that DBNPA dust is problematic. Generally, DBNPA particle sizes of about 160-180 microns×50-70 microns×50-70 microns are very effective when used with a thixotrope such as xantham gum, locust bean gum or such clays as bentonites or mixtures thereof. Water comprises the remainder of the formulation and functions as the suspending medium in which the DBNPA is substantially uniformly dispersed. It is not necessary that the water be distilled or purified. Normal water, for example tap, well, or distilled, may be employed in most applications. Typically, water is employed in an amount of from at least about 30, preferably at least about 40, to at most about 97, preferably at most about 95 weight percent of the total formulation. Although it is not necessary in most instances, it may be desirable to acidify the formulation before adding the DBNPA to the water if the pH of the water is initially above 7. This is due to the fact that DBNPA will degrade more rapidly and to a greater extent at higher pH's. In general, almost any acidifying agent may be used, for example oxalic acid, acetic acid, citric acid, carboxylic acids, and mineral acids such as phosphoric, sulfuric and hydrobromic may be usefully employed. The type of acid and amount may be varied based upon the particular thixotrope, amount of DBNPA, and the desired application. The amount that should be employed will be apparent to one skilled in the art in that the pH of the water should be reduced below about 7 before addition of the DBNPA. Upon addition of the DBNPA, the pH of the formulation will usually equilibrate to about 1 to about 4 and no further acidification is usually needed. Although the ingredients of the formulation may be mixed together in any order, for ease of mixing it is desirable to slowly add the suspending amount of thixotrope to a known amount of tap water while agitating until the thixotrope is well dispersed. The DBNPA is then added with agitation. The temperature is conveniently about 25° C. although higher temperatures may cause the thixotrope and DBNPA to mix more rapidly with the water but the temperature should not be so high that the water boils. The formulation of the present invention can optionally have other active or inert ingredients conventionally employed in such types of formulations such as corrosion inhibitors, scale inhibitors, colorants, fragrances, etc. The formulations of the present invention are useful for many different applications. Among useful applications are controlling bacteria in cooling systems and controlling bacteria, fungi, and algae in recirculating water cooling towers and air washer systems. Although dosage rates vary by application, typical dosage rates are from about 0.5 to about 5 parts per million of active DBNPA with a higher initial dose than subsequent doses. The present invention is illustrated by the following examples; however, the examples should not be interpreted as a limitation upon the scope of the present invention. All percentages are by weight of total formulation unless otherwise indicated. EXAMPLE 1 A premeasured amount of a mixture of xanthan gum and locust bean gum was slowly added to well stirred tap water. Mixing was continued until the gum mixture was thoroughly dispersed in the solution. The solution was held at room temperature for thirty minutes. While mixing again, a predetermined amount of oxalic acid was then added followed by a predetermined amount of DBNPA. The percentage of each of the ingredients utilized, as well as the pH of the formulations, are exemplified in Table I. Examples 2, 3, and 4 were prepared in substantially the same manner employing varying amounts of xanthan gum, locust bean gum, water, oxalic acid, and DBNPA as shown in Table I. The xanthan gum employed was TICAXAN Xanthan Powder™ (available from TIC Gums) and the locust bean gum employed was Locust Bean POR/A TIC Powder™ (available from TIC Gums). TABLE I______________________________________ Locust Oxalic DBNPAXanthan Bean Water Acid (1) pH______________________________________Example 1 1.000 0.335 48.67 0.030 49.97 2.4Example 2 0.772 0.259 48.94 0.023 50.01 2.4Example 3 0.516 0.173 49.45 0.015 49.85 2.4Example 4 0.305 0.102 49.62 0.009 49.96 2.4______________________________________ (1) All values in weight percent except pH. Stability tests involving aging studies and freeze-thaw cycles were conducted on the formulations of Examples 1-4. The aging studies upon Examples 1-4 consisted of storing the suspensions at a temperature of about 22° C. for a period of 12 months. When measured by high pressure liquid chromatography, no measurable loss in the total DBNPA was detected for the formulations of Examples 1-4. Freeze-thaw cycles consisted of subjecting the formulations of Examples 1-4 to a temperature of -29° C. for a period of 16 hours followed by 8 hours at room temperature with no agitation. No appreciable degradation of DBNPA occurred in Examples 1-4 and all remained suspended over the course of 23 days. By the 30th day the formulation of Example 4 had settled. The chemical oxygen demand of the formulations of Examples 1-4 can be calculated to be about 1.08 parts per million (ppm) for every one ppm of DBNPA employed. This compares very favorably to commercial formulations which employ 20 percent DBNPA, 20 percent water, and 60 percent tetraethylene glycol and exhibit a calculated chemical oxygen demand of 5.85 ppm for every one ppm of DBNPA. The stability of the formulations of Examples 1-4, at a constant temperature of 20° C. and pH of 3.0, can be calculated to chow that 99.82 percent DBNPA remains after 9 months. This compares very favorably to the stability of commercial formulations which employ 20 percent DBNPA, 20 percent water, and 60 percent tetraethylene glycol at a constant temperature of 20° C. and pH of 3.0 which exhibit a calculated amount of only 91.8 percent of the DBNPA remaining after 9 months. The antimicrobial activity of the compounds of the present invention, illustrated by compound Example No. I and II of Table II, is demonstrated by the following techniques. TABLE II______________________________________Identification of Compounds Used inAntimicrobial Activity TestsCompoundExampleNo. Chemical Identity______________________________________I Suspension of 50 weight percent DBNPA, 0.75 weight percent xanthan gum, 0.25 weight percent locust bean gum, and 49 weight percent water which suspension was freshly prepared before antimicrobial activity testII Suspension of 50 weight percent DBNPA, 0.75 weight percent xanthan gum, 0.25 weight percent locust bean gum, and 49 weight percent water which suspension was aged for over 15 months before antimicrobial activity test______________________________________ The minimum inhibitory concentration (MIC) for the compounds listed in Table II is determined for 9 bacteria, using nutrient agar, and 7 yeast and fungi, using malt yeast agar. A one percent solution of the test compound is prepared in a mixture of acetone and water. Nutrient agar is prepared at pH 6.8, representing a neutral medium, and at pH 8.2, representing an alkaline medium. The nutrient agars are prepared by adding 23 g of nutrient agar to one liter of deionized water. In addition, the alkaline medium is prepared by adjusting a 0.04M solution of N-[tris-(hydroxymethyl)methyl]glycine buffered deionized water with concentrated sodium hydroxide to a pH of 8.5. Malt yeast agar is prepared by adding 3 g yeast extract and 45 g malt agar per liter of deionized water. The specific agar is dispensed in 30 mL aliquots into 25×200 mm test tubes, capped and autoclaved for 15 minutes at 115° C. The test tubes containing the agar are cooled in a water bath until the temperature of the agar is 48° C. Then, an appropriate amount of the one percent solution of the test compound is added (except in the controls where no compound is added) to the respective test tubes so that the final concentrations are 500, 250, 100, 50, 25, 10, 5, 2.5, 1.0 and zero parts per million of the test compound in the agar, thus having a known concentration of test compound dispersed therein. The contents of the test tubes are then transferred to respective petri plates. After drying for 24 hours, the petri plates containing nutrient agar are inoculated with bacteria and those containing malt yeast agar are inoculated with yeast and fungi. The inoculation with bacteria is accomplished by using the following procedure. Twenty-four hour cultures of each of the bacteria are prepared by incubating the respective bacteria in tubes containing nutrient broth for 24 hours at 30° C. in a shaker. Dilutions of each of the 24 hour-cultures are made so that nine separate suspensions (one for each of the nine test bacteria) are made, each containing 108 colony forming units (CFU) per mL of suspension of a particular bacteria. Aliquots of 0.3 mL of each of the bacterial suspensions are used to fill the individual wells of Steer's Replicator. For each microbial suspension, 0.3 mL was used to fill three wells (that is, three wells of 0.3 mL each) so that for the nine different bacteria, 27 wells are filled. The Steer's Replicator is then used to inoculate both the neutral and alkaline pH nutrient agar petri plates. The inoculated petri plates are incubated at 30° C. for 48 hours and then read to determine if the test compound which is incorporated into the agar prevented growth of the respective bacteria. The inoculation with the yeast and fungi is accomplished as follows. Cultures of yeast and fungi are incubated for seven days on malt yeast agar at 30° C. These cultures are used to prepare suspensions by the following procedure. A suspension of each organism is prepared by adding 10 mL of sterile saline and 10 microliters of octylphenoxy polyethoxy ethanol to the agar slant of yeast or fungi. The sterile saline/octylphenoxy polyethoxy ethanol solution is then agitated with a sterile swab to suspend the microorganism grown on the slant. Each resulting suspension is diluted into sterile saline (1 part suspension to 9 parts sterile saline). Aliquots of these dilutions are placed in individual wells of Steer's Replicator and petri plates inoculated as previously described. The petri plates are incubated at 30° C. and read after 48 hours for yeast and 72 hours for fungi. Table III lists the bacteria, yeast and fungi used in the MIC test described above along with their respective American Type Culture Collection (ATCC) identification numbers. TABLE III______________________________________Organisms Used in the MinimumInhibitory Concentration TestOrganism ATCC No.______________________________________BacteriaBacillus subtilis (Bs) 8473Enterobacter aerogenes (Ea) 13048Escherichia coli (Ec) 11229Klebsiella pneumoniae (Kp) 8308Proteus vulgaris (Pv) 881Pseudomonas aeruginosa (Pa) 10145Pseudomonas aeruginosa (PRD-10) 15442Salmonella choleraesuis (Sc) 10708Staphylococcus aureus (Sa) 6538Yeast/FungiAspergillus niger (An) 16404Candida albicans (Ca) 10231Penicillium chrysogenum (Pc) 9480Saccharomyces cerevisiae (Sc) 4105Trichoderma viride (Tv) 8678Aureobasidium pullulan (Ap) 16622Fusarium oxysporum (Fo) 48112______________________________________ In Tables IV and V, the MIC values of the compounds described in Table II as compared to the MIC of a standard commercial preservative (with 1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride as the active agent and referred to in Tables IV and V as "STANDARD I") are set forth for the bacteria organisms and yeast/fungi organisms which are listed in Table III. TABLE IV__________________________________________________________________________Minimum Inhibitory Concentrations for Test Compoundsin Bacteria Species (in ppm) ORGANISMSCompound Bs Ea Ec Kp Pv PRD Pa Sc Sa__________________________________________________________________________STANDARDpH 6.8 50 100 100 50 50 100 100 50 100pH 8.2 250 250 250 250 250 500 >500 100 250(I)pH 6.8 100 100 100 100 100 100 100 100 100pH 8.2 500 501 501 501 500 501 501 501 501(II)pH 6.8 100 100 100 100 100 100 100 100 100pH 8.2 500 501 501 501 500 501 501 501 501__________________________________________________________________________ TABLE V__________________________________________________________________________Minimum Inhibitory Concentrations for TestCompounds in Yeast/Fungi Species (in ppm) ORGANISMSCOMPOUND An Ca Pc Sc Tv Ap Fo__________________________________________________________________________STANDARD >500 >500 >500 500 >500 >500 >500I 250 50 250 50 500 25 50II 250 50 250 50 500 50 50__________________________________________________________________________
Stable, concentrated aqueous suspensions of 2,2-dibromo-3-nitrilopropionamide which contribute minimal chemical oxygen demand to systems treated therewith and methods of preparing and using said suspensions in biocidal applications have been discovered. The formulations comprise from about 3 to about 70 weight percent 2,2-dibromo-3-nitrilopropionamide suspended in about 30 to about 97 weight percent water in the presence of a suspending amount of a thixotrope that exhibits Ellis-Plastic behavior, such as xantham gum and locust bean gum, at a pH of from about 1 to about 4.
8
BACKGROUND OF THE INVENTION 1. Field of the Invention: The invention concerns a process control circuit for the control and monitoring of at least one metal-depositing bath, particularly, a gold bath. 2. Description of the Prior Art: For the purpose of automatic analyses of liquid substances, it is obvious to use a program-controlled automatic analysis machine (German Offenlegungsschrift Nos. 2 341 149 or 2 113 854), consisting of a control device, a measuring stage and a regulating stage, as well as a dosing device. In the case of an analysis device for metal-depositing baths, it is necessary that the analysis of several parameters and/or components in a bath be carried out as rapidly as possible and, particularly, in the case of gold baths, with a high degree of precision. Thus, for example, in the case of a gold bath, the gold concentration level must be kept within a narrow range of a predetermined nominal value. The smaller this range, the more uniform the deposited layer becomes such that the consumption of the precious metal is optimally minimized. It is necessary to detect as measured quantities all the parameters which effect the function of the bath or baths. Parameters of this type are the pH-value, the concentration of the metal components in the bath fluids, as well as the temperature at the time of analysis. Also, the measuring electrode of a pH-value regulator degenerates in the course of time; i.e., it demonstrates a divergence vis-a-vis a calibration-buffer solution. In addition, in the case of a gold bath-analysis device with a colorimeter stage, it was determined that the windows of the colorimeter vessel become turbid as a result of condensation formation. Such turbidity leads to an erroneous result in a subsequent measurement. The pH-value regulator as well as the analyzer-section which determines the metal concentration, such as the gold bath analysis device, indirectly controls the influx of correction fluid to the bath. It is therefore important that the measured values be permitted to exhibit only a small deviation of ± 1%, at the most, from the actual values. The individual analyses must be capable of being carried out at as high a speed as possible, since only a repeated analysis of each of the baths makes it possible to maintain narrow ranges of individual bath temperatures to be measured and regulated. SUMMARY OF THE INVENTION An object of the invention is therefore to produce a process control circuit for the monitoring as well as the control of one or more metal-depositing baths, particularly for one or more gold baths, whereby the circuit analyses for the individual parameters of the bath fluid which are to be carried out take place simultaneously. Furthermore, prior to each analysis to be carried out, there should be an automatic adjustment or calibration of the circuit. Also, it is an object of the circuit to provide an interrogation of several baths regarding their respective temperatures, the pH-values, and the concentration of the metal or metals at any time and selectively. If any measuring value exceeds a predetermined boundary value, a warning should take place and the dosage to the respective bath should be blocked. According to the invention, the objects are achieved by providing a process control circuit which has a plurality of parameter control circuit blocks, each circuit block comprising a measuring stage, a calibration adjustment or balancing device, a nominal value generator or comparator, and a doser circuit. The circuit blocks are capable of being switched and actuated by a program generator such that they operate simultaneously and independently of one another. The process control circuit of this invention permits analyses with high precision and relative rapidity and maintains the baths within a permitted range around the nominal values of the individual parameters of the bath fluids. Prior or subsequent to several analyses of a bath fluid, whether it be regarding the pH-value or the metal content, there is an automatic adjustment or balance of the respective measuring stage. Adjusting devices serve this purpose. A nominal value generator or comparator is connected to the measuring stage and the difference between the measured value and the nominal value is determined in a difference circuit inserted after the nominal value generator. If there is a divergence between the actual and nominal values, a signal is presented to the dosing device which indirectly controls the dosage valve assigned to it. The dosing device serves the purpose of supplying the specific correction fluid to the bath being subjected to analysis. As is known, a temperature compensator is assigned to the respective measuring stage circuit. This compensator corrects the measured value if it deviates from a predetermined standard temperature since the pH value measurement and the measurement for determining the gold content are very temperature dependent. Only this corrected measurement value reaches the measuring value calibrator device. Thus, the adjustment by the calibrator device takes place for a measuring value which has already been corrected with regard to temperature. The process control circuit comprises at least one parameter control circuit block for monitoring and regulating the metal concentration, and at least one additional parameter control circuit block for monitoring and regulating the pH value of the bath fluid to be monitored. The circuit block for monitoring the metal concentration of the bath fluid has in its measuring stage two photoconductive resistors which are connected to a colorimeter, an amplifier, and an automatically operated potentiometer, the center tap of which is situated at the input of the amplifier. One of the photoconductive resistances is arranged in a feedback line of the amplifier and is connected to the potentiometer. The other end of the potentiometer is connected to the other photoconductive resistor. During one operating condition, which may be activated by means of a program switch, the measured value output from the amplifier indirectly drives a servomotor operating the potentiometer. Depending upon the polarity of the voltage amplitude, the servomotor drives the potentiometer towards an ideal position so that an ideal voltage is connected to the output of the amplifier. In this condition, the aforementioned switch opens. The measuring stage has now been calibrated and is ready for operation. Each parameter control circuit block is provided only once in the process control circuit, whereas the number of measured value storage units and boundary value monitors provided in the process control circuit are proportionate to the number of baths which are to be monitored with the process control circuit multiplied by the number of parameters to be measured in the individual baths being monitored. The measured value storage units as well as the boundary value monitors for the individual bath parameters of the various baths are of uniform construction so that they are capable of being inserted in the process control circuit as similar printed circuit boards. According to a prescribed program, the bath to be analyzed is selected from a plurality of baths. The bath fluid is supplied to an analyzer comprising a plurality of analysis sections. The individual analysis section construction depends upon the type of chemical composition of the bath which is to be monitored. If a gold bath is to be monitored and controlled, the analyzer has an analysis section for determining the gold concentration consisting, among other things, of a colorimeter and an additional analysis section with a pH-value regulator, as well as an analysis section for determining the cobalt concentration of the bath fluid. A parameter control circuit block is assigned to each analysis section of the analyzer. The measured values output by the circuit blocks are connected to the measured value storage units assigned to the bath which is to be analyzed and to which the boundary value monitors are also assigned. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 illustrates the parameter control circuit block for determining the gold concentration for a gold-depositing bath. FIG. 2 illustrates a block circuit diagram of the process control circuit with two parameter control circuit blocks, one for determining the gold concentration and an additional circuit block for determining the pH-value; also shown is the assignment of the measured value storage units and boundary value monitors to the circuit blocks. FIG. 3 illustrates the parameter control circuit block for determining the pH-value. FIG. 4 illustrates a measured value storage unit with a boundary value monitor. FIG. 5 illustrates the assignment of the measured value storage units and boundary value monitors to the parameter control circuit blocks. DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 illustrates a component or parameter control circuit block for determining a metal concentration such as gold in a gold-depositing bath. The component or parameter circuit block comprises a measuring stage A, an adjustment or calibrating device B, a nominal value generator C, and a dosing device D. In addition, the circuit block has a temperature-compensated voltage source E. In the present example, determination of the metal concentration of the bath fluid takes place colorimetrically, namely, by means of a two-beam colorimeter, which exhibits a photoelectric cell 1 for the measuring beam, and a photoelectric cell 2 for the reference beam. In the measuring stage, photoelectric cells are constructed as photoconductive resistors. A temperature compensation stage E is connected to the measuring stage A. This stage has a thermistor 4 which is connected to an extraction receptacle of the gold bath analyzer. This thermistor 4 is connected to a voltage path 6' which is stabilized by a zener diode 5 at a voltage divider-tap 6. The sensitivity of the thermistor is adjustable on a trimmer potentiometer 7. In addition, the measuring voltage is adjustable to +0.2V by an additional trimmer potentiometer 8. If there is a temperature change in thermistor 4, the measuring voltage fluctuates for example, around +0.2V (10 mV/° C), in proportion to the temperature change. Potentiometer 7, thermistor 4, and resistance 7' form a voltage divider. The measuring voltage tapped from the divider is connected to the input 9 of an amplifier 11 having a feedback loop 10 connected at the other input 12 which is also connected to the voltage tapped from potentiometer 8. When switch 13 is activated by a program generator and rests in the illustrated position, a voltage which has been corrected with regard to the temperature of the bath under measurement is connected to 3 at reference photoconductive resistor 2. For example, if the temperature of the fluid subjected to a colorimeter examination differs by 2° C from the standard temperature (20° C) a voltage difference deviating from +0.2V (at 20° C) results at inputs 9 and 12 of amplifier 11 such that a proportional voltage change occurs at photoconductive resistor 2. As is apparent, a measuring beam photoresistor 1 is located within measuring stage A in the feedback loop of measured value amplifier 15 whereby the photoconductive resistors 1 and 2 respectively form the feedback resistance and the input resistance. If the exposure at photoconductive resistor 1 differs as compared with the exposure at photoconductive resistor 2, the amplification factor of amplifier 15 is thereby changed. The circuit is designed such that, given equal exposure intensity on both photoconductive resistors 1 and 2, the amplification is equal to 1, and the output voltage on line 16 becomes +0.2V (at 20° C); in the case of a divergence of the resistance values, the amplification factor is changed; the output voltage differs from +0.2V (at 20° C) and the signal connects via line 16 to an amplifier 18, at the output 22 of which provides the measured value. This measured value output at 22 is also connected to the adjustment device B which has an input amplifier 23. A potentiometer 39 serves to reset the device B for ideal operational voltage during calibration. In the following, the calibrating or adjustment circuit B shall be more closely described with regard to its construction and function. As already stated, the colorimeter measuring vessel or its windows become covered with vapors or condensation caused by the fluid line which is connected to the vessel. As a result, the absorption of the light, as limited by the measuring fluid, undergoes an additional attenuation due to the coating on the vessel windows. To avoid an error in measurement caused thereby, an ideal voltage adjustment of the colorimeter takes place prior to each measurement. In order to effect the ideal voltage adjustment, the temperature compensator E is first separated from measuring stage A; this takes place through the program control device, not illustrated here, by way of switching program switch 13 to the position illustrated with broken lines. Now, a defined measuring voltage of +0.2V is connected to photoconductive resistor 2. Program switch 21 is likewise closed by means of the program control device in the ideal voltage adjustment circuit B. If, in this switched condition, a voltage is connected to amplifier 15 which deviates from 0.2V, a signal will be connected to the output or junction 22 of amplifier 18 and also at the input of ideal voltage adjustment or calibrating device B. A servomotor 24, connected to potentiometer 14, is operated by a transistor switch 25 which obtains drive voltage via feedback input amplifier 23. When the switch 21 is closed, the motor starts in right or left operation, depending upon the connection potential; it sets the potentiometer 14 until the absolute value of the voltage at junction 22 is equal to the ideal adjustment voltage, at which point it automatically shuts off. Switch 13 is re-set and switch 21 is opened by the program generator; motor 24 has no current drive, and the circuit is now ready for measurement. Now follows the filling of the measuring vessel (not shown) of the colorimeter stage with the fluid to be analyzed. The voltage on the terminals of the measuring beam photoconductive resistor 1 changes. As a result, a measuring signal is connected at 22, and therefore also to the dosing device D. The dosing device is operated by an amplifier 26 after which a switch 27, controlled by the program generator, is inserted. During the dosing operation the switch is in the position illustrated by broken lines. A nominal value generator, consisting of a voltage divider 28 constructed as a manually operated potentiometer adjusts the desired nominal value (grams of gold per liter of bath fluid), and thus provides the nominal value adjustment at measuring input 29 of master amplifier 26. Simultaneously with the closing of program switch 27, a switch 30 of an integrator 31 also closes. The signal voltage emitted from amplifier 26 is connected to input 32 of a dosing amplifier 33. As a result, a safety switch 34 is closed and the dosing relay 35 is actuated when the output voltage on master amplifier 26 is positive. Correction fluid now flows to the bath. During this time, there is a positive increase in voltage at the output 31 of the integrator or timer such that at a given time the voltage on input 32 of amplifier 33 becomes zero and current passage to switching transistor 38 is thus interrupted to de-energize relay 35. Thus, the dosing operation terminates. FIG. 2 illustrates a block circuit diagram of the process control circuit, whereby the component circuit block for monitoring and regulating the metal concentration is illustrated in block I defined by broken lines. This block has been described above and illustrated in FIG. 1, as well as the component circuit block for monitoring and regulating the pH-value, which is illustrated in block II. Component circuit block I consists of measuring stage A, comprising photoconductive resistors 1 and 2, adjustment device B, which operates only during the adjustment or calibration of the colorimeter (here generally designated by 40) nominal value generator C with the adjustment potentiometer 28, amplifier stage 33 with the connected integrator or timer 31 as well as dosing device 38. As shown in FIG. 2, the parameter control circuit block for monitoring and regulating the pH-value of the bath fluid to be monitored likewise has a measuring stage A', a calibrating or adjustment device B', a nominal value generator 74, and a dosing device 42. As is apparent, each circuit block has a measuring output 43, or 43'. Graphic recorders (not illustrated here) and analog storage units 44 are connected to the measuring outputs. A boundary value monitor 45 is connected to the analog storage units respectively and which, when the respective allowable boundary value is exceeded, actuates an alarm system 46 and blocks the respective dosing devices, for example, 38 or 42, via line branches 38' and 42'. As shown in FIG. 1, blocking of the dosing operation takes place by means of opening relay switch 34. The warning or alarm system 46 also serves the purpose of monitoring the supply of correction fluids, flushing fluids, buffer solutions, and the like, which are necessary for the operation of the process control system. The supply control device is generally designated by 47. In addition, the alarm system is activated if a signal is triggered either from the monitoring circuit 48 of one or more bath circulatory systems or from a signal triggered by drop indicator 49 during the filling of the waste container. Each analysis section assigned to the measuring stage is flushed with distilled water after a predetermined number of analyses. A preselection counter 51 serves this purpose. During the flushing operation, a flushing indicator 50 delivers a signal to the warning system 46, which indicates the flushing process. The gold bath analyzer is equipped in such a manner that, after each analysis, a rinsing operation of the colorimeter with acetone automatically takes place. The process control circuit has a program control mechanism 52, which is constructed according to known methods as a camshaft gear, but which may also be constructed as a magnetic band with a decoding device inserted thereafter, such as a process control logic. The program control mechanism activates the analysis section for determining the values of the bath parameters. In the case of a process control circuit for monitoring and regulating a gold bath, the analysis sections are activated for measurement of the gold concentration, cobalt concentration, and the pH-value. In addition, the program control mechanism directly or indirectly activates the program circuit contacts illustrated in the corresponding component-circuit blocks I, II, etc. A measured value interrogation device 56 (shown in FIG. 2 as a block and in FIGS. 4 and 5 as switch 88) is connected to an analog storage unit 44. The device 56 interrogates by switching at any time the values of the bath fluid parameters, such as the metal concentration, the pH value, the temperature, and the like, by means of activating a selector switch which is assigned to a specific bath. If several baths are monitored and regulated by means of the process control circuit, the illustrated and described circuit may be switched over from one bath to another bath by means of a multi-bath change-over switch 57. The pumps for maintaining the respective bath circulatory systems of the individual baths, including the respective dosing devices 58 and 59, are also operated by control 57. FIG. 3 explicitly illustrates the parameter control circuit block II for monitoring and controlling the pH value for the bath fluid of one of the baths. The circuit blocks I, II, etc. are provided only once in the analyzer portion of the process control circuit, whereas the number of measured value storage units and boundary value monitors corresponds to the number of parameters in the bath fluids of the individual baths to be monitored. The conventional measuring stage A' (FIG. 3) consists of a pH-measuring electrode 60, a temperature compensator 61, and a measured value compensation device 62. An automatically operating regulating potentiometer 63 is in contact with the measured value compensation device and functions as a calibration or adjustment device. A calibration adjustment takes place after a specific number of measurements of the pH value by means of a calibrated buffer solution supplied to the measuring vessel which is not illustrated here, and which contains the pH-measuring electrodes and the temperature compensator 61. As has already been described regarding the parameter control circuit block 1, a calibration adjustment can take place only if switch 64 of current circuit 66, which contains the potentiometer-servomotor 65, is closed. If switch 64 is open, the entire circuit containing a feedback amplifier 67 and control transistors 68 and 68' (for the right and left operation of servomotor 65) is shut off. The measured value determined by measured value derivation device 62 is connected to impedance transformer 69, the output of which is connected to a graphic recorder (not shown) via a measured value line 43'. In addition, a branch 78 is connected to an adding device 71, which is connected to the measured value storage unit or units 44 (FIGS. 2, 4 and 5) via a line 79. A third branch of measurement output 70 is connected to dosing amplifier 72 at the input 73, to which an adjustment potentiometer 74 is also connected for the purpose of adjusting the nominal value. This circuit ensures that only when a voltage amplitude analogous to the measured value is exceeded (which corresponds to the nominal value) will a voltage be provided to open switching transistor 76 connected to output 75 of the amplifier 72. In such a case, dosing relay 77 is actuated for the purpose of supplying correction fluid to the bath. FIG. 5 illustrates analog storage units combined with boundary value monitors 45a 1 to 45d 3 . Many circuits of this type are present in the process control circuit and are provided as uniformly constructed printed circuit boards. The number of such circuits (the specific construction of which is shown in FIG. 2) corresponds to the number of baths which are to be monitored with the process control circuit, multiplied by the number of parameters of the respective bath fluids, each of which are to be monitored and regulated for the individual baths. The circuit illustrated in FIG. 4 is, for example, assigned to the component circuit block II. The measured value supplied as an analog voltage amplitude by measured value amplifier 71 connects to switches 80 and 81 via line 79. Switches 80 and 81 may be selectively activated by a bath selection program switch. Switches 81 or 80, for example, are closed by such a bath selection-program switching mechanism. As a result, capacitor 83 is charged up to the measuring voltage. After the measuring operation has been completed, switch 81 opens again, so that capacitor 83 remains charged. This capacitor is situated at the input 84 of a measured value amplifier 85, at the output 86 of which a contact 87 of a manually operable selector switch 88 is located. If selector switch 88 is on contact 87, measuring device 90 shows the measured value which corresponds to the voltage value of capacitor 83 which may correspond, for example, to the pH value of the bath fluid of a bath assigned to that position of the selector switch. If selector switch is on another contact 89, for example, measuring device 90 shows the pH value of the bath fluid of another bath, etc. Lines 91 and 92 are connected to identical circuits mounted on printed circuit boards, as specified in FIG. 4 and which are assigned to other baths. The boundary value monitors as indicated by 45 in FIG. 4 are likewise located at measurement outputs 86 of measured value amplifiers 85. By means of potentiometer 93, an upper voltage value may be adjusted on a differential amplifier 95. A lower value may be adjusted on a master amplifier 96. These voltage values analogously correspond to a specific pH value which cannot be permitted to drop below or exceed the upper and lower voltage values. If the voltage which is connected to the respective differential amplifier 95, or master amplifier 96 exceeds of falls below the allowable voltage which has been adjusted on the respective potentiometer, a voltage signal is created at output 97 or 98 of differential amplifier 95 or 96 such that a switching transistor 99 turns on the alarm relay 100. The alarm relay triggers an acoustical or optical alarm. In addition, switches are opened which are located in the control supply lines to the dosing valves such that no dosing supply or correction fluid, such as gold salt solution, will flow to the respective baths. Through this measurement, losses of expensive operating materials may be effectively avoided. FIG. 5 illustrates in a block circuit diagram the measured value interrogation and boundary value monitors 45a 1 through 45d 3 , all of which are constructed according to the circuit illustrated at 45 in FIG. 4. In the example of FIG. 4, the process control circuit comprises for the gold bath a circuit block I for the gold concentration analysis, a circuit block II for the pH value analysis, and a circuit block III for cobalt analysis. Four similar baths labeled a, b, c and d (not illustrated) are monitored and regulated by the process control circuit. Thus, three measured value interrogator and limiting value indicator-units (as shown in FIG. 4) are respectively assigned to each bath. Thus, for example, the measured value interrogator and boundary value monitor 45a 1 is assigned to bath A and to parameter control circuit block I, whereas the measured value interrogator and limiting value indicator 45d 3 is assigned to bath D and to circuit block III for a cobalt analysis of the bath fluid. Measured value lines 86a 1 to 86d 3 connected to units 45a 1 to 45d 3 are respectively connected to measuring devices 901 or 902 or 903 via manually operated ganged switches (in general) 88a 1 to 88d 3 . If the measured values for the bath fluid of bath B, for example, are to be interrogated with respect to one of the individual parameters such as the value of the gold concentration, cobalt concentration, or the pH of the bath fluid, hand operable key b' is activated, so that the measuring instruments 901 through 903 will indicate the respective magnitudes of the bath parameters of bath b which is being subjected to interrogation. The switches are closed only for obtaining measurements. Normally, however, they are open in order that the measured value storage-capacitors 83 illustrated in FIG. 4 cannot discharge. Each circuit block has an alarm relay 1001 to 1003. A relay is triggered if the allowable upper or lower limiting value of the respective bath parameters is exceeded within the limiting value unit 45 belonging to a circuit block. If the limiting value is exceeded, the alarm relay assigned to each bath and to the individual bath parameter also blocks the influx of correction fluid to the respective bath such that the membrane pumps for the purpose of dosing the correction fluid for the respective parameter is switched off, and the dosing valves for the supply of correction fluid to the bath are blocked. Although various minor modifications may be suggested by those versed in the art, it should be understood that we wish to embody within the scope of the patent warranted hereon, all such embodiments as reasonably and properly come within the scope of my contribution to the art.
A process control circuit which is adapted for the control and monitoring of a plurality of parameters in one or more metal-depositing baths, has parameter control circuit blocks for each of the parameters to be measured. Each of the parameter control circuit blocks has a measuring stage for producing a measured value corresponding to one of the parameters, a calibration stage for calibrating the measuring stage, a comparison stage for comparing the measured value to a stored nominal value, and a dosing circuit which is connected to the comparator and which doses the metal-depositing bath in response to a comparison signal from the comparator.
2
CROSS REFERENCE TO RELATED APPLICATIONS [0001] This application is based on and hereby claims priority to German Application No. 10 2006 017 031.8 filed on Apr. 11, 2006, the contents of which are hereby incorporated by reference. BACKGROUND [0002] The invention relates to a method for analyzing risks in a technical project for developing or manufacturing a technical system or technical components or a technical process. [0003] The analysis of risks in technical projects is one of the most important processes for reducing project risks and the associated potential cost of errors. Nowadays, guidelines are increasingly applied at company level that define the handling of such project risks for balance sheet purposes. An example of these guidelines, which every public limited company must observe, comprises the accounting principles according to US-GAAP (United States Generally Accepted Accounting Principles). These guidelines provide a concrete description of the US accounting regulations and the associated processes. In order to be able to include project risks in a suitable manner in financial balance sheets, the technical risks in the project must be estimated in a suitable manner, where the accounting regulations do indeed specify how risks are to be included in the balance sheet but do not explain how qualitatively determined technical risks are to be converted into quantitatively recordable risks for use in the balance sheet. [0004] At the technical level, a large number of methods for technical risk analysis already exists, such as the well-known FMEA method (FMEA=Failure Mode and Effects Analysis), for example. These methods are primarily applied in the field of product development, but bear no relation to an assessment of economic viability, that is to say the risks are only evaluated qualitatively and not quantitatively as well. [0005] However, it is desirable with regard to the major projects implemented by a company that risk assessments are implemented from the company viewpoint that also evaluate the existing technical project risks in economic terms. In the case of very large projects, in fact, unconsidered risks involving a large amount of economic damage can result in an incorrect balance sheet classification, and in the event of the occurrence of such risks, this can also bring with it the insolvency of the company in certain circumstances. SUMMARY [0006] One possible object of the invention is therefore to create a method for risk analysis in a technical project, which includes not only a qualitative risk evaluation but also the economic evaluation of the risks. [0007] The inventors propose a method that incorporates a risk identification process, in which the following steps are carried out: a) provision or determination of a large number of qualitative evaluations of risks in the technical project; b) determination of a large number of quantitative evaluations of the risks; c) comparison of the qualitative and quantitative evaluations for each risk, as a result of which a comparison outcome is established for each risk; d) definition of a permissible region of comparison outcomes; e) classification of the risks that are situated outside the permissible region as implausible risks; f) analysis of the implausible risks in order to identify uncertainties in the risk analysis and further risks. [0014] The method therefore provides a comparison of qualitative and quantitative evaluations and establishes, by the definition of a permissible region of comparison outcomes, the points in the risk identification at which uncertainties exist in the form of implausible risks. In this respect, the term “region” can comprise one or more continuous blocks of comparison outcomes, but also a discrete set of comparison outcomes. The implausible risks are analyzed again in more detail with the method in order to uncover as yet unrecognized risks and/or uncertainties in the risk evaluation and where relevant extract corresponding consequences for improving the risk analysis. In particular, the knowledge base providing support for the persons involved in the technical project is analyzed in the method, where it is possible to estimate, by way of the identification of implausible risks, whether the knowledge base brought in is suitable for implementing the technical project successfully. With the aid of the method, in particular, all risks and the resultant potential cost of errors can be established and represented transparently in order to bring concrete need for action to bear at the correct point. [0015] In order to make it possible to include the evaluated risks in a business administration balance sheet also, the quantitative evaluations of the risks are, in particular, monetary evaluations in units of money. [0016] For the purposes of an especially vivid comparison of the qualitative and quantitative evaluations, steps c) and d) of the method are implemented in such a way that the comparison outcome for a risk is the position of the qualitative and quantitative evaluation of the risk in a two-dimensional graph, the qualitative evaluation scale being plotted on one axis of the graph and the quantitative evaluation scale on the other axis of the graph. In this case, the permissible region is defined as a delimited region in the two-dimensional graph. [0017] In a further preferred embodiment of the method, each risk is assigned a probability of occurrence and a monetary amount of damage in the event of the occurrence of the risk, the quantitative evaluation of a respective risk being a function of the probability of occurrence multiplied by the monetary amount of damage. A simple and intuitive scheme for evaluating the risk quantitatively is created in this way. [0018] In order to also represent the probabilities of occurrence of the risks transparently in the above-mentioned two-dimensional graph, the risks are, in an especially preferred embodiment of the method, depicted as flat objects at their positions in the two-dimensional graph, the size of a flat object depicting the probability of occurrence of the corresponding risk. [0019] In a further embodiment, one or more of the risks are respectively assigned one or more events, the occurrence of which corresponds to the occurrence of the risk. In this respect, the events can define both causes for the respective risk and consequences of the respective risk. [0020] Any desired risks can be taken into consideration with the aid of the method; preferably, the risks within the project are included, that is to say those risks that relate to the successful implementation of the project. It is also possible, however, for the risks not to be directly connected with the project sequence; for example, the risks can also be warranty risks that arise after the implementation of the project. In this respect, the probability of occurrence of a warranty risk is preferably given by the probability of damage covered by warranty to a technical component with reference to a predefined operating period of the technical component multiplied by the quantity of technical components and the monetary amount of the damage covered by warranty to the technical component. [0021] In an especially preferred embodiment of the method, the qualitative evaluations are intuitive evaluations of the respective risks, the intuitive evaluations being determined by questioning of the persons involved in the technical project. Where relevant, however, it is also possible for the qualitative evaluations to originate at least partly from a technical risk analysis, in particular from the FMEA analysis. [0022] The risk identification process of the method is preferably followed by a risk assessment process. Preferably, in this risk assessment process, the risks are subdivided into evaluation classes as a function of their respective quantitative evaluation, which comprise in particular the classes “tolerable”, “critical”, and “catastrophic”. Where relevant, further classes can also be defined for further detail. For example, the classification can be effected according to a standard, such as e.g. IEC 61508. [0023] The assessed risks are preferably also output on the basis of a two-dimensional graph. In this respect, the quantitative evaluations (QN) of the risks (R) are respectively characterized by a probability of occurrence (P) and a monetary amount of damage (DH) of the risk (R) and the risks are depicted as positions in the graph, the scale for the amount of damage being plotted on one axis of the graph and the scale for the probability of occurrence of the risk on the other axis of the graph. Delimited regions are then defined in the graph, each region corresponding to an evaluation class and the evaluation class of a risk being produced by the delimited region in which the position of the risk is situated in the two-dimensional graph. For the purposes of comparing the quantitative risk evaluations and the qualitative risk evaluations, the risks are preferably depicted as flat objects at their positions in the two-dimensional graph, the size of a flat object corresponding to the qualitative evaluation of the risk. [0024] In a further version of the risk assessment process, the quantitative evaluations of the risks are again respectively characterized by a probability of occurrence and a monetary amount of damage of the risk and the risks are subdivided into accounting groups as a function of their probabilities of occurrence, the risks being treated differently in a company financial balance sheet as a function of the accounting group. By a quantitative evaluation of this type, while making allowance for accounting rules, the method allows the possibility of incorporating the risks for balance sheet purposes according to predefined international standards. For example, allowance can be made for the US-GAAP standard referred to in the introduction. This is accomplished by the fact that risks with a probability of occurrence of more than 80% are included in the balance sheet with their overall monetary amount of damage and risks with a probability of occurrence of 80% or less are inserted in the balance sheet with their quantitative evaluation, that is to say with the product of probability of occurrence and amount of damage. Moreover, risks with a probability of occurrence of less than 50% are preferably added together and reported in the balance sheet as a single item. [0025] The processes of risk identification and risk assessment described above are preferably also followed in the method by an action planning process, with the aid of which the risks are reduced. The quantitative and qualitative evaluations of the risks are then preferably established again following the implementation of the action planning process, the risks before and after the action planning process then being compared with each other. This makes it possible to verify whether the defined action planning process results in an adequate reduction in the risks. In the action planning process, the monetary costs of the planned measures are preferably also estimated and compared with the cumulative quantitative evaluations of the risks before and after the action planning. This makes it possible in particular to establish the cost/benefit effect of the measures, it being possible in the case of excessively high costs of specific action plans to give consideration to implementing other or modified measures for reducing the costs. [0026] In a further embodiment, the quantitative and qualitative evaluations of the risks are assessed according to one of the embodiments of the risk assessment process described in the foregoing following the action planning process. BRIEF DESCRIPTION OF THE DRAWINGS [0027] These and other objects and advantages will become more apparent and more readily appreciated from the following description of the preferred embodiments, taken in conjunction with the accompanying drawings of which: [0028] FIG. 1 A schematic representation of the project phases of a customer project in which the method according to one possible embodiment of the invention can be utilized; [0029] FIG. 2 Two graphs which are generated in accordance with an embodiment of the method and which are used for identifying implausible risks; [0030] FIG. 3 and FIG. 4 Graphs which are generated in accordance with an embodiment of the method and which depict in graphic form the classification of risks before and after an action planning phase; and [0031] FIG. 5 A schematic representation which shows the balance sheet-oriented evaluation of risks in accordance with an embodiment of the method. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT [0032] Reference will now be made in detail to the preferred embodiments, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to like elements throughout. [0033] FIG. 1 shows in schematic form the individual processes in a technical customer project in which a technical system and/or a technical plant is to be developed according to the specifications of a customer. The processes comprise, at the beginning, the project acquisition phase PA, which is followed by the project execution phase PE. Various sub-processes are implemented in the project acquisition phase: in particular, a pre-acquisition process, the actual project acquisition, contractual negotiations and, in the case of successful acquisition, the project handover PH for implementation of the project. The project handover PH is succeeded by the project execution phase which also comprises a large number of sub-processes: in particular, a more detailed project planning process, the purchasing and manufacturing of the components of the technical system, the construction/installation of the components, the commissioning, and also the release to the customer for acceptance of the technical system that has been developed. The project is ultimately brought to a close with the final customer acceptance CA. The actual project is then finished and it is then followed by a further warranty phase W. [0034] The method of risk analysis can be implemented at any point in the project between the project start 0 and the project end E. The method preferably accompanies the overall project from start to end. It is also possible, however, for the risk analysis to also only come into use if a project is in crisis, that is to say if there is a danger that the technical project is failing. In such a case, corresponding unrecognized risks can still be identified and corresponding measures evaluated where relevant with the aid of the method in order to still guide the project to a successful close. [0035] In the foregoing, the utilization of the method has been described on the basis of a customer project. It is also conceivable, however, for the method to be utilized in any desired other types of project. In particular, the risk analysis method can also be used in development projects in which a new product is to be designed, developed, and manufactured for the market independently of a customer. [0036] FIG. 2 shows two graphs D 1 and D 2 which clarify step of the method. In this respect, the graph D 1 shows the outcome of a risk identification with the method where the technical project is supported by a poor knowledge base, that is to say the project is affected by uncertainties and the risks are not always correctly classified by those involved in the project and/or there is not sufficient information available to be able to evaluate the risks correctly. In contrast, D 2 shows a risk identification in a project with a very good knowledge base where the technical project is affected by little uncertainty and the risks are classified correctly by the persons involved in the project. [0037] The method is distinguished by the fact that not only is a qualitative evaluation of the risks performed but also a quantitative evaluation of the risks in the technical project. A comparison of the qualitative and quantitative risks then makes it possible to establish which risks are implausible, these plausible risks being further evaluated and analyzed in a next step in order to identify further risks and/or recognize uncertainties in the project and take counter-measures. [0038] In the embodiment of the method described here, a monetary evaluation in euro is used as the quantitative risk evaluation, which is dependent firstly on the probability of the occurrence of the risk and secondly on the amount of damage in the event of the occurrence of the risk. In FIG. 2 , the quantitative evaluation QN is plotted along the abscissa. In this respect, the quantitative evaluation is the product of the probability of the occurrence of the risk and the amount of damage. This quantitative evaluation QN is set against a qualitative evaluation QL which is plotted on the ordinate in the graphs in FIG. 2 . Any desired types of qualitative evaluation can be used. An intuitive evaluation is preferably utilized as the qualitative evaluation, where the persons involved in the project are questioned with regard to the risks and are to state how they rate a specific risk on a scale. In this respect, a scale from 0 to 6 has been chosen in FIG. 2 , where 0 means no risk and 6 a very high risk. The individual scale values 1 to 6 can also be linked to corresponding textual descriptions. [0039] The individual risks are represented as bubbles in the graphs D 1 and D 2 in FIG. 2 , where the size of a bubble, and in particular the diameter of the bubble, stands for the probability of the risk occurring. By way of example, a bubble is designated as a risk R in FIG. 2 . The risks can be defined as desired in the method. For example, the risks can be defined by way of the causes that result in the corresponding damage, but it is also possible for the risks to be defined as a consequence, that is to say as a corresponding damaging event, independently of the causes. [0040] In place of an intuitive qualitative evaluation of the risk, outcomes from known technical risk analysis methods can also be plotted along the scale QL, for example from the FMEA method (FMEA=Failure Mode and Effects Analysis), which is sufficiently well-known. [0041] In the method, the quantitative evaluations of the risks are set against the qualitative evaluations. In the graph D 1 , which is supported by a poor knowledge base, a large amount of scatter is apparent which means that the quantitative evaluations of a risk frequently do not coincide with the qualitative evaluation of the corresponding risk. In order to identify such implausible risks, a permissible region is defined in the two-dimensional graphs D 1 and D 2 according to the method, where all risks outside this region are classified as implausible. The region is indicated in D 1 and D 2 by an upper boundary line L 1 and a lower boundary line L 2 . In this respect, the graph is scaled in such a way that all risks are situated on the bisector of the angle L 3 in the ideal case. [0042] It can be seen in graph D 1 that the risks R 1 , R 2 , and R 3 situated in the upper region, in particular, are not plausible since they are situated above the boundary line L 1 . These risks are rated as very high intuitively, whereas the quantitative evaluation classifies the risk with a low value. Moreover, these risks exhibit a low amount of damage since the probability of the risks is relatively large and the amount of damage is the quotient of risk and probability. According to the method, it is therefore possible to identify, on the basis of the graph D 1 , the facts that certain risks are not plausible and the knowledge base of the project is affected by uncertainties. As a consequence, workshops and interviews can ultimately be implemented with all those involved in the project, in particular with the persons providing the financing and with the persons responsible for the project planning and implementation, in order to uncover blockages in the evaluation of the project where relevant and/or recognize further risks and possible causes of risks. In this way, the knowledge base of the project can be improved and risks that have not been recognized as yet can already be uncovered in the preliminary stages. [0043] The graph D 2 in FIG. 2 shows a technical project which is supported by a very good knowledge base. This can be seen from the fact that most of the risks are situated within the permissible region between the lines L 1 and L 2 . Nevertheless, further risks can be uncovered even in the case of a good knowledge base, which were not recognized in the known qualitative evaluation techniques of the technical project. In particular, the risks R 4 and R 5 with very small bubbles below the line L 2 are of interest here. These risks are classified as relatively insignificant with the qualitative evaluation. Although the risks exhibit a low probability based on their small bubble diameter, it is now recognized that allowance should definitely be made for the risks. In fact, the risks exhibit a very high amount of damage because the already quite high risk value of R 4 and R 5 is divided, for the purposes of establishing the amount of damage, by the very small probability of the risks, from which a very large number is produced. These risks can therefore result in catastrophic consequences not only for the technical project itself but also for the overall company that is developing the project. In fact, the amount of damage is so high in certain circumstances that it can no longer be borne by the resources of the company and therefore can result in the insolvency of the company. The graph D 2 therefore produces a clear indication of how, by a linking of the quantitative and the qualitative evaluation of risks, risks not recognized as relevant originally nevertheless go into the risk analysis based on the exorbitant amount of damage. [0044] FIG. 3 and FIG. 4 show the outcome of an assessment process of the method which is implemented following the identification of the risks as shown in FIG. 2 . In this assessment process, the individual risks are classified and represented in a corresponding two-dimensional graph. Any desired standardized classification can be utilized as the classification. In the embodiment described here, the classification groups “tolerable” (designated by T), “critical” (designated by CR), and “catastrophic” (designated by CA) are used. In this respect, the classification of the risks is effected in such a way that—in contrast to FIG. 2 —the amount of damage DH is now plotted along the abscissa and the probabilities of occurrence of the risks according to the quantitative evaluation on the ordinate, where the probabilities are subdivided into groups P 1 , P 2 , . . . , P 6 . Each of these groups P 1 -P 6 is assigned a textual description as follows: P 0 =no risk P 1 =improbable risk P 2 =not very probable risk P 3 =occasional risk P 4 =probable risk P 5 =frequent risk P 6 =very high risk [0052] The risks are again represented as bubbles, where the diameter of the bubbles now depicts the qualitative evaluation of the risk. In the graphs in FIGS. 3 and 4 , the individual classification regions T, CR, and CA are defined by different regions in the graph. These regions are respectively separated from each other by lines L 4 and L 5 . In this respect, the lines are stepped delimitations, where each vertical and horizontal section of the line is designated by the corresponding line symbol L 4 or L 5 for the purposes of clear identification of the course of the lines. In this respect, all risks that are situated below the line L 4 are classified as tolerable and all risks that are situated above the line L 5 are evaluated as catastrophic. In contrast, the risks above the line L 4 and below the line L 5 are evaluated as critical. Three classes of risks are therefore produced, which are depicted by different representations of the bubbles in FIG. 3 . All critical risks in the region CR are represented as light bubbles in this respect, all tolerable risks below the line L 4 are represented as dark bubbles, and all catastrophic risks above the line L 5 are depicted as dark, spotted bubbles. In this respect, FIG. 3 shows the representation of the risks before measures have been planned. It can be seen that there are three catastrophic risks above the line L 5 , and corresponding measures are then planned in order to attempt to eliminate these catastrophic risks and also to substantially reduce the quantity of critical risks. [0053] The outcome of such action planning is represented in FIG. 4 . FIG. 4 shows a similar representation to FIG. 3 , but here the risks are depicted after the action planning. In order to enable a comparison with FIG. 3 , the coloring of the bubbles assigned to the risks in FIG. 3 has not been changed so that it can be seen in FIG. 4 how the corresponding risks were classified before the action planning. It can be seen that the action planning delivers success. In particular, two catastrophic risks have been completely eliminated and the third catastrophic risk has migrated into the region CR so that it is now only a critical risk. Moreover, a large number of critical risks have also been eliminated or reduced in such a way that they are now tolerable risks. The risk assessment just described therefore makes it possible to implement a comparison of the risks before and after action planning very effectively and to recognize intuitively and rapidly whether the action planning produced success. [0054] Since the risks are classified quantitatively on the basis of a monetary evaluation scheme in the embodiment of the method described here, an economic evaluation of the risks can be performed in a simple manner. In particular, the risks can be included in the financial balance sheet of a company according to their monetary values in terms of damage. A special advantage relates to in the fact that the risks can be inserted in the balance sheet according to the well-known accounting rules under US-GAAP (United States Generally Accepted Accounting Principles). This is clarified in FIG. 5 . FIG. 5 shows the cumulative value of all monetary quantitative risk evaluations before action planning as column B 1 . The cumulative value of all quantitative risk evaluations after the action planning is represented as column B 2 . Moreover, a column B 3 is depicted, which depicts the costs for the implementation of the measures. It can be seen in FIG. 5 that the action planning results in a reduction in risk which is indicated by the arrow A 1 in FIG. 5 . In particular, original risks of 15 million euro are set against risks of 5 million euro plus action costs of 2.6 million euro. This results in a monetary benefit of (15 million euro−(5 million euro+2.6 million euro))=7.4 million euro. [0055] The risks assessed with the method can be subdivided into the groups G 1 and G 2 as shown in FIG. 5 for recording for balance sheet purposes, where the group G 2 is subdivided again into the sub-groups G 2 . 1 and G 2 . 2 . The step comprising the balance sheet-oriented subdivision of the risks is indicated by the arrow A 2 in FIG. 5 . In the embodiment described here, the accounting rules according to US-GAAP are used. According to these, all risks that exhibit a probability of more than 80% are inserted in the balance sheet with their amount of damage. These risks belong to the group G 1 . All other risks that exhibit a probability of 80% or less are included in the balance sheet with their respective quantitative values, that is to say amount of damage multiplied by probability of occurrence. These risks belong to the group G 2 . The group G 2 is subdivided again into the groups G 2 . 1 and G 2 . 2 . The group G 2 . 1 contains all risks with a probability between 50% and 80%. These risks must all be reported separately in the balance sheet. In contrast, risks with a probability of less than 50% can be inserted in the balance sheet as overall items (so-called “Net Risk Exposure”). As is shown by the foregoing description, not only can an improved identification of risks therefore be achieved with the method but, based on their quantitative evaluation, the risks can also be assessed very effectively in economic terms while making allowance for accounting rules. [0056] A description has been provided with particular reference to preferred embodiments thereof and examples, but it will be understood that variations and modifications can be effected within the spirit and scope of the claims which may include the phrase “at least one of A, B and C” as an alternative expression that means one or more of A, B and C may be used, contrary to the holding in Superguide v. DIRECTV, 358 F3d 870, 69 USPQ2d 1865 (Fed. Cir. 2004).
A method analyzes risks in a technical project for developing or manufacturing a technical system or technical components or a technical process, wherein the following steps are carried out in a risk identification process: a) provision or determination of a large number of qualitative evaluations of risks in the technical project; b) determination of a large number of quantitative evaluations of the risks; c) comparison of the qualitative and quantitative evaluations for each risk, as a result of which a comparison outcome is established for each risk; d) definition of a permissible region of comparison outcomes; e) classification of the risks that are situated outside the permissible region as implausible risks; f) analysis of the implausible risks in order to identify uncertainties in the risk analysis and further risks.
6
BACKGROUND OF THE INVENTION It has been desirable to place on the surface of seats and backrests inflatable devices which will press on the body of the occupant in order to produce a massaging effect and thereby extend the time in which the seat can be used without discomfort to the occupant. In some of these devices, inflatable air cells have been provided on the seat surface and the inflation of the cells has produced a simple pulsating or intermittent surface pressure variation without producing a transitional pressure wave movement. While such movement has some effect in relieving discomfort, it has been long known that directional massage movement is more effective to relieve discomfort. An example of a device which provides a transitional pressure wave movement for a massaging effect on a seat is disclosed in U.S. Pat. No. 3,613,671 to John H. Poor and Charles H. Logan. This patented device utilizes a rotating valve for sequentially inflating a plurality of inflatable air cells which are contained in a plurality of pockets in a fabric seat cover. A backing for the cells rests on the bottom and back seat surfaces to position the device on the seat. Thus, this patented device is entirely separate from the seat and is simply added threto when desired. SUMMARY OF THE INVENTION The present invention provides an inflatable seat unit which is designed to be incorporated as an integral part of the seat structure. The unit is adopted for installation into a pocket in the surface of a large seat or is adapted to cover the entire top surface of a single seat. The unit can comprise foam material on opposite sides of the air cells so that the unit can rest on a solid support and still be comfortable. Also, the material can be on only one side and the air cells can be directly supported by coil springs. A control mechanism is provided to control the sequential inflation of the air cells to produce a translational wave of approximate sinusoidal form along the seat surface where the cells are located. The mechanism comprises a rotating valve which can vary the rate of the wave movement by varying the rotating speed. Also, the pressurized air supply forces the rotor against the stator which contains the air passage so an effective rotary seal is obtained. The tops of all the air cells are covered by a layer portion of plastic foam of a thickness that permits the movement of the cells to be transmitted to the body of the occupant. By providing a seat surface of plastic foam, the appearance and construction of the seat is compatible with most types of seat construction and provides a comfortable seat surface when the unit is not being inflated. Since the construction of the unit is similar in appearance to the remaining seat structure, the fact that a seat incorporates the inflatable unit is not apparent from casual observation of the seat. The complete control mechanism and tubes, as well as the air cells themselves, can be fully contained within the unit so that the only external components are the electrical line for the motor and the air pressure and exhaust lines. Therefore, the present invention provides an inflatable seat unit which can be incorporated as a modification to the seat construction and, in both cases, the unit does not detract from the seat appearance. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an expanded perspective view of a large seat having a cavity for receiving the inflatable seat unit; FIG. 2 is a perspective of a single occupant seat with the inflatable seat unit covering the entire bottom seat surface; FIG. 3 is an elevational view along line 3--3 of FIG. 1 showing one side of the control panel for the seat unit; FIG. 3A is a bottom plan view of the inflatable unit; FIG. 4 is a horizontal section along line 4--4 of FIG. 1 illustrating the cavity in the seat unit containing the air cells and control mechanism; FIG. 5 is a vertical section along line 5--5 of FIG. 4 showing the control mechanism for distributing air to the inflatable cells; FIG. 6 is a transverse vertical section along line 6--6 of FIG. 4 illustrating the air cells in deflated condition; FIG. 7 is a sectional view similar to FIG. 6 showing several of the air cells inflated to raise the top foam surface portion. FIG. 8 is a vertical section along line 8--8 of FIG. 7 illustrating the dual tube construction of each of the air cells; FIG. 9 is a vertical section of a modified seat unit incorporated into a seat structure utilizing coil springs; FIG. 10 is a perspective view of the base board to which the individual inflatable cells are attached, showing the openings for the ischial tuberosities of the occupant. FIG. 11 is an expanded perspective of the control mechanism showing the drive motor, the valve rotor and the valve stator for distributing air pressure to the air cells. FIG. 12 is an expanded perspective showing the relationship between the valve opening in the rotor and the air passages in the stator for a seven cell unit; FIGS. 13a, 13b and 13c show progressive positions of the valve opening relative to the air passages. FIG. 14 is an expanded perspective of a modified valve rotor and stator for an inflatable seat unit having ten individual air cells. FIG. 15 is an expanded perspective of the device of FIG. 14 showing the passages in the stator for the 10 cell unit. FIGS. 16a, 16b and 16c show progressive positions of the rotor valve opening with respect to the passages in the stator of FIG. 15. FIG. 17a is a plan view of the seat of FIG. 2 utilizing a single 7-cell unit with one control mechanism. FIG. 17b is a plan view of a modified seat utilizing a single 10-cell unit and one control mechanism. FIG. 17c is a plan view of another modified seat utilizing one 10-cell unit and one 7-cell unit, each with a separate control mechanism, and, FIG. 17d is another modification of a seat utilizing two 10-cell units with separate control mechanisms. DESCRIPTION OF THE PREFERRED EMBODIMENT Referring to FIG. 1, the inflatable seat unit 18 is shown in position for insertion into cavity 23 in a large foam rubber seat 20 for multiple occupants. The unit 18 comprises a top foam layer 21 and a bottom foam layer 22 which contains a cavity 23, and the layers are cemented together along the dividing line 24. The bottom layer 22 (FIG. 3A) contains opening 25 for electrical line 26, opening 27 for pressurized air line 28, and opening 29 for exhaust air line 30. Cavity 23 of seat 20 contains openings 25', 27' and 29' for the lines leaving openings 25, 27 and 29, respectively, so that the lines can reach to the exterior of the seat 22. Referring to FIG. 4, cavity 23 in foam layer 22 has straight side walls 37 and 38, a front wall 39, and a bottom surface 36. Back sidewall 40 is a side of a foam extension 41 which forms a cavity 42 terminating with wall 43. Cavity 42 contains control mechanism 44 comprising motor 45, gear reduction box 46, valve rotor housing 47, and stator 48. The complete control mechanism is cemented to the surfaces of cavity 42. Motor 45 can be air driven or a twelve volt DC motor driving a gear reduction 46 of standard construction which has a flat rectangular drive end 50. Rotor housing 47 is secured to the end of the gear reduction train by means of a plurality of screws 53, and the housing has a central opening 54 for receiving output member 50. A sleeve 55 extends from the opening 54 and contains a cross-member 56 having an opening for the drive end 50. The sleeve 55 also receives an enlargement or mounting projection 60 on flat surface 61a of valve rotor 61 and the enlargement has a slot opening 62 which receives the drive end 50. Valve rotor 61 has a circumferential rim 63 across which extends a projecting wall 64 to form an exhaust space 65 and define a valve opening 66 through the valve. The wall 64 projects outwardly from the flat valve surface 61a by the same amount as rim 63. The rotor housing 47 has an extension pipe 67 which connects with high pressure air line 28 and introduces pressurized air into chamber 68 in the rotor housing which is in continual communication with valve opening 66. Rotor housing 47 receives reduced end 48a of valve stator 48 and the stator has a small projection 69 (see FIG. 11) which enters into an edge groove 69a in housing 47 in order to properly locate stator 48 with respect to the housing 47. The stator 48 contains seven passages 70a-70g equally spaced around the circumference and extending completely through the stator. The ends of plastic air tubes 71a-71g are secured into the passages 70a-70g, respectively. Also, the housing 48 has a central passage 72 into which is secured the end of exhaust tube 73 which connects to the exterior of the unit through line 30. Exhaust air leaving the passages 70a-70g enter valve space 65 and leaves through passages 72 and 73. As illustrated, the end of rim 63 and of wall 64 engage the end of stator 48a so that the pressure in chamber 68 will seal the rotor 61 against the stator. The air tubes 71a-71g pass along the side wall 37 of cavity 23 and connect with individual air cells 75a-75g. Each of the air cells 75a-75g comprise double overlapping tubes 76 and 77 (see FIG. 8) which are sealed together at end 78. The opposite end 80 of each cell has an opening receiving an angular fitting 81 which connects the interior of the overlapping tubes to one of the tubes 71a-71g. The overlapping tube 76 comprises layers 82 and 83 and overlapping tube 77 comprises layers 84 and 85. The layers 83 and 84 stop short of the fitting 81 to permit air to enter both of the overlapping tubes 76 and 77, and inflate the air cell. A thin plastic board 86 (approx. 1/16" thick) is positioned on bottom surface 36 of cavity 23 and the cells are secured to the backing board by a strap 87 which loosely passes over each cell and is secured to the board between each cell. As illustrated in FIG. 4, the tubes 71a-71g pass along the wall 37 of cavity 36 in order to connect the individual inflatable cells 75a-75g to the stator 48 of the control mechanism 44. Both the tubes 71a-71g and air cells 75a-75g are constructed to flexible material, such as rubber or plastic. Each of the cells 75a-75g in the non-inflated condition lie flat against a backing board 86 and the loops 87 are loose enough to permit the individual cells to rise above the backing 86 when inflated, as illustrated in FIG. 8. In FIG. 7, three adjacent cells 75a, 75b, and 75c are shown at least partially inflated and the remainder of the cells 75d-75g are shown uninflated. As illustrated, the backing board 86 causes the cells to rise above the board without depressing the board 86 into the bottom cavity surface 36. As illustrated in FIGS. 4 and 10, the backing board 86 contains two openings 88 and 89 which are located opposite the ischial tuberosities of the seat occupant for comfort. The control mechanism 44 is cemented or otherwise secured to the side wall 43 and bottom surface 36 in order to be rigidly held in the seat unit 18. A portion of layer 21 covers all the air cells and another portion covers the control mechanism and all air tubes after layer 21 is sealed to the bottom foam layer 22. The inflatable unit 18 can be constructed of any flexible foam material and the top foam layer 21 can be of a thickness (preferably one-half to one inch) which will transmit the rise and fall of the air cells firmly to the occupant so that the occupant can be massaged by the translational wave motion created by the air cells in a manner to be described. Also, the layer 21 will be thick enough to comfortably support the seat occupant when none of the cells are inflated. As an example, the top layer can be fabricated of a foam having a density of about 2.6 lbs./cu. ft. and the lower layer fabricated of a foam which a density of about 3.9 lbs./cu. ft. The lower layer can be more dense to provide a firm base for the inflatable action. Examples of suitable foam materials are polyether and polyurethane. It is apparent that as the valve rotor 61 is rotated by motor 45, the valve opening 66 will open successive air passages 70a-70g and will inflate the air cells sequentially. As illustrated in FIG. 7, the cells 75a and 75b are fully inflated and cell 75c is being inflated. This inflation causes a portion of top foam layer 21 to rise and push against the seat occupant to massage the occupant. Position A of the valve opening at this time is illustrated in FIGS. 11, 12 and 13a. In FIG. 13a, opening 66 is rotating in the direction of arrow 90 and the forward end of opening 66 is commencing to uncover opening 70c. The remaining openings 70d-70g are all connected to exhausts through tubes 71d-70g, exhaust space 65, exhaust space 72 and exhaust tube 73. The length of opening 66 is such as to open a maximum of 2.6 passages. Further rotation of the valve rotor to Position B in FIG. 13b causes passages 70a, 70b and 70c to have a maximum of 2.6 passages open, passages 70a and 70c each having 0.2 of their area closed. Further rotation to position C of FIG. 13c starts the closing of passages 70a and the deflation of cell 75a. Further rotation to the dashed line position D of FIG. 13c causes passage 70a to close and passage 70b and 70c are fully open, with passage 70d the next to start opening. The various positions of the top foam layer 21 are roughly indicated in FIG. 7 without the pressure of an occupant and each position line is labeled with the corresponding valve position in FIGS. 13a-13c. It is apparent that as the valve rotor moves, an approximate sinusoidal wave form will travel across the unit 18 by inflation and deflation of the various air cells. The control mechanism 44 is controlled by a switch 92 on panel 93 (see FIG. 3) and the switch is connected to a 12V d.c. source through lead 92a and fuse 94. The switch controls motor 45 through leads 26a and also controls solenoid valve 95 through additional leads (not shown). As source of air pressure is connected by passage 96 to a pressure regulator 97 mounted on panel 93 and the regulator is connected through solenoid valve 95 to passage 28 leading to the valve housing 47. When the switch 92 is turned on, the solenoid valve 95 opens to introduce pressurized air to the valve rotor and also the motor 45 starts to rotate the valve. As long as the switch 92 is on, the translational wave will move across the seat unit. The control panel can be located on the instrument panel of a vehicle or attached to the seat (see FIG. 2) or located in any other convenient place. It is preferable that the reduction gearing 46 drive the valve rotor at about 17 rpm but the speed can be reduced to approximately 7 rpm without destroying the massage effect. Below 7 rpm the occupant will feel the separate pulses developed by each air cell. At 23 rpm and above, the occupant will feel a rapid sensation with less massage effect. The speed of the motor 45 can be varied by the occupant by adjusting a potentiometer (not shown) in the motor circuit. Also, by suitable connections (not shown), the direction of rotation of the motor 45 can be changed. As illustrated in FIG. 2, the seat unit 18 can be cut to the shape of a single seat 98 so that it can rest upon a support surface of the seat structure. Another modification 18' of the seat unit is illustrated in FIG. 9 wherein backing board 86' extends along the bottom of layer 21' to the outside edges thereof in order to form the cavity 23' in the layer 21'. The individual inflated air cells 75a-75g are located in the cavity 23' and are supported by the back plate 86'. Also, the control mechanism 44' is located in cavity 42' of layer 21' and the air tubes 71a-71g are also located at one side of cavity 23'. The unit 18' is constructed to be incorporated in a seat structure which utilizes metal coil springs 100 supported on a base plate 101. The backing plate 86' can rest firmly on the top of coil springs to support the seat unit over any given section of the seat. In FIGS. 14 and 15, a modified valve rotor 61' for a 10 cell seat inflating unit is shown and the unit can be constructed similar to unit 18 or unit 18', with the addition of two air cells. The stator 48' contains ten air passages 102a-102j, and the valve rotor 61' contains a valve opening 66' which is large enough to open a maximum of 2.6 passages (see FIG. 16a). The rotor 61' has an opening 62' for receiving the drive end 50 of the motor 45. As illustrated in FIG. 16a-16c, the valve opening 66' controls the passages 102a-102j in a similar manner as the seven passages 70a-70g are controlled by the opening 66. In position B' of FIG. 16a, opening 66' opens 2.6 openings 102f-102h similar to Position B of FIG. 13b. In the position C' of FIG. 16b, opening 66' is closing passage 102f similar to Position C of FIG. 13c. In position D' of FIG. 16c, opening 66' opens only passages 102g and 102h similar to Position D of FIG. 13c. Thus, the same type of approximate sinusoidal translational movement can be obtained from seven or ten air cells. Various seat configurations using one or both of the seven and ten cell units are illustrated in FIGS. 17a-17d. In FIG. 17a, a seven cell unit (cells 1-1 to 1-7) is used in the bottom of the seat while in FIG. 17b, a ten cell unit has seven cells (1-1 to 1-7) on the bottom and three cells (1-8 to 1-10) at the lower back. In FIG. 17c, a ten cell unit has the cells located as in FIG. 17b and a separate seven cell unit has been added to the back to provide cells 2-11 to 2-17. FIG. 17d provides a seat with two 10 cell units, the first providing cells 1-1 to 1-10 on the bottom and back of seat, and the second providing the smaller cell 2-11 to 2-20 on the seat back. Separate valves and motors are used when two separate units are combined in the same seat. It is understood that the individual units of FIGS. 17a-17d can be constructed as described in connection with units 18 and 18'. Various other modifications of inflatable units are contemplated in different seat arrangements. Also, various valves can be used to control the cell inflation. However, a novel control mechanism is provided having a valve in which the rotor is continuously driven and receives air pressure at a location to hold the rotor against the face of the stator so that air leakage is held to a minimum. Also the same rotor is utilized to exhaust the cells through a much enlarged exhaust passage in the stator. The small size of the control mechanizm permits it to be securely mounted inside the seat unit by cement or other attachment without interfering with seat comfort.
An inflatable seat unit having a plurality of air cells positioned longitudinally adjacent to each other and fully contained within a cavity in a piece of foam material, the cells being covered by a portion of the foam material to form a seat surface, the portion having a thickness which permits the rise and fall of the air cells to be felt by the occupant of the seat, a back plate for supporting the cells and causing the cells to rise in the direction of the portion of foam material, and a control mechanism for admitting air into the air cells in a controlled manner and fully contained within said piece of foam material and rigidly secured thereto, said control mechanism having a rotating valve which is forced against the valve openings by pressurized air introduced to one side of the valve during rotation.
0
FIELD OF TECHNOLOGY [0001] This invention relates to lock spindles divided into two parts and interconnected by a connecting pin. The invention also relates to locks with a divided spindle. The invention particularly relates to solenoid lock types and corresponding mechanical lock types. PRIOR ART [0002] FIG. 1 illustrates a prior art divided spindle composed of two spindle parts 4 , 5 and a connecting pin 6 interconnecting these. In the embodiment of FIG. 1 , the connecting pin is a one-piece bolt that is screwed into a hole in one of the spindle parts 4 by bolt threads so that the driving end 15 of the bolt 6 remains within an extension of the hole going through the other spindle part 5 . The driving end 15 can be turned through the hole in the spindle part 5 by an Allen wrench, for example, depending on the type of tool for which the driving end is machined. The spindle parts 4 , 5 of the divided spindle can rotate independently of each other. [0003] A handle of the desired type can be attached to each of the spindle parts. In the example in FIG. 1 , the spindle parts 5 , 4 are fitted with lever handles 3 , 2 . The lock cover plates are not shown in FIG. 1 . In some embodiments the handles are not attached to the spindle but to the lock cover plates using bearings and a locking ring, for example. [0004] In the embodiment of FIG. 1 , a solenoid lock (or a corresponding mechanical type of lock) is fitted to the door 1 , and the divided spindle is installed into this. Only the parts of the lock necessary for this description are illustrated. The lock body 8 is fitted with a follower 9 and drivers 10 , 11 for both spindle parts 5 , 4 . When the handle 3 is turned to open the door 1 , the spindle part 5 turns, simultaneously turning the driver 10 specific to the spindle part. The driver 10 transfers the torsional force applied to the spindle to the follower 9 , which is linked to the lock bolt and opens the lock. Correspondingly, when the handle 2 is turned to open the door 1 from the opposite side of the door, the spindle part 4 turns, simultaneously turning the driver 11 specific to the spindle part. The driver transfers the torsional force to the follower 9 . [0005] Furthermore, there is a separate washer 7 between the spindle parts 5 and 4 . A separate washer is not required in some embodiments, as the follower 9 is fitted with a sleeve ring that settles into the gap between the spindle parts. [0006] In FIG. 1 , the handle 3 and spindle part 5 are inside the door, on the so-called exit side. This means that the door can always be opened using handle 3 as necessary. This example does not account for any deadlocking arrangement. In other words, there is always a link from the spindle part 5 through the driver 10 to the follower 9 . [0007] The handle 2 and spindle part 4 are outside the door, on the so-called control side. This means that the transmission of torsional force applied to the handle 2 and spindle part 4 to the follower of the lock can be prevented. In this case, the handle 2 makes a dead turn, and the door can only be opened if the lock is opened by a mechanical key, for example. The transmission of torsional force is prevented on the control side using a solenoid, which results in the door becoming locked. [0008] The problem with the embodiment of FIG. 1 lies in the fact that a locked door can nevertheless be opened from the outside if a sufficient force affecting the spindle is applied to the handle 2 and the spindle part 4 , particularly in the longitudinal direction of the spindle, while the handle is turned. The force 12 can be either a pushing force, a pulling force, or a lateral force. [0009] For example, if the handle 2 is pushed with force, the spindle part 4 moves towards the inner side of the door, simultaneously pushing the driver 11 towards the follower 9 . Sufficient friction surfaces 13 are formed at the contact surfaces between the follower 9 and the driver 11 , which creates a link from the handle 2 to the follower 9 . Simultaneous forceful pushing and turning of the handle causes unwanted opening of the lock. [0010] If the handle 2 is pulled with force, a friction surface 14 is formed between the inside spindle part 5 and the driving end 15 of the bolt. Due to the strong pulling force, the friction surface is sufficient to transfer the torque of simultaneous turning force on the handle 2 through the inside spindle part 5 to the driver 10 and the follower 9 . Simultaneous strong pulling and turning force on the handle 2 causes unwanted opening of the lock through its inside driver 10 . [0011] It is also possible that in certain types of locks and/or handles, a force applied on the spindle that contains a lateral component will result in either of the cases of unwanted opening of the lock described in the above. [0012] The objective of the invention is to eliminate the described problem. The objective will be achieved as presented in the claims. SHORT DESCRIPTION OF INVENTION [0013] The invention eliminates the effect of an external force applied to a divided spindle on the opposite-side spindle and other parts of the lock. The divided spindle comprises a connecting pin that is round in cross-section, an inside spindle and an outside spindle. The connecting pin is mountable to the spindles so that the spindles rotate in relation to the connecting pin. The attachments between the connecting pin and the spindles are arranged so that a force imposed on the inside or outside spindle in the direction of the spindle shaft and simultaneous turning will not create a sufficient transmission connection to the connecting pin and the opposite shaft. [0014] There are grooves close to the ends of the connecting pin, going around the outer surface of the connecting pin. The spindle parts have bores for the connecting pin and mounting holes for fitting cotter pins. When the connecting pin is in the bore within the spindle part, the cotter pin can be fitted into the transverse groove close to the end of the connecting pin, thus connecting the spindle part and the cotter pin together in a rotating fashion. This prevents the creation of a sufficiently large frictional force caused by pushing or lateral pulling/pushing as sufficient friction will not develop between the cotter pin and the connecting pin due to rotation and the relatively small surface area. LIST OF FIGURES [0015] In the following, the invention is described in more detail by reference to the enclosed drawings, where [0016] FIG. 1 illustrates an example of a prior art divided spindle, [0017] FIG. 2 illustrates an example of a divided spindle according to the invention with the parts separated, and [0018] FIG. 3 illustrates an example of a divided spindle according to the invention when assembled. DESCRIPTION OF THE INVENTION [0019] FIG. 2 illustrates an example of a divided spindle according to the invention with the parts separated. The divided spindle comprises a first spindle part 21 , a second spindle part 22 and a connecting pin 23 connecting the spindle parts. Both spindle parts comprise a bore 27 , 28 for the connecting pin 23 . The connecting pin 23 is round in cross-section, and there are grooves 31 , 32 close to both of its ends in transverse direction to the shaft of the connecting pin, going around the surface of the pin. Both spindle parts 21 , 22 have a mounting hole 29 , 30 transverse to the spindle shaft, touching the bore 28 , 27 for the connecting pin. [0020] The divided spindle also comprises cotters 24 , 25 specific to each spindle part that can be fitted to the mounting holes 29 , 30 . The cotters can be used to connect the spindle parts to the connecting pin in a rotating fashion when the connecting pin is fitted to the bores 28 , 27 in the spindle parts and the cotters are fitted to the mounting holes 29 , 30 so that the cotter specific to the spindle part settles into the transverse groove close to the end of the connecting pin. FIG. 3 illustrates an example in which the divided spindle is assembled. [0021] In order to make it possible to install the spindle into the lock body without separate tools, it is recommended that at least one of the cotters 25 comprises an installation rod 33 transverse to the shaft of the cotter, and that at least one of the spindle parts 21 , 22 comprises a groove 34 on its surface that is connected to the mounting hole 30 . The installation rod of the cotter is mountable to the groove 34 on the surface of the spindle part so that the cotter 25 is in the spindle part's mounting hole. The groove 24 on the surface of the spindle part can be oblique or parallel to the shaft of the spindle part. [0022] The cross-section of the cotter 24 , 25 is preferably round. A round shape is preferable in terms of manufacturing and the shape of the mounting hole 29 , 30 . The round shape is also preferable in order to minimise the friction between the cotter 24 , and the transverse groove in the connecting pin 23 and to simultaneously promote rotation of the spindle part in relation to the connecting pin 23 with the lowest possible friction. An embodiment of the invention can naturally also be implemented with cotters having some other cross-sections. [0023] The connecting pin 23 can be symmetrical in the longitudinal direction in relation to its midpoint. In this case, the bores 28 , 27 in the spindle parts have equal diameters and the connecting pin is mountable either way in relation to the spindle parts. The connecting pin can also be asymmetrical, for example so that one end of the connecting pin is thicker than the other. In this case, the diameter of the bore in the spindle part also differs from the diameter of the bore in the other spindle part. FIGS. 2 and 3 illustrate such a connecting pin. [0024] At least one of the spindle parts 21 , 22 may comprise a third bore 26 for attaching a handle. The bore makes it possible to attach a handle to the spindle part of the divided spindle either directly to the spindle using a screw or to the lock cover plate using bearings and a locking ring, for example. [0025] The cross-section of the transverse groove 31 , 32 in the connecting pin can be a rectangle or a segment, for example. The ends of the connecting pin 23 can also be bevelled as illustrated in the embodiments of FIGS. 2 and 3 . It is also possible that at least one of the ends of the spindle part 21 , 22 is bevelled. [0026] The divided spindle of FIGS. 2 and 3 can be installed in a door either way round. For example, the first spindle part 21 can serve as the inside spindle, while the second spindle part 22 serves as the outside spindle. When one of the cotters 25 has an installation rod 33 , the installer does not need any separate tools to fit the cotter into the mounting hole 30 . In accordance with the example of FIGS. 2 and 3 , the assembled inside spindle 21 can be pushed through the spindle hole in the lock, after which the outside spindle part 22 can be pushed to the connecting pin and the cotter 25 can be pressed into place using the installation rod 33 . The outside handle locks the installation rod to the groove 34 on the surface of the outside spindle. If necessary, both of the cotters in the divided spindle can be fitted with installation rods. A divided spindle delivered with an installation rod is easy to install. [0027] A divided spindle according to the invention is mountable in a solenoid lock or a mechanical lock implementing a corresponding function as illustrated in FIG. 1 . If a force 12 particularly in the longitudinal direction of the spindle is applied to the outside spindle part 22 , the rotation between the connecting pin and the spindle part, as well as the small contact area, prevent unwanted transmission of force to the follower 9 . The described examples also account for unwanted transmission of force to the follower due to a lateral force being applied to the spindle part. [0028] It is preferred that the divided spindle according to the invention be constructed so that when an attempt is made to open the lock by force, the handle will break first, followed by the spindle and finally the lock. [0029] The spindle structure according to the invention can be used to achieve a durable structure that is easy to manufacture. The structure is strong and secure against break-in, fulfilling the requirements of several burglary and vandalism tests. [0030] It is evident from the examples presented above that an embodiment of the invention can be created using a variety of different solutions. It is also evident that the invention is not limited to the examples mentioned in this text but can be implemented in many other different embodiments within the scope of the inventive idea.
This invention relates to lock spindles divided into two parts and interconnected by a connecting pin. The invention particularly relates to solenoid locks. The invention eliminates the effect of an external force applied to a divided spindle on the opposite-side spindle and other parts of the lock. The divided spindle comprises a connecting pin that is round in cross-section, a first spindle and a second spindle. The connecting pin can be connected to the spindle parts so that the spindle parts rotate in relation to the connecting pin.
8
CROSS REFERENCE TO RELATED APPLICATIONS This is a National Phase Application in the United States of International Patent Application PCT/EP2010/057255 filed May 26, 2010, which claims priority on European Patent Application No. 09162638.2 of Jun. 12, 2009, the entire disclosures of the above patent applications are hereby incorporated by reference. FIELD OF THE INVENTION The present invention concerns a method of fabricating a metallic microstructure by LIGA type technology. In particular, the invention concerns a method of this type for fabricating a microstructure having more precise and better controlled dimensional features than the methods of the prior art. The invention also concerns a metallic part of this type obtained via this method. BACKGROUND OF THE INVENTION LIGA (Lithographie Galvanik Abformung) technology, developed in the 1980s by W. Ehrfeld of the Karlsruhe Nuclear Research Centre, Germany, has proved advantageous for the fabrication of high precision metallic microstructures. The principle of the LIGA technique consists in depositing, on a conductive substrate or substrate coated with a conductive layer, a layer of photosensitive resin; in performing X-irradiation through a mask matching the contour of the desired microstructure, by means of a synchrotron; in developing, i.e. removing by physical or chemical means, the non-irradiated portions of the photosensitive resin layer, so as to define a mould having the contour of the microstructure; in the galvanic deposition of a metal, typically nickel, in the photosensitive resin mould and then removing the mould to release the microstructure. The quality of the microstructures obtained is beyond reproach, but the requirement to implement an expensive piece of equipment (the synchrotron) makes this technique incompatible with the mass production of microstructures that have a low unit cost. This is why similar methods, based on the LIGA method but using UV photosensitive resins, have been developed. A method of this type is described, for example, in the publication by A. B. Frazier et al. entitled “Metallic Microstructures Fabricated Using Photosensitive Polyimide Electroplating Molds”, Journal of Microelectromechanical systems, Vol. 2, N deg. 2, June 1993 for fabricating metallic structures by electroplating metal in photosensitive polyimide based moulds. This method includes the following steps: creating a sacrificial metallic layer and a seed layer for a subsequent electroplating step; applying a photosensitive polyimide resin layer; exposing the polyimide resin layer to UV radiation through a mask matching the contour of the desired microstructure; developing, by dissolving, the non-irradiated parts of the polyimide layer so as to obtain a plurality of polyimide moulds; galvanic deposition of nickel in the open parts of the moulds up to the height of said moulds; separating the metallic structures obtained from the substrate; and removing the polyimide moulds to release the electroformed metallic parts. The electroformed microstructures or parts are thus obtained in bulk. Once obtained, these parts are separated and have to be bonded back to a plate in order to be machined and/or ground to the desired thickness and surface state. These steps require lengthy handling time and include significant risks of the parts being arranged the wrong way on said plate, in particular when the electroformed parts have small dimensions, typically parts with dimensions of less than a millimeter. These methods involve a scrap rate and thus production costs which are incompatible with the requirements of an industrial method. Moreover, the methods of the prior art require a deposition of electroformed material that is sufficiently large to ensure that all of the parts attain their minimum thickness regardless of variations in thickness of the resin at the substrate surface. This thus leads to a waste of electroplated material. Indeed, the thickness variations in the resin deposited to form the moulds are intrinsic to current deposition methods, typically spin or spray coating. It will be noted in this regard that the non-uniformity of the resin layer in which the moulds are formed means that the resin has to be irradiated with a setting that takes account of the maximum and minimum thickness. This leads to an increase in the dispersion of geometric dimensions in the plane of the moulds. There therefore exists a requirement for a method that overcomes these drawbacks. SUMMARY OF THE INVENTION It is an object of the present invention to overcome the aforementioned drawbacks, in addition to others, by providing a method for fabricating parts or microstructures having a better controlled and more precise thickness and surface state than the parts or microstructures obtained by the methods of the prior art. The invention also concerns a method of this type that reduces electroforming costs, both from the point of view of fabrication time and the quantity of electroplated material. It is also an object of the invention to improve the uniformity of photolithographic exposure and thus to improve the geometric uniformity of the parts produced on the surface of the same substrate. It is another object of the present invention to provide a method of this type which is simple and inexpensive to implement. The invention therefore concerns a method of fabricating a plurality of metallic parts or microstructures, characterized in that it includes the steps consisting in: a) taking a conductive substrate or an insulating substrate coated with a conductive seed layer; b) applying a layer of photosensitive resin over the conductive part of the substrate surface; c) flattening or levelling the surface of the photosensitive resin layer to the desired thickness and/or surface state; d) irradiating the resin layer through a mask defining the contour of the desired microstructure; e) dissolving the non-polymerised areas of the photosensitive resin layer to reveal, in places, the conductive surface of the substrate or the substrate if the latter is conductive; f) the galvanic deposition of at least one layer of metal from said conductive layer, to form units that substantially reach the upper surface of the photosensitive resin; g) flattening or levelling the resin and the electroformed metal to bring the resin and the electroformed units to the same level and thereby form electroformed parts or microstructures; h) separating the resin layer and the electroformed parts from the substrate; and i) removing the layer of photosensitive resin from the parts or microstructures obtained at the end of step h) to release the parts or microstructures thereby formed. This method thus enables a resin layer of determined constant thickness to be obtained over the entire surface of the substrate. This therefore exhibits a resin layer having a uniform thickness, which enables moulds, and then finished parts, to be made with uniform dimensional precision in the plane for the parts of the same substrate. Typically, the method of the invention ensures a precision of +/−2 μm for the deposited resin thickness, whereas the methods of the prior art are limited to a precision on the order of +/−30 μm (spin coating). Moreover, flattening or levelling the resin before the step of electroforming the parts not only limits the quantity of metal required to be plated to obtain bridges at an earlier stage between the parts, as will be explained hereinafter (saving time), but also provides a wafer, i.e. a set of electroformed parts connected to each other by bridges of material, of much more regular thickness on the upper side, to ensure more regular bonding onto the work plate for subsequent machining operations. In the case of a multi-level LIGA method, flattening the resin means that close tolerance is obtained on the thickness of the different levels over the entire substrate, and thus over all the parts of the substrate. According to a feature of the invention, the flattening step c) is achieved using a cutting tool and preferably via a tool including a cutting edge portion made of hard metal, ceramic, metal carbide, metallic nitride or diamond. The use of such a tool to perform the flattening step prevents any contamination of the resin and/or the electroformed metal by residues which could result from the grinding or polishing processes. Further, machining that uses a cutting tool is not sensitive to the differences in thickness in the material to be machined (resin or resin and electroformed parts or parts bonded onto a work plate). According to an advantageous variant of the invention, during step f), the metal is deposited beyond the height of the mould to extend onto the flattened surface of the resin and thus connect the parts to each other by metallic bridges, to form a wafer, step g) is omitted and after step h), the metallic parts connected to each other by said bridges are subject to the following steps: j) the parts are fixed to a work plate by the reference face thereof opposite the bridges; k) the exposed faces thereof are machined to the desired thickness and/or surface state, removing the bridges, and thereby releasing said parts from each other; l) said finished parts are released from the work plate. According to this first variant, the metallic bridges between the parts: 1. Enable the parts to be transferred onto the work plate for the thickness adjustment; 2. Ensure that the parts are regularly pressed onto the work plate when fixed thereto, which reduces the dispersion of the finished thickness dimension; 3. Ensure that the parts are arranged precisely and regularly for any subsequent additional machining operation (electro-erosion, swarf removal machining, diamond grinding, polishing, decorations, etc.). In other words, an excess growth of metal is formed during the LIGA deposition to create bridges between all of the parts and thus to enable the wafer to be handled, which preserves the very regular and precise localisation of the parts obtained by the LIGA method. This wafer may then be secured to a work plate. The parts can thus be mechanically machined on a CNC machine taking advantage of the precise positioning of the parts (markings may be electroformed straight onto the wafer). The method according to the invention advantageously maintains the precise and regular arrangement of the parts after removal of the bridges of electroformed material, so as to form multi-level parts by machining, to form decorations, to form coatings (selective or complete), to form chamfers or spot facing, batch assembly etc., by means of numerically controlled machines, or robots, for commercial production. According to a second variant, step g) is omitted and after separation step h), the electroformed parts are no longer connected to each other, and the parts are subject to the following steps: m) a transfer strip is applied to the opposite face to the reference face of said parts; n) said parts are fixed to a work plate via the reference face thereof opposite the strip; o) the exposed faces are machined to give said parts the desired thickness and/or surface state; p) said finished parts are released from the work plate. According to a third variant, after separation step h), the electroformed parts are not connected to each other by metallic bridges, but by the resin. These parts are then subject to the following steps: q) the parts are fixed to the work plate by the reference face thereof; r) the exposed faces are machined to give said parts the desired thickness and/or surface state; s) said finished parts are released from the work plate. According to an advantageous feature of the invention, prior to step k), while still fixed to the work plate, the parts are subject to a step of machining into the thickness thereof. Steps k), o), r) described hereinbefore may of course be performed by cutting tools. The method of the invention finds a particularly advantageous application in the fabrication of micromechanical parts for timepiece movements or tools. In particular, the parts could be selected from among the group comprising toothed wheels, escape wheels, pallets, pivoted parts, jumper springs, balance springs and passive parts, cams, push-buttons, collets, moulds, spindles, stakes, and electrodes for electro-erosion. BRIEF DESCRIPTION OF THE DRAWINGS Other features and advantages of the present invention will appear more clearly from the following detailed description of one embodiment of a method according to the invention, this example being given solely by way of non-limiting illustration with reference to the annexed drawing, in which: FIGS. 1 a to 1 h illustrate the method steps of a first embodiment of the invention for making a plurality of toothed wheels; FIGS. 2 a to 2 k illustrate a first variant of the invention; FIGS. 3 a to 3 k illustrate a second variant of the invention; FIGS. 4 a to 4 j illustrate a third variant of the invention. DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS A first embodiment will be described with reference to FIGS. 1 a to 1 h. Substrate 1 used in step a) of the method of the invention is, for example, formed by a silicon, glass or ceramic wafer, on which a seed layer, i.e. a layer able to start an electroforming reaction, has been deposited by evaporation. Typically, the seed layer is formed of a sub-layer of chromium 2 and a gold layer 3 ( FIG. 1 a ). Alternatively, the substrate may be made of stainless steel or another metal able to start an electroforming reaction. In such case, seed layer 2 , 3 is no longer necessary. In the case of a stainless steel substrate, the substrate will be cleaned before used. Photosensitive resin 4 used in step b) of the method according to the invention is preferably an octofunctional epoxy-based resin available from Shell Chemical under the reference SU-8 and a photoinitiator selected from amongst triarylsulfonium salts such as those described in U.S. Pat. No. 4,058,401. This resin is capable of being polymerized by the action of UV radiation. It will be noted that a solvent which has proved suitable for this resin is gamma butyrolactone (GBL) ( FIG. 1 b ). Alternatively, a phenol-formaldehyde novolac-based resin in the presence of a DNQ (Diazonaphotoquinone) photoinitiator may also be used. Resin 4 is deposited on substrate 1 by any suitable means, typically using a spin coater, to the desired thickness. Typically, the resin thickness is comprised between 150 μm and 1 mm. Depending upon the desired thickness and the deposition technique used, resin 4 may be deposited one or several times. Alternatively, resin 4 may be deposited by spray coating. Resin 4 is then heated to between 80 and 95° for a duration dependent on the deposited thickness, in order to eliminate the solvent. The heating dries and hardens the resin. In step c), the substrate is mounted on the work holder of a machine tool, on which the surface of the hardened photosensitive resin layer is flattened to the desired thickness and/or surface state ( FIG. 1 c ). This flattening operation is achieved by means of a cutting tool 5 , to prevent any contamination of the resin by any residue which could cause flattening by a conventional abrasion tool. It will be noted that this flattening operation is preferably achieved dry, i.e. without any lubrication to prevent any chemical pollution of the resin. Typically, the cutting tool is a tool comprising a hard metal, ceramic, metallic carbide, metallic nitride or diamond cutting edge portion. At the end of this step, there is obtained a substrate, which is coated with a resin layer 4 , whose surface is perfectly flat and parallel to the substrate. The resin also has a surface state or roughness having a Ra value of <25 nm and the desired thickness with a tolerance of ±2 μm. The surface state thus obtained and the geometric precision of the resin thickness are particularly advantageous in the case of a multi-level method, since the surface state determines the surface state of the galvanic deposition grown from said surface and the controlled thickness guarantees the dimensions of each level of each part. The next step d) illustrated in FIG. 1 d consists in irradiating the flattened resin layer by means of UV radiation through a mask 6 defining the contour of the desired microstructures and thus insulated areas 4 a and non-insulated areas 4 b . Typically, this UV radiation is from 200 to 1,000 mJ·cm −2 , measured at a wavelength of 365 nm through the length of the layer. If appropriate, a step of annealing the layer may be required to complete the photopolymerization resulting from the UV irradiation. This annealing step is preferably performed between 90° C. and 95° C. for 15 to 30 min. The insulated (photopolymerized) areas become insensitive to the vast majority of solvents. However, the non-insulated areas will subsequently be able to be dissolved by a solvent. The next step e) illustrated in FIG. 1 e consists in developing the non-insulated areas 4 b of the photosensitive resin layer to reveal, in places, the conductive layer 3 of substrate 1 . This operation is achieved by dissolving non-insulated areas 4 b by means of a solvent chosen from among GBL (gamma butyrolactone) and PGMEA (propylene glycol methyl ether acetate). A plurality of insulated photosensitive resin moulds 4 a having the contours of the metallic structures are thus formed. The next step f) illustrated in FIG. 1 f consists of the galvanic deposition into the moulds of a metal layer, from said conductive layer 3 , to form a plurality of units 7 1 , 7 2 , 7 3 that reach and go beyond the height of the moulds. Metal in this context of course includes metal alloys. Typically, the metal will be selected from among the group including nickel, copper, gold or silver, and, as alloys, copper-gold, nickel-cobalt, nickel-iron, nickel-phosphorus or nickel-tungsten. The electroforming conditions, in particular the composition of the baths, system geometry, current densities and voltage are selected for each metal or alloy to be electroplated in accordance with techniques that are well known in the art of electroforming, (cf. for example Di Bari G. A. “Electroforming” in Electroplating Engineering Handbook 4th Edition edited by L. J. Durney, published by Van Nostrand Reinhold Company Inc., N.Y. USA 1984). In a subsequent step g) illustrated in FIG. 1 g , the electroformed unit is levelled with the resin layer. This step may be performed by abrasion and polishing or machining by a cutting tool so as to immediately obtain microstructures having a flat top surface, with, in particular, a surface state compatible with the requirements of the horological industry for realising up market movements. The next step h) illustrated in FIG. 1 h consists in separating the resin layer 4 a and the electroplated unit 7 1 , 7 2 , 7 3 from substrate 1 . Once this delaminating operation has been performed, photosensitive resin layer 4 a is removed from the delaminated structure to release the microstructures 7 1 , 7 2 , 7 3 thereby formed. In order to do this, in a final step the resin is removed by plasma etching. The microstructure thereby released can either be used immediately or, if necessary, after suitable machining. A first variant of the invention will now be described with reference to FIGS. 2 a to 2 k . In this first variant, the steps illustrated in FIGS. 2 a to 2 e are identical to those described and illustrated in FIGS. 1 a to 1 e . In this first variant, during step f), the galvanic deposition is carried out in the moulds until a plurality of units 7 1 , 7 2 , 7 3 is formed, which reach and go beyond the height of the moulds so as to extend onto the top surface of photosensitive resin 4 a and form metallic bridges 8 for connecting the various units 7 1 , 7 2 , and 7 3 to each other ( FIG. 2 f ). Step g) is omitted. Substrate 1 is then separated from the assembly comprising resin 4 a and electroformed units 7 1 , 7 2 , 7 3 in a delaminating step ( FIG. 2 g ). Resin 4 a is then removed to release units 7 1 , 7 2 , 7 3 , connected to each other by bridges 8 forming a wafer 9 . Typically, the removal of resin 4 a is carried out by plasma etching ( FIG. 2 h ). Wafer 9 is then typically bonded (adhesive 12 ) to a work plate 10 via the reference face F ref thereof opposite the bridges, i.e. the face which was in contact with substrate 1 ( FIG. 2 i ). The exposed faces are machined to bring units 7 1 , 7 2 , 7 3 to the desired thickness and/or surface state, by removing bridges 8 to form the finished or semi-finished parts. During this step, said units 7 1 , 7 2 , 7 3 are released from each other, yet still held in a precise, defined position in adhesive 12 ( FIG. 2 i ). At the end of this step, said obtained parts may either be released from work plate 10 and then cleaned ( FIG. 2 j ), or reworked on a machine tool for batch machining ( FIG. 2 k ). At this stage, the parts may be subject to various decorative and/or functional treatments, typically physical or chemical depositions. A second variant of the invention will now be described with reference to FIGS. 3 a to 3 k . In this second variant, the steps illustrated in FIGS. 3 a to 3 f are identical to those described and illustrated in FIGS. 1 a to 1 f . In this second variant, step g) is also removed and after step f), substrate 1 is separated from the assembly comprising resin 4 a and electroformed units 7 1 , 7 2 et 7 3 during a delaminating step ( FIG. 3 g ). Resin 4 a is then removed to release units 7 1 , 7 2 et 7 3 . Typically, the removal of the resin is achieved by plasma etching ( FIG. 3 h ). Electroformed units 7 1 , 7 2 , 7 3 are no longer connected to each other. A transfer strip stretched over a frame 11 is then applied to the opposite face to reference face F ref of said units, i.e. the face which was in contact with substrate 1 ( FIG. 3 i ). Units 7 1 , 7 2 , 7 3 bonded to the transfer strip are then typically bonded to a work plate 10 via the reference face thereof, i.e. the face which was in contact with substrate 1 ( FIG. 3 j ). The frame is removed, leaving the transfer strip. The exposed faces of the units are then machined to form parts 7 1 , 7 2 , and 7 3 with the desired thickness and/or surface state by removing the transfer strip. During this step, said parts are released from each other and the transfer strip, yet still held in the adhesive 12 ( FIG. 3 k ). At the end of this step, said parts are released from the work plate 10 and then cleaned. A third variant of the invention will now be described with reference to FIGS. 4 a to 4 j . In this third variant, the steps illustrated in FIGS. 4 a to 4 f are identical to those described and illustrated in FIGS. 1 a to 1 f . In this third variant, step g) is also omitted. This variant applies in the case where the adherence of the assembly comprising the resin and electroformed units is not sufficient to allow direct machining of units 7 1 , 7 2 , 7 3 on substrate 1 . In this case, substrate 1 is separated from the assembly comprising resin 4 a and electroformed units 7 1 , 7 2 and 7 3 in a delaminating step ( FIG. 4 g ). The resin-electroformed unit assembly is then bonded to a work plate 10 via the reference face F ref thereof, i.e. the face which was in contact with substrate 1 ( FIG. 4 h ). The exposed faces of the units 7 1 , 7 2 and 7 3 are then machined to form parts with the desired thickness and/or surface state. The parts are held by resin 4 a and adhesive 12 ( FIG. 4 i ). At the end of this step, said parts are released from the work plate 10 , and resin 4 a is then removed to release the obtained parts. Typically, the removal of the resin is achieved by plasma etching ( FIG. 4 j ). According to the invention, it will also be noted that, prior to the step illustrated respectively in FIGS. 1 e , 2 e , 3 e and 4 e , the steps illustrated and described with reference to FIGS. 1 b to 1 d , 2 b to 2 d , 3 b to 3 d and 4 b to 4 d are repeated at least once to obtain multi-level parts. The number of levels is not therefore limited. For horological applications, the typical number of levels is 1 to 5. Where multi-level resin moulds are made, it is advantageous to deposit a conductive layer on the resin after step 1 d , 2 d , 3 d , 4 d to allow regular growth of the electroplated material during the subsequent step 1 f , 2 f , 3 f , 4 f.
A method of fabricating a plurality of metallic microstructures by LIGA process, the method including a flattening step or a levelling step of the resin layer before the step of electroforming the metallic microstructures permitting the resin layer to have a uniform thickness, which enables molds, and then finished metallic microstructures, to be made with uniform dimensional precision in the plane for the metallic microstructures of the same substrate.
1
RELATED APPLICATIONS This application is a continuation in part of U.S. patent application Ser. No. 08/440,268 filed on May 12, 1995. FIELD OF INVENTION The present invention relates to the control of magnetic storage systems for digital computers, and particularly, to a sampled amplitude read channel incorporating a fault tolerant sync mark detector. CROSS REFERENCE TO RELATED APPLICATIONS AND PATENTS This application is related to other co-pending U.S. patent applications, namely application Ser. Nos. 08/341,251 entitled "Sampled Amplitude Read Channel Comprising Sample Estimation Equalization, Defect Scanning, Channel Quality, Digital Servo Demodulation, PID Filter for Timing Recovery, and DC Offset Control," 08/701,572 entitled "Improved Timing Recovery For Synchronous Partial Response Recording." This application is also related to several U.S. patents, namely U.S. Pat. No. 5,359,631 entitled "Timing Recovery Circuit for Synchronous Waveform Sampling," U.S. Pat. No. 5,291,499 entitled "Method and Apparatus for Reduced-Complexity Viterbi-Type Sequence Detectors," U.S. Pat. No. 5,297,184 entitled "Gain Control Circuit for Synchronous Waveform Sampling," U.S. Pat. No. 5,329,554 entitled "Digital Pulse Detector," and U.S. Pat. No. 5,424,881 entitled "Synchronous Read Channel." All of the above-named patent applications and patents are assigned to the same entity, and all are incorporated herein by reference. BACKGROUND OF THE INVENTION In magnetic disk storage systems for computers, digital data serves to modulate the current in a read/write head coil so that a sequence of corresponding magnetic flux transitions are written onto the surface of a magnetic medium in concentric tracks. To read this recorded data, the read/write head passes over the magnetic medium and transduces the magnetic transitions into pulses in an analog signal that alternate in polarity. These pulses are then detected and decoded by read channel circuitry to reproduce the digital data. Detecting and decoding the pulses into a digital sequence can be performed by a simple peak detector in a conventional analog read channel or, as in more recent designs, by a discrete time sequence detector in a sampled amplitude read channel. Discrete time sequence detectors are preferred over simple analog pulse detectors because they compensate for intersymbol interference (ISI) and channel noise. As a result, discrete time sequence detectors increase the capacity and reliability of the storage system. There are several well known discrete time sequence detection methods including discrete time pulse detection (DPD), partial response (PR) with Viterbi detection, maximum likelihood sequence detection (MLSD), decision-feedback equalization (DFE), enhanced decision-feedback equalization (EDFE), and fixed-delay tree-search with decision-feedback (FDTS/DF). In conventional peak detection schemes, analog circuitry, responsive to threshold crossing or derivative information, detects peaks in the continuous time analog signal generated by the read head. The analog read signal is "segmented" into bit cell periods and interpreted during these segments of time. The presence of a peak during the bit cell period is detected as a "1" bit, whereas the absence of a peak is detected as a "0" bit. The most common errors in detection occur when the bit cells are not correctly aligned with the analog pulse data. Timing recovery, then, adjusts the bit cell periods so that the peaks occur in the center of the bit cells on average in order to minimize detection errors. Since timing information is derived only when peaks are detected, the input data stream is normally run length limited (RLL) to limit the number of consecutive "0" bits. As the pulses are packed closer together on the concentric data tracks in the effort to increase data density, detection errors can also occur due to intersymbol interference , a distortion in the read signal caused by closely spaced overlapping pulses. This interference can cause a peak to shift out of its bit cell, or its magnitude to decrease, resulting in a detection error. The ISI effect is reduced by decreasing the data density or by employing an encoding scheme to ensure that a minimum number of "0" bits occur between "1" bits. For example, a (d,k) run length limited (RLL) code constrains to d the minimum number of "0" bits between "1" bits, and to k the maximum number of consecutive "0" bits. A typical RLL code is a (1,7) 2/3 rate code which encodes 8 bit data words into 12 bit codewords to satisfy the (1,7) constraint. Sampled amplitude detection, such as partial response (PR) with Viterbi detection, allows for increased data density by compensating for intersymbol interference. Unlike conventional peak detection systems, sampled amplitude recording detects digital data by interpreting, at discrete time instances, the actual value of the pulse data. The analog pulses are sampled at the baud rate (code bit rate) and the digital data is detected from these discrete time sample values. A discrete time sequence detector, such as a Viterbi detector, interprets the discrete time sample values in context to determine a most likely sequence for the data. In this manner, the effect of ISI can be taken into account during the detection process, thereby decreasing the probability of a detection error. This increases the effective signal to noise ratio and, for a given (d,k) constraint, allows for significantly higher data density as compared to conventional analog peak detection read channels. The application of sampled amplitude techniques to digital communication channels is well documented. See Y. Kabal and S. Pasupathy, "Partial Response Signaling", IEEE Trans. Commun. Tech., Vol. COM-23, pp. 921-934, Sept. 1975; and Edward A. Lee and David G. Messerschmitt, "Digital Communication", Kluwer Academic Publishers, Boston, 1990; and G. D. Forney, Jr., "The Viterbi Algorithm", Proc. IEEE, Vol. 61, pp. 268-278, March 1973. Applying sampled amplitude techniques to magnetic storage systems is also well documented. See Roy D. Cideciyan, Francois Dolivo, Walter Hirt, and Wolfgang Schott, "A PRML System for Digital Magnetic Recording", IEEE Journal on Selected Areas in Communications, Vol. 10 No. 1, January 1992, pp. 38-56; and Wood et al, "Viterbi Detection of Class IV Partial Response on a Magnetic Recording Channel", IEEE Trans. Commun., Vol. Com-34, No. 5, pp. 454-461, May 1986; and Coker et al, "Implementation of PRML in a Rigid Disk Drive", IEEE Trans. on Magnetics, Vol. 27, No. 6, Nov. 1991; and Carley et al, "Adaptive Continous-Time Equalization Followed By FDTS/DF Sequence Detection", Digest of The Magnetic Recording Conference, Aug. 15-17, 1994, pp. C3; and Moon et al, "Constrained-Complexity Equalizer Design for Fixed Delay Tree Search with Decision Feedback", IEEE Trans. on Magnetics, Vol. 30, No. 5, Sept. 1994; and Abbott et al, "Timing Recovery For Adaptive Decision Feedback Equalization of The Magnetic Storage Channel", Globecom'90 IEEE Global Telecommunications Conference 1990, San Diego, Calif., Nov. 1990, pp. 1794-1799; and Abbott et al, "Performance of Digital Magnetic Recording with Equalization and Offtrack Interference", IEEE Transactions on Magnetics, Vol. 27, No. 1, Jan. 1991; and Cioffi et al, "Adaptive Equalization in Magnetic-Disk Storage Channels", IEEE Communication Magazine, Feb. 1990; and Roger Wood, "Enhanced Decision Feedback Equalization", Intermag'90. The format of the data stored on the magnetic disk, as shown in FIG. 2A and 2B, is similar for both peak detection and sampled amplitude read channels. The data is stored as a series of concentric tracks 13 each comprising a number of user data sectors 15 and embedded servo data sectors 17. As illustrated in FIG. 2A, the embedded servo data sectors 17 are recorded at the same data rate across the disk's radius. For the user data sectors 15, however, the disk is partitioned into a number of zones (e.g., an outer zone 11 and an inner zone 27) and the data rate increased in the outer zones in order to achieve a more constant linear bit density. This "zoned" recording technique allows more data to be stored in the outer diameter tracks, thereby increasing the overall capacity of the disk. FIG. 2B shows the format of a user data sector 15 and a servo data sector 17 comprising a preamble (68,5), sync mark (70,7) and data field (72,3). The read channel processes the preamble (68,5) to adjust the magnitude of the read signal (and synchronize timing recovery in sampled amplitude read channels) so that it can accurately read the data field (72,3). The sync mark (70,7) demarks the beginning of the data field (72,3), and when the read channel detects the sync mark (70,7), it signals a disk controller (not shown) to begin processing the detected data. The sync mark (70,7) must be detected at the correct time or the read channel cannot synchronize to the data field (72,3). Errors due to noise in the system can cause the read channel to detect the sync mark (70,7) too early or fail to detect it altogether. That is, errors in the detected read signal can cause the read channel to falsely detect the sync mark as the end of the preamble concatenated with the beginning of the sync mark. When this happens, error detection circuitry within the disk controller will recognize that the sync mark was falsely detected and initiate a re-try. The storage system will wait for the disk to complete a revolution, which increases the overall access time, and again attempt to accurately detect the sync mark. A sync detector in the read channel detects the sync mark (70,7) by correlating a target sync mark with the bit sequence detected from the read signal. In order to minimize the probability of early misdetection, the sync mark (70,7) is selected to have a minimum correlation with the sync mark (70,7) concatenated with the preamble (68,5). It is also selected for maximum probability of correct detection when the sync mark is corrupted by errors due to noise. This is accomplished with a computer search program which searches for an appropriate sync mark by correlating a target sync mark with shifted values of the target sync mark appended to the preamble. The search program also correlates the target sync mark with corrupted versions of the sync mark appended to the preamble. Selecting a sync mark to have minimum correlation with the preamble increases the fault tolerance of the sync mark detector. Prior art sync mark detectors do not use the preamble (68,5) to assist in detecting the sync mark (70,7). Instead, conventional sync mark detectors execute a correlation with each new bit detected from the read signal. For example, U.S. Pat. No. 5,384,671 issued to Fisher discloses a sync mark detection technique that selects a sync mark to have minimum correlation with the preamble but does not use information from the preamble in the detection process. Furthermore, prior art sync mark detectors do not use the sign of the sampled data in order to improve the correlation sensitivity. What is needed is a sync mark detection technique that uses information from the preamble and sign of the sampled data in order to further increase the fault tolerance of the sync mark detector. SUMMARY OF THE INVENTION In a storage device for storing digital data on a magnetic disk in a series of concentric tracks comprising a number of user data sectors and embedded servo data sectors where each sector comprises a preamble, sync mark and data field, a sampled amplitude read channel employs a fault tolerant sync mark detector that uses information from the preamble to improve the sync mark detection process. A state machine generates expected sample values used by a timing recovery circuit to acquire the preamble field. The preamble is recorded to the disk in a manner that ensures the state machine will be in a predetermined state when the end of the preamble is encountered. In this manner, the sync mark detector need only execute a correlation of the detected bit sequence with a target sync mark when the state machine is in the predetermined state. As the bit sequence is detected from the read signal with each, new sample period, it is shifted into a shift register. The sync mark detector correlates the detected bit sequence with a target sync mark and outputs a sync mark detected signal when the sync mark is found. The output of the sync mark detector is enabled according to the current state of the state machine, i.e., at a predetermined sample period interval. In one example, the end of preamble can occur only when the state machine is in two of four states. Therefore, the sync detector is enabled at every other sample period. In another, embodiment, the sync mark detector processes the even and odd interleaves of the detected bit sequence in parallel, and the current state of the state machine initializes the sync mark detector rather than enable its output. In both of these embodiments, the sync mark detector's output represents the correlation of the bit sequence with the target sync mark only during a predetermined sample period interval. This increases the fault tolerance of the sync mark detector and the fault tolerant characteristics of the sync mark itself by allowing the computer search program to search for a sync mark having minimum correlation with the preamble at the predetermined interval. The present invention achieves further fault tolerance by minimizing a mean squared error between a partial response representation of the detected sync mark and the target sync mark. This increases the correlation sensitivity since a partial response signal provides both sign and magnitude information. The read channel's discrete time sequence detector outputs a sign and magnitude of estimated sample values corresponding to a PR4 representation of the detected digital data. For read channels employing PR4 sequence detectors, the PR4 sync mark data is generated by appending a sign bit to the detected binary sequence and normalizing the PR4 values from (-2,0,+2) to (-1,0,-1). For EPR4 and EEPR4 sequence detectors, the PR4 sync mark data is generated by appending a sign bit to the detected binary sequence (NRZI data) and then encoding the signed NRZI data into a PR4 representation. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a block diagram of a conventional sampled amplitude recording channel. FIG. 2A shows an exemplary data format of a magnetic disk having a plurality of concentric tracks recorded in zones at varying data rates where each track contains a plurality of user data and embedded servo data sectors. FIG. 2B shows an exemplary format of a user data sector and an embedded servo data sector. FIG. 3 is a block diagram of the sampled amplitude read channel of the present invention comprising automatic gain control, DC offset control, timing recovery, a first and second synthesizer for processing user and servo data respectively, an asynchronous servo address mark detector, and a sync mark detector for detecting user data and servo data sync marks. FIG. 4 is a block diagram of a sampled amplitude read channel timing recovery circuit comprising a VFO for generating a sampling frequency. FIG. 5 shows more details of the data/servo sync detector and particularly the operation with respect to the timing recovery control signal. FIG. 6A shows the acquisition read signal with corresponding actual and estimated sample values. FIG. 6B is a detailed diagram of the preferred embodiment for the expected sample value generator and phase error detector used in the timing recovery circuit. FIG. 7 is an alternative embodiment for the data/servo sync detector which processes the even and odd interleaves of the read signal in parallel. FIG. 8 shows an EPR4 or EEPR4 sequence detector having a signed NRZI to PR4 data encoder. FIG. 9 shows an implementation of a sync mark detector that compares a PR4 representation of the detected sync mark with the target sync mark. FIG. 10 shows yet another implementation of the sync mark detector having a preamble synthesizer for generating an enable and sign control signals in response to the recorded preamble. FIG. 11 shows an implementation of the preamble synthesizer of FIG. 10. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT Conventional Sampled Amplitude Read Channel FIG. 1 is a detailed block diagram of a conventional sampled amplitude read channel. During a write operation, either user data 2 or preamble data from a data generator 4 (for example, 2 T preamble data) is written onto the medium. An RLL encoder 6 encodes the user data 2 into a binary sequence b(n) 8 according to an RLL constraint. For PR4 read channels, a precoder 10 precodes the binary sequence b(n) 8 in order to compensate, for the transfer function of the recording channel 18 and equalizing filters to form a precoded sequence ˜b(n) 12. The precoded sequence ˜b(n) 12 is converted into symbols a(n) (or NRZ data) 16 by translating 14 ˜b(N)=0 into a(N)=-1, and ˜b(N)=1 into a(N)=+1. Write circuitry 9, responsive to the symbols a(n) 16, modulates the current in the recording head coil at the baud rate 1/T to record the binary sequence onto the medium. A frequency synthesizer 52 provides a baud rate write clock 54 to the write circuitry 9. The recorded data are referred to as NRZI data where each magnetic transition represents a "1" bit and each non-transition represents a "0" bit. When reading the recorded binary sequence from the media, timing recovery 28 first locks to the write frequency by selecting, as the input to the read channel, the write clock 54 through a multiplexer 60. Once locked to the write frequency, the multiplexer 60 selects the signal 19 from the read head as the input to the read channel in order to acquire the acquisition preamble. A variable gain amplifier 22 adjusts the amplitude of the analog read signal 58, and an analog filter 20 provides initial equalization toward the desired response. A sampling device 24 samples the analog read signal 62 from the analog filter 20, and a discrete time filter 26 provides further equalization of the sample values 25 toward the desired response. In partial response recording, for example, the desired response is often selected from Table 1. A DC offset circuit 1 responsive to the equalized sample values 32 computes and subtracts the DC offset 29 from the analog read signal 62. The equalized sample values 32 are applied to decision directed gain control 50 and timing recovery 28 for adjusting the amplitude of the read signal 58 and the frequency and phase of the sampling device 24, respectively. Timing recovery adjusts the frequency of sampling device 24 over line 23 in order to synchronize the equalized samples 32 to the baud rate. Frequency synthesizer 52 provides a coarse center frequency setting to the timing recovery circuit 28 over line 64 in order to center the timing recovery frequency over temperature, voltage, and process variations. Gain control 50 adjusts the gain of variable gain amplifier 22 over line 21. The equalized samples Y(n) 32 are sent to a discrete time sequence detector 34, such as a maximum likelihood (ML) Viterbi sequence detector, to detect an estimated binary sequence b(n) 33. The discrete time sequence detector operates according to the selected equalization (PR4, EPR4, EEPR4, etc.), and for PR4 equalization, the preferred embodiment is two sliding threshold detectors for processing the even and odd interleaves, respectively. An RLL decoder 36 decodes the estimated binary sequence b(n) 33 into estimated user data 37. A data sync mark detector 66 detects the sync mark 70 (shown in FIG. 2B) in the data sector 15 in order to frame the operation of the RLL decoder 36 and signal the beginning of user data 72. In the absence of errors, the estimated binary sequence b(n) 33 equals the recorded binary sequence b(n) 8, and the decoded user data 37 equals the recorded user data 2. Improved Sampled Amplitude Read Channel FIG. 3 is a block diagram of the improved sampled amplitude read channel of the present invention comprising a user data frequency synthesizer A100 and a servo data frequency synthesizer A102. When reading user data, a control line U/S selects the output A114 of the user data synthesizer A100 as the lock to reference frequency through a multiplexer A104. The control line U/S also selects the coarse center frequency setting A110 of the user data synthesizer A100 through multiplexer A112 as the timing recovery control signal 64. When the read channel switches into servo data mode in order to read a servo wedge, the control line U/S selects the output A106 of the servo data synthesizer A102 as the lock to reference frequency through multiplexer A104. The control line U/S also selects the coarse center frequency setting A108 from the servo data synthesizer A102 through multiplexer A112 as the timing recovery control signal 64. The read channel further comprises an asynchronous servo address mark detector A126 for generating a control signal A118 indicating when the servo address mark has been detected. The servo address mark detector A126 switches operation of the gain control circuit over line A118 to compensate for the unpredictable amplitude fluctuations caused by the inter-track head position and the wide range of user to servo data densities. A data/servo sync mark detector A120, responsive to the detected data sequence 33 from the sequence detector 34, detects both user data and servo data sync marks and generates framing signals (A121,A119) to frame operation of a user data RLL decoder 36 and a servo data RLL decoder A122, respectively. The sync detector A120 is also responsive to a control signal A124 from the timing recovery circuit 28 to aid in the sync mark detection process. The read channel further comprises auxiliary analog inputs for sampling other analog signals generated within the disk drive such as the driving current for a Voice Coil Motor in a servo system, or the output of a temperature sensor. A multiplexer A101 selects, as the input to sampling device 24, the analog read signal 62 from the analog receive filter 20 or one of a plurality of auxiliary input signals A103. When an auxiliary input is selected for sampling, the output 25 of the sampling device 24 is stored into registers for subsequent processing by a microcontroller such as a servo controller. Data/Servo Sync Mark Detector After acquiring the preamble (68,5) (shown in FIG. 2B), a data/servo sync mark detector A120 of FIG. 3 searches for the sync mark (70,7) which demarks the beginning of the user or servo data fields. When the sync mark (70,7) is detected, the data/servo sync detector A120 enables operation of the RLL data decoder 36 or the RLL servo decoder A122 in order to frame the user or servo data fields. The data/servo sync mark detector A120 detects the sync mark (70,7) by correlating a target sync mark with the estimated bit sequence b(n) 33 from the discrete time sequence detector. In order to minimize the probability of early misdetection, the sync mark (70,7) is selected to have a minimum correlation with the sync mark (70,7) concatenated with the preamble (68,5). It is also selected for maximum probability of correct detection when the sync mark is corrupted by errors due to noise. This is accomplished with a computer search program which searches for an appropriate sync mark by correlating a target sync mark with shifted values of the target sync mark appended to the preamble. The search program also correlates the target sync mark with corrupted versions of the sync mark appended to the preamble. In a first embodiment of the present invention, operation of the correlation process is understood with reference to FIG. 5. The estimated bit sequence b(n) 33 is shifted into a shift register C100 and the target sync mark (servo or data) is loaded into register C102. Registers C100 and C102 are programmable to accommodate various sync mark lengths. The corresponding bits of registers C100 and C102 are correlated (using an exclusive-nor gate not shown) and summed with an adder C104. A threshold comparator C118 compares the output of the adder C104 to a predetermined programmable threshold and outputs a threshold correlation signal C106. The threshold correlation signal C106 is enabled through an AND gate C108 by a control signal C194 generated in response to a timing recovery control signal A124. The output C114 of the AND gate C108 is applied to the RLL decoder framing signals (A121,A119) through a demultiplexer C116 according to the state of the U/S control signal. The control signal C194 for enabling the threshold correlation signal C106 is understood in relation to the operation of the timing recovery circuit 28, an overview of which is provided in FIG. 4. In FIG. 4, the output 23 of a variable frequency oscillator (VFO) B164 controls the sampling clock of a sampling device 24 which is typically an analog-to-digital converter (A/D) in digital read channels. A frequency error detector B157 and phase error detector B155 control the frequency of the VFO B164, and a loop filter B160 provides control over the closed loop characteristics. A multiplexer B159 may select the unequalized sample values 25 during acquisition, and the equalized sample values 32 during tracking. From the sample values received over line B149, the frequency error detector B157 generates a frequency error, and the phase error detector B155 generates a phase error. The phase error is also computed from expected sample values X(n) from an expected sample generator B151 during acquisition, and estimated sample values ˜X(n) from a sample value estimator B141, such as a slicer according to Table B2, during tracking. Referring again to FIG. 2B, before acquiring the acquisition preamble (68,5) the phase-lock-loop first locks onto a predetermined nominal sampling frequency according to the zone where the current track is located. In this manner, the phase-lock-loop is close to the desired acquisition frequency when it switches to acquisition mode. As previously mentioned, the acquisition preamble (68,5) is processed during acquisition mode in order to lock the PLL to the desired sampling phase and frequency before sampling the user or servo data fields (72,3). Once locked onto the acquisition preamble, the phase-lock-loop switches into tracking mode and, after detecting the sync mark (70,7), begins tracking user or servo data (72,3). To record the acquisition preamble to the disk, a data generator 4 connected to the input of the precoder 10 outputs a series of "1" bits to generate a 2T training preamble sequence at the output of the precoder 10 of the form (1,1,0,0,1,1,0,0,1,1,0,0, . . . ). This 2T preamble maximizes the magnitude of a PR4 read channel, and during acquisition, it is "side sampled" to generate the following sample sequence: (+A, +A, -A, -A, +A, +A, -A, -A, +A, +A, -A, -A, . . . ). FIG. 6A shows the 2T preamble "side sampled" with the expected samples C120 in relation to the signal samples C122 and a corresponding phase error T. FIG. 6B shows an implementation of the phase error detector B155 and the expected sample value generator B151 of FIG. 4. To adjust the initial sampling timing phase, the phase error detector B155 computes a timing gradient which minimizes the mean squared error between read signal sample values and expected sample values. The timing gradient value Δt C124 is computed as: Δt(n)=Y(n-1)·X(n)-Y(n)·X(n-1) where Y(n) are the read signal sample values B149 and X(n) are the expected sample values C126. Referring again to FIG. 6B, the outputs (C137,C138) of a 2-bit counter C128 correspond to the expected "side sampled" preamble sequence: 00→+A,-A 01→-A,-A, 10→-A,+A 11→+A,+A. The expected sample value is scaled to |A|=1 so that the multipliers (C130a,C130b) of the phase error detector B155 multiply by +1, -1 or 0. Thus, the expected sample values X(n) C126 are two bits wide in order to represent the ternary values: (00=0, 01=1, and 11=-1). A multiplexer C132, responsive to the outputs (C137,C138) of the counter C128, selects the expected sample values X(n) C126 which correspond to the current counter state. The counter C128 is loaded C134 with an initial starting state by logic C136 in response to two consecutive sample values Y(n) B149. The counter output bits C0 C138 and C1 C137 are initialized to: C1=sgn(Y(n-1)); and C0=sgn(Y(n)) XOR sgn(Y(n-1)) where sgn(x) returns a 0 if x is positive and 1 if negative. Table C2 shows the "side sampled" starting state values loaded into counter C128 corresponding to the two consecutive sample values. After the counter C128 is loaded with the initial starting state, it sequences through the states according to the expected samples in the 2T preamble at each sample clock 23. The four possible sequences are: (+A,-A,-A,+A,+A,-A, . . . ); and (-A,-A,+A,+A,-A,-A, . . . ); and (-A,+A,+A,-A,-A,+A, . . . ); and (+A,+A,-A,-A,+A,+A, . . . ). Using a counter to generate expected sample values avoids a "hang up" problem associated with the prior art, and, in addition, the state of the counter C128 can be advantageously used in the selection and detection of the sync mark (70,7). If the 2T acquisition preamble (68,5) always ends with two positive samples ++ or two negative samples -- (e.g., samples C120d in FIG. 6A), then the output 25 of the A/D converter 24 will be X the last preamble sample only when the counter C128 of FIG. 6B is in state (-A,-A) or (+A,+A) which corresponds to counter C128 outputs 01 (i.e., the count is one) or 11 (i.e., the count is three). Therefore, the output 25 of the A/D converter 24 will be the first sample of the sync mark only when the counter C128 output is 10 (ie., the count is two) or 00 (i.e., the count is zero). Assuming the discrete time equalzing filter 26 and the discrete time sequence detector 34 of FIG. 3 contain d bits of delay, then the output 33 of the sequence detector 34 will be the first bit of the sync mark only when the counter C128 output is (2+d) MOD 4 or (0+d) MOD 4. Finally, assuming the sync mark register C100 is k bits in length, then the sync mark will be completely loaded into the register C100 only when the counter C128 output is (2+d+k) MOD 4 or (0+d+k) MOD 4. Thus, the data/servo sync mark detector A120 is enabled only during these two counts, i.e., only at every other sample period. Counter decode logic C190 enables the output of the data/servo sync mark detector A120 through AND gate C108 only when the counter C128 output (C137,C138) equals either of the two counts (2+d+k) MOD 4 or (0+d+k) MOD 4. To ensure that the acquisition preamble (68,5) always ends in the desired phase state (such as two positive samples or two negative samples), the state of the precoder 10 is initialized to an appropriate value when writing the preamble (68,5) to the disk. For a PR4 read channel, for example, the delay registers in the 1/1+D 2 precoder 10 are initialized to zero and an even number of 1 bits are output by the data generator 4 to ensure that the preamble ends in either two positive samples or two negative samples. Enabling the data/servo sync mark detector A120 at every other sample period aids in the computer search for the optimum fault tolerant sync mark. The search program can search for minimum correlation between the sync mark and shifted versions of the sync mark concatenated with the preamble at every other shift rather than at every shift. This increases the probability of finding a sync mark having a higher degree of fault tolerance. The sync mark detection technique of the present invention can be easily extended to search for the sync mark at every fourth sample period rather than at every other sample period. This requires that the preamble always end in the same two sample values (i.e., the preamble ends with the counter C128 in one out of the four possible states). Further, this technique can easily be extended for use with other preamble formats (e.g., 3T, 4T, 6T, etc) and with other types of PR read channels (e.g., EPR4 and EEPR4). In an alternative embodiment of the present invention shown in FIG. 7, the data/servo sync mark detector A120 processes two bits of the detected sequence 33 at a time. The target sync mark C102 is separated into in an even and odd interleave and stored in an even register C150 and an odd register C152, respectively. Control logic C140 loads the even and odd interleaves (C142,C144) of the detected sequence 33 into respective shift registers (C146,C148) in response to an enable signal C194 from counter decode logic C190. The control logic C140 delays loading the shift registers (C146,C148) with the detected sequence 33 until the counter C128 of FIG. 6B is in one of the two enabling states ((2+d) MOD 4 or (0+d) MOD 4). In yet another embodiment of the present invention, the data/servo sync mark detector A120 correlates estimated sample values with expected sample values that corresponded to the target sync mark. For the purpose of this disclosure, then, the data/servo sync mark detector A120 is specified, in general, as generating channel values in response to the discrete time sample values and correlating the channel values with target values of a target sync mark. The estimated and expected sample values of the detected and target sync mark are represented by Partial Response Class-IV (PR4) signals. The discrete time sequence detector 34 of FIG. 3 outputs a sign and magnitude of the detected binary sequence (i.e., a two bit wide sequence). The signed binary output sequence is then encoded into a PR4 signal of estimated sample values. If the discrete time sequence detector 34 is a PR4 detector, then the signed binary output sequence is already in the PR4 format with the estimated samples normalized to (-1,0,+1). If the discrete time sequence detector 34 is an EPR4 or EEPR4 detector, then the output of the detector (NRZI format) is converted into a PR4 signal by passing the sign and magnitude bits through a (1+D) filter as shown in FIG. 8. Once in the PR4 representation, the sync mark detector computes a squared error between the detected PR4 sync mark and the target PR4 sync mark. When the squared error falls below a predetermined programmable threshold Th, the sync mark has been detected. Mathematically, the squared error signal is computed according to: e.sup.2 =Σ(S.sub.k -t.sub.k).sup.2 =ΣS.sub.k.sup.2 -2·ΣS.sub.k ·t.sub.k +Σt.sub.k.sup.2 where: S k is the sign and magnitude of the estimated sample values; and t k is the sign and magnitude of the target sample values. Since the polarity of the write signal may be opposite that of the read signal, the computed error signal is: e.sup.2 =ΣS.sub.k.sup.2 -2·COR+Σt.sub.k.sup.2 where: COR is either +ΣS k ·t k or -ΣS k ·t k depending on the polarity of the read signal as determined by the timing recovery control signal C138 of FIG. 6B. The term Σt k 2 equals the number of ones in the target sync mark, a constant. Therefore, the test for the sync mark becomes: ΣS.sub.k.sup.2 -2·COR<Th'; where: Th' is a programmable threshold=Th-Σt k 2 . The term ΣS k 2 equals the number of ones in the estimated samples and can be computed by counting the number of ones input into the sync mark detector. By initializing a counter with -Th', incrementing the counter for each one input into the sync mark detector, and decrementing the counter with each one output from the detector, the content CNT of the counter is: ΣS.sub.k.sup.2 -Th'. (1) The test for the sync mark is then: 2·COR>CNT. (2) A circuit for implementing equations (1) and (2) is illustrated in FIG. 9. A 9-bit target sync mark 010010001 has been selected for the purpose of illustration, but other sync mark lengths and values are equally applicable. The circuit of FIG. 9 assumes that the preamble always ends in two negative samples resulting in PR4 sample values for the target sync mark of 0+00+000-. If the preamble ends in two positive samples, then the PR4 values for the target sync mark are 0-00-000+ and the correlation is negated as described below. Referring now to FIG. 9, the PR4 sign and magnitude bits from the discrete time sequence detector 34 are input into control logic C140 similar to that of FIG. 7. The control logic C140, responsive to a control signal C194 from counter decode logic C190, delays loading the shift registers with the PR4 data until the counter C128 of FIG. 6B is in one of the enabling states as described above. In order to implement the COR function of equation (2), an adder C160 adds the estimated PR4 values corresponding to the non-zero target PR4 values. Since the last target PR4 value is a "-1" when the preamble ends in two negative samples, an AND gate C162 negates the last bit of the estimated PR4 values. A multiplying circuit C164 multiplies the COR signal by 2, and a multiplexer C166, responsive to the decoded timing recovery control signal C192, selects between an unmodified or a negated 2·COR signal (i.e., multiplied by -1 C188) depending on whether the preamble ends in -- or ++, respectively. That is, the control signal C192 from the counter decode logic C190 will negate the correlation signal C186 when the output of the timing recovery counter C128 equals (0+d+k) MOD 4 which corresponds to the preamble ending in two positive samples (i.e., the target PR4 sample values are 0-00-000+). The circuit C168 for generating the CNT threshold value of equation (1) operates as follows. First, a storage register C170 is loaded with a predetermined prgrammable threshold -Th' C172 through a multiplexor C174, and the sync mark detector shift registers are cleared. Then for each clock cycle, counter logic C176 counts the number of non-zero values entering the sync mark detector and subtracts the number of non-zero values exiting the sync mark detector. The output of counter logic C176 (which can take on the values {0,±1,±2}) is input into an adder C178, added to the content of the storage register C170, and restored to the storage register C170 through multiplexer C174. To complete the implementation of equation (2), the storage register C170, which contains the CNT value C180 of equation (1), is compared to the 2·COR value C182 at the output of the multiplexor C166 using a comparator C184. The output of the comparator C184 is the output C114 of the sync mark detector. FIG. 10 illustrates yet another embodiment of the sync mark detector which correlates the PR4 representation of the detected and target sync marks independent of the timing recovery expected sample generator B151 (i.e., independent of the counter C128). In this embodiment, a preamble synthesizer C196 generates the input control signal C194 and the sign control signal C192 in response to the recorded preamble. The preamble synthesizer C196 locks onto the recorded preamble sequence and then generates the 2T preamble independent of the sampled input sequence. Operation of the preamble synthesizer C196 is understood with reference to FIG. 11. In FIG. 11, a counter C208 is cleared and a first shift register C202 is initialized with the sequence 1,1,0,0,1,1, . . . , 0,0 which corresponds to the PR4 sign bit sequence of the 2T preamble. The PR4 sign bit C200 from the sequence detector 34 is then input into a second shift register C204 and correlated with the first shift register C202 using an adder C206 and exclusive-nor gates not shown. The output of the adder C206 is compared to a predetermined threshold using a comparator C210. When the correlation exceeds the predetermined threshold, the preamble synthesizer has locked onto the recorded preamble. The counter C208 is enabled and clocked at each sample period to generate the sync mark detector input enable signal C194 and the sign control signal C192 through counter decode logic C190. Operation of the counter decode logic C190 is as described above except that it does not need to compensate for the delay associated with the equalizing filter 26 and sequence detector 34. That is, the input enable signal C194 is active when the output of the counter C208 is 00 or 10, and the sign control signal C192 is active when the output of the counter C208 is (0+k) MOD 4. The C0 output of counter C208 is also shifted into the first shift register C202 so that the preamble synthesizer C196 continues to track the recorded 2T preamble. In this manner, the preamble synthesizer filters out errors in the detected 2T preamble caused by noise in the channel. The operation of the data/servo sync mark detector A120 can be described mathematically by the following equation: Y(k)=( t.sub.0,t.sub.1 . . . t.sub.N-1 !· S.sub.k,S.sub.k+1, . . . , S.sub.k+N-1 !.sup.t ·I)<Th; where: Y(k): output C114 of the data/servo sync mark detector A120; k: the sample value index; t 0 ,t 1 , . . . t N-1 !: the target values of the target sync mark; S k ,S k+1 , . . . , S k+N-1 !: the channel values; N: length of the target sync mark; I: a sample period interval enable signal that is equal to 1 when k modulo Q is a member of a set S and 0 otherwise, where Q is a predetermined integer not equal to 1; and Th: a predetermined threshold. For the 2T acquisition preamble (68,5) described in the above examples where the output of the data/servo sync mark detector A120 is enabled at every other sample value, Q=2 and the set S={0}. Many changes in form and detail could be made without departing from the spirit and scope of the present invention; the particular embodiments disclosed herein are not intended to be limiting. The scope of the invention is properly construed from the following claims. TABLE 1______________________________________Channel Transfer Function Dipulse Response______________________________________PR4 (1 - D) (1 + D) 0, 1, 0, -1, 0, 0, 0, . . .EPR4 (1 - D) (1 + D).sup.2 0, 1, 1, -1, -1, 0, 0, . . .EEPR4 (1 - D) (1 + D).sup.3 0, 1, 2, 0, -2, -1, 0, . . .______________________________________ TABLE B2______________________________________Sample Value Slicer Output______________________________________y >= T1 +1-T2 <= y < T1 0y < -T2 -1______________________________________ TABLE C2______________________________________State Y(n - 1) Y(n) C1,C0______________________________________+A,-A +y +y 00-A,-A +y -y 01-A,+A -y -y 10+A,+A -y +y 11______________________________________
A sampled amplitude read channel reads data from a magnetic medium by detecting digital data from a sequence of discrete time sample values generated by sampling pulses in an analog read signal from a read head positioned over the magnetic medium. The digital data comprises a preamble field followed by a sync mark followed by a data field. Timing recovery in the read channel synchronizes to a phase and frequency of the preamble field and a sync detector detects the sync mark in order to frame operation of an RLL decoder for decoding the detected data field. To decrease the probability of early misdetection, the sync mark is chosen to have minimum correlation with shifted versions of the sync mark concatenated with the preamble field. To further increase the fault tolerance, the sync mark detector is enabled by timing recovery relative to the end of the preamble field. A timing recovery state machine generates expected sample values used to acquire the preamble field, and a current state of the state machine indicates when the preamble ends relative to a predetermined clock interval. As a result, the search for an appropriate sync mark need only look for minimum correlation during shifts at the predetermined clock interval, thereby increasing the fault tolerant characteristic of the sync mark. In one embodiment, both the sign and magnitude of the data are used in the correlation to further increase the fault tolerance.
6
BACKGROUND OF THE INVENTION 1. Field of the Invention The invention relates to a process for aluminizing steel in which a steel is dipped in a liquid bath containing aluminum. 2. Discussion of the Background When a dipping process is used to provide an aluminum layer on steel, the coating which is obtained on the steel generally is stratified into several layers. These include: an inner layer in contact with the steel, composed of one or more alloys of aluminum from the bath and iron from the steel. It also is referred to as an alloyed layer; and an outer layer, generally thicker, comprising an aluminum-based main phase. Since the inner alloy layer tends to be brittle in nature, steps are generally taken to limit thickness. These include the addition of materials to the dipping baths to inhibit alloying between aluminum and steel. Silicon is the most widely used alloying inhibitor. Its weight concentration in the dipping bath generally ranges between 3 and 13%. In continuous aluminizing processes, the dipping baths are saturated with iron due to a partial dissolution of the steel in the bath. This saturation is known to lead to the formation of mattes and the liquid bath is in equilibrium with the solid phase of these mattes. Under the usual conditions of aluminizing, the two previously cited layers which form the aluminized coating may be more precisely described as follows. The alloyed interfacial layer is composed essentially of a phase designated as τ5 and/or a phase designated as τ6. According to the conditions of aluminizing, this layer may be subdivided into several alloyed sub-layers, particularly in the case of the present invention. The outer layer is composed principally of aluminum in the form of broad dendrites. These dendrites are saturated with iron and, as the case may be, with silicon in solid solution. The τ5 phase has a hexagonal structure and crystallizes in the form of globular grains; it sometimes is referred to as α H or H. The iron content of this phase generally ranges between about 29 and about 36% by weight; the silicon content of this phase generally ranges between about 6 and about 12% by weight; the balance is composed principally of aluminum. The chemical composition corresponds approximately to the formula Fe 3 Si 2 A 12 . The τ6 phase has a monoclinic structure and crystallizes in the form of elongated, flat grains; it sometimes is referred to as β or M. The iron content of this phase generally ranges between about 26 and about 29% by weight; the silicon content of this phase generally ranges between about 13 and about 16% by weight; the balance is composed principally of aluminum. The chemical composition corresponds approximately to the formula Fe 2 Si 2 Al 9 . FIG. 1 is a three-dimensional representation of an Al—Si—Fe ternary phase diagram, where the variations—vertical axis—of the temperature of equilibrium of a liquid phase with different solid phases are designated as follows: FeAl 3 ≡Θ, Fe 3 Si 2 Al 12 ≡τ 5 , Fe 2 Si 2 Al 9 ≡τ 6 , FeSiAl 3 , ≡τ 2 , FeSi 2 Al 4 ≡δ, Al≡aluminum, Si≡silicon, and other phases such as τ 3 τ 4 . The θ phase plays a significant role in the present invention. Its structure is monoclinic and it may contain up to about 6% by weight of silicon in solid solution; the chemical composition therefore corresponds approximately to the formula FeAl 3 . In FIG. 1, Si=0% and Fe=0% which means Al=100%. This Figure makes it possible to establish the nature of the solid phases which are capable of being in equilibrium with an aluminizing bath in the liquid state, in terms of the composition of the bath, and the temperature of the bath at equilibrium. FIG. 2 is a projection of FIG. 1; the liquid-solid equilibrium temperature is determined with the aid of isothermal curves. The temperature interval between each curve is 20° C. Table 1 summarizes the possible composition of the θ, τ5 and τ6 phases. TABLE 1 Composition of the bath and of the main pbases obtained after solidification of the aluminum coating Composition Weight % Al Si Fe Bath >86 3 to 13% Saturation (ex.: 3%) Eutectic 87 12.2 0.8 τ6 Phase 55 to 61 13 to 16 26 to 29 τ5 Phase 55 to 62 6 to 12 29 to 36 θ Phase 52 to 64 0 to 6% 36 to 40 An Al—Si—Fe eutectic with a melting temperature of 578° C. is shown in Table 1. As indicated above, the inner interfacial layer of the aluminum-based coating tends to be brittle and has a tendency to crack at the time of shaping of the aluminized castings. This cracking results in a decrease in the corrosion protection provided by the coating. To obtain coatings which are more resistant to cracking during shaping and to corrosion, it is desirable to limit the thickness of this interfacial layer. According to the prior art, in order to achieve this purpose, the following two conditions should be maintained: 1. dipping the steel casting in the bath at a temperature as low as possible to limit the growth of the interfacial alloy layer; 2. using a liquid aluminizing bath whose composition corresponds, at liquid-solid equilibrium, to the area of existence of the τ 6 or τ 5 solid phases. Condition 2 leads to the use of baths with silicon contents in excess of 7.5%, and preferably 9% (see FIG. 1 and 2 ). According to document EP 0 760 399 (NISSHIN STEEL) and document JP 4 176 854-A (NIPPON STEEL), in a continuous process for aluminizing a steel strip, it is recommended that the strip be immersed at a temperature below the mean temperature of the bath. Thus, for a bath containing 9% silicon with the temperature generally ranging between 650 and 680° C., the immersion temperature of the strip should be at a maximum of 640° C. SUMMARY OF THE INVENTION It is an object of the present invention to provide an improved method for aluminizing steel which yields an appreciably smaller interfacial layer thickness. It is another object of the invention to provide an aluminized steel having an improved Al—Fe—Si alloy layer. These and other objects of the invention have been attained by a process for aluminizing a steel in which the steel is dipped in an aluminum-based liquid bath, wherein the composition and mean temperature of the bath and the temperature of immersion of the steel in the bath, are adjusted to obtain in the immersion zone a local bath temperature and composition which results in an equilibrium with the solid phase designated as θ, the composition of which corresponds approximately to the chemical formula FeAl 3 . The process of the invention also may include one or more of the following: the composition and mean temperature of the bath are adjusted to be in equilibrium with the phase designated as τ 5 or the phase designated as τ 6 , preferably with the τ 6 phase. this liquid bath is saturated with iron. the immersion temperature of the steel is higher than the bath temperature. if the silicon content in the bath is approximately 8%, the immersion temperature ranges between about 700 and about 740° C., preferably about 720° C. if the silicon content in the bath is approximately 9%, the immersion temperature ranges between about 720 and about 765° C., preferably about 730° C. if the silicon content in the bath is approximately 9.5%, the immersion temperature ranges between about 740 and about 760° C., preferably about 740° C. The invention also provides an aluminized steel sheet having an Al—Fe—Si alloy layer and a surface aluminum layer wherein the alloy layer comprises, at the point of contact with the steel substrate, a sub-layer composed essentially of θ phase. The thickness of this alloy layer preferably is less than or equal to about 3 μm. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 represents a three-dimensional Al—Si—Fe ternary phase diagram. FIG. 2 is a projection of FIG. 1, in which the liquid-solid equilibrium temperatures are represented with the aid of isothermal curves 20° C. apart. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The aluminizing process according to the invention now will be described in the context of continuous coating of a steel strip. The aluminizing plant conventionally includes means for cleaning, means for annealing, means for dipping in an aluminizing bath, means for drying the aluminum-based layer produced on the strip, means for cooling and means for moving the strip continuously in the plant. To proceed with aluminizing, there is used, as in the prior art, a bath the composition of which corresponds to the area of existence of the τ 6 or τ 5 phase (condition 2 above). According to the invention, the temperature of the strip when it enters the bath (i.e., the immersion temperature of the strip) is higher than the mean temperature of the bath. Since the strip enters the bath at a temperature higher than that of equilibrium with the τ 6 or τ 5 phase, it causes a local heating of the bath in the strip-immersion zone. This local heating brings about a dissolution of the surface ferrite of the strip and an iron enrichment of the immersion zone. Also in accordance with the invention, the temperature and iron enrichment of the immersion zone should be sufficiently high so that, in this zone, the solid phase capable of being in equilibrium with the liquid phase corresponds to the θ≡FeAl 3 phase. Accordingly, in the immersion zone, the first solid sub-layer being deposited on the steel strip corresponds to the FeAl 3 ≡θphase. Thus, the immersion zone is therefore a zone of the bath which is locally in equilibrium with the θ phase; this immersion zone corresponds to a zone which extends: in thickness, up to a distance of approximately 30 μm from the surface of the strip; in length, along the strip between the starting point of direct contact between the solid surface of the steel and the liquid bath and the point at which the conventional interfacial layer composed of τ 5 or τ 6 phase on the first θ-phase sub-layer characteristic of the invention, begins to solidify. Continuing its progression in the bath after the immersion zone, the strip temperature is at the mean temperature of the bath which corresponds to the temperature of equilibrium with the τ 5 or τ 6 solid phase. In this way the main interfacial layer composed of τ 5 or τ 6 phase, is formed on the first θ-phase sub-layer. At the bath outlet, the strip layer is dried and solidifies on cooling. The aluminized strip thus produced according to the invention, has an interfacial alloyed layer which includes, at the point of contact with the steel surface, a sub-layer composed essentially of the θ phase. In the process of the invention, the main characteristic is a strip-immersion temperature which is both: sufficiently high so that the first solid component formed at the contact surface with the steel crystallizes in the θ phase, sufficiently low to limit the thickness of the interfacial alloyed layer. Even though the immersion temperatures according to the invention are significantly higher than those used in the prior art to limit the thickness of the interfacial alloyed layer, contrary to all expectations, the interfacial alloyed layer obtained according to the invention has a much smaller thickness than that in the prior art. Accordingly, the aluminized strip according to the invention is much more resistive to both corrosion and cracking. Without intending to be confined to any definitive explanation of the invention, it is postulated that, among the alloyed phases, the θ phase might be the one which can be formed most rapidly on the strip at the outset of immersion. This rapid formation is thought to limit the quantity of ferrite which passes into solution in the bath, which also limits the thickness of the alloyed layer. In accordance with the teaching of the previously cited document EP 0 760 399, the prior art has advised practitioners to shorten the duration of immersion and/or the duration between exit from the bath and the end of solidification of the coating. The present invention, provides conditions appropriate for forming the θ phase on the substrate as a priority. The invention is applicable to cold sheets and hot sheets, to all types of steel which can be aluminized by dipping. These include: type IF carbon steels (see example 1), aluminum killed, microalloyed or multiphase steels such as the so-called “Dual Phase” or “TRIPS” steels; ferritic steels comprising between 0.5% and 20% by weight chromium, in particular stainless steels generally comprising between 6% and 20% chromium. Suitable steels may contain alloy elements such as Ti (generally between 0.1% and 1% by weight), and Al (generally between 0.01% and 0.1% by weight), for example ferritic stainless steel referenced as AISI 409. Other addition elements appropriate for the properties sought and/or other residual elements may be present in these steels. When the steel contains these alloying, addition and/or residual elements, the coating obtained on the sheet generally is enriched in these elements. In the case of aluminizing a steel containing at least 0.5% by weight chromium, the invention makes it possible to limit, within an aluminum-based surface layer of the coating, the occurrence of phases enriched in chromium. These phases are related to the previously described τ 5 phase. They generally contain the same proportion of Si as this τ 5 phase, and generally contain more than 5% by weight chromium, usually between 6% and 17% chromium. The presence of this phase in the surface layer of the coating is detrimental to the quality of the coating and the present invention makes it possible to limit if not eliminate this phase in the surface layer of the coating. Advantageously, in the aluminizing process according to the invention, since the strip to be coated is at a temperature higher than that of the bath, the strip may be used to reheat the bath, to offset thermal losses in the bath and/or to maintain the bath at the desired temperature. In terms of energy conservation, this process is advantageous since in the succession of stages through which the strip passes, i.e., annealing, cooling to immersion temperature, dipping, drying, cooling for solidification—a lesser degree of cooling is necessary after annealing than in the prior art. To implement the process, the composition and mean temperature of the bath preferably are adjusted to be in equilibrium with the τ 6 phase. It is noted that the mattes which result from these baths are less likely to adversely affect the quality of the coating obtained than with the mattes which result from other baths and particularly those in which the composition and mean temperature are adjusted to be in equilibrium with the τ 5 phase. To proceed according to this variant, it suffices, in accordance with the indications provided by FIG. 2, to increase the silicon content and/or to lower the mean temperature of the bath. For implementation of the invention, reliance should be placed on the phase diagrams corresponding to the grade of steel used. The boundaries between areas of existence of phases represented in the diagrams of FIGS. 1 and 2 may vary according to the grade of steel used, for example according to the chromium content. The following examples are for illustrative purposes only and are not intended to limit the invention unless stated otherwise. EXAMPLE 1 This example illustrates the invention wherein a steel strip of grade IF-TI (“IF” means “Interstitial Free”, “Ti” means that the carbon in the steel is blocked by titanium) was dipped into a conventional aluminizing bath saturated with iron, containing 9% by weight silicon and maintained at a mean temperature of approximately 675° C. Under these conditions, the bath becomes naturally saturated with iron until the occurrence of solid mattes. The liquid phase of the bath is in equilibrium with the τ 5 ≡Fe 3 Si 2 Al 12 solid phase. Different aluminizing tests were conducted on the steel strips under conditions identical in all respects except for the strip-immersion temperature; the cumulative duration of immersion in the bath and solidification of the coating was on the order of 13 seconds. The thickness of the alloyed interfacial layer of the coating was evaluated in a normal manner; for example, metallographic observations were effected on sections of these samples. Table II summarizes the results obtained in terms of immersion temperature. TABLE II Thickness in terms of strip temperature on immersion. Strip Temperature: 675° C. 720° C. 730° C. 750° C. 765° C. Thickness of the alloyed 5-6 6-7 2-3 4-5 7 layer (μm) On the basis of the teachings of the prior art, with a view to obtaining an interfacial alloyed layer thickness as small as possible, the strip would have been dipped at a temperature lower than or equal to 675° C. (=bath temperature). According to the invention as illustrated by these results, with a view to the same purpose, it is advisable to dip the strip at a temperature higher than 720° C. and lower than 765° C., preferably on the order of 730° C. By referring to FIGS. 1 and 2, it is seen clearly that, for this silicon content (9%), the temperature range indeed corresponds to the area of equilibrium of the iron-saturated bath with the θ solid phase. When one proceeds in this temperature range, in particular at 730° C., there is obtained a coated sheet wherein the interfacial alloyed layer has a sub-layer composed essentially of θ phase directly in contact with the steel, and the remainder of the alloyed layer comprising essentially τ 5 phase. Overall, the total thickness of the alloyed layer is much smaller than in the prior art since, in accordance with the results hereinabove, an average thickness less than or equal to 3 μm is attained. EXAMPLE 2 Proceeding as in Example 1, except that the bath contained 8% by weight silicon and its temperature was maintained at approximately 650° C.: the cumulative duration of immersion in the bath and solidification of the coating was on the order of 11 seconds. Table III summarizes the results obtained in terms of the immersion temperature. TABLE III Thickness in terms of strip temperature on immersion. Strip Temperature: 650° C. 680° C. 720° C. 730° C. 740° C. Thickness of the alloyed 4 5 2-3 3 >3 layer (μm) In this Example, the optimal immersion temperature ranged between 680° C. and 740° C., preferably close to 720° C. According to FIG. 2, in order to reach the area of existence of the θ phase, the temperature should be higher than or equal to approximately 700° C.; the preferred temperature area therefore would correspond to a range of 700°-740° C. EXAMPLE 3 Proceeding as in Example 1, except that the bath contained 9.5% by weight silicon and the temperature was maintained at approximately 650° C.; the cumulative duration of immersion in the bath and solidification of the coating was on the order of 10 seconds. TABLE IV Thickness in terms of strip temperature on immersion. Strip Temperature: 650° C. 700° C. 715° C. 740° C. 765° 760° Thickness of the alloyed layer (μm) 5-6 6-7 7 3 5 7-8 It is noted that the optimal immersion temperature ranged between 715° C. and 760° C., preferably close to 740° C. According to FIG. 2, in order to reach the area of existence of the θ phase, the temperature should be higher than or equal to approximately 740° C.; the preferred temperature area therefore would correspond to a range of 740°-760° C. TABLE V Immersion temperature#in terrns df Si content in the bath. Si content in bath: 8% 9%. 9.5% Immersion temperature range (° C.) 700-740 720-765 740-760 Optimal temperature 720° C. 730° C. 740° C. This application is based on French Application No. 99 02050, filed Feb. 18, 1999, the disclosure of which is incorporated herein in its entirety.
A process in which a steel is dipped in an aluminum-based bath wherein the composition and mean temperature of the bath and the immersion temperature of the steel are adjusted to obtain, in the immersion zone of the steel, a local bath temperature and composition resulting in an equilibrium with the solid phase designated as θ≡FeAl 3 . Dipping is performed at a temperature higher than the temperatures normally employed in the art and a coating is obtained having at the interface with the steel an alloy layer significantly smaller in thickness than the art. The coating obtained better resists cracking and corrosion.
8
BACKGROUND OF THE INVENTION The subject matter of the present invention relates to a method and apparatus for isolating a first section of a wellbore from a second section of the wellbore which is disposed below the first section and adjacent a formation penetrated by the wellbore in order that a wellbore tool string of any desired length may be made up in the first section prior to opening a ball valve, and lowering the tool string downhole into the second section of the wellbore for performing one or more wellbore operations downhole in the second section. When performing wellbore operations downhole, it is necessary to first make up a tool string at the surface of the wellbore prior to lowering that tool string downhole for performing the wellbore operations. In the past, the length of the tool string was limited and a longer tool string length was often desired. Therefore, when the tool string performed the wellbore operations downhole, that tool string was raised uphole and another, second tool string was made up at the surface of the wellbore. The second tool string was lowered downhole for performing additional wellbore operations. However, it is time consuming and expensive to continually make up additional tool strings at the wellbore surface, following the performance of the initial wellbore operation by the first tool string, and sequentially lower those additional tool strings downhole for performing additional wellbore operations. It would be desirable to make up one tool string having the desired length at the wellbore surface and to lower that desired tool string downhole for performing a wellbore operation during one trip into the wellbore. For example, when the tool strings include perforating guns, in the past, it was necessary to implement the following perforating procedure when perforating long length intervals of a wellbore: perforate the long length interval during multiple trips into the wellbore by making up, at the wellbore surface, a first perforating gun having a limited first length, lowering the first perforating gun downhole, perforating a formation penetrated by the wellbore, raising the first perforating gun uphole (or dropping that perforating gun to the bottom of the wellbore), making up a second perforating gun having another second limited length at the wellbore surface, lowering the second perforating gun downhole, perforating another section of the formation, raising the second perforating gun uphole (or dropping it to a bottom of the wellbore), etc. The above referenced perforating procedure is time consuming and costly. As a result, it became necessary to design a method and apparatus for creating a tool string, of any desired length, uphole at the surface of the wellbore, so that the tool string may be lowered downhole and wellbore operations performed downhole during only one trip into the wellbore. U.S. Pat. No. 5,509,481 to Huber et al discussed one method for perforating long length intervals of a formation during a single run into the wellbore. The Huber apparatus disclosed an automatic release apparatus which would disconnect one part of a long gun string from a second part of the gun string just before the perforating guns of that gun string would detonate. Another prior pending application also discloses a method and apparatus for making up, at the wellbore surface, a tool string of any desired length prior to lowering that tool string downhole for performing a wellbore operation in the wellbore during one trip into the wellbore. In a prior pending application entitled "Completions Insertion and Retrieval Under Pressure (CIRP) Apparatus including the Snaplock Connector", filed on Apr. 25, 1996, corresponding to attorney docket number 22.1183, and corresponding to a prior filed provisional application Ser. No. 60/010,500 filed Jan. 24, 1996 (hereinafter, the "CIRP application"), a tool string of any desired length is built uphole prior to lowering that tool string downhole by first holding a first tool, having a first and a second section of a snaplock connector connected thereto, in a deployment BOP or snaplock operator while suspending a second tool, also having a third section of the snaplock connector connected thereto, by wireline in a lubricator. The second tool is lowered down through the lubricator and through a master valve by operating a winch until the third section of the snaplock connector on the second tool connects to the second section of the snaplock connector on the first tool thereby forming a first tool string having a length which corresponds to the first tool and the second tool. The hold by the deployment BOP is released from the first tool, the first tool string is lowered, and the deployment BOP grips the second tool. The second tool also includes another first, second, and third section of a snaplock connector connected to its opposite side, the third section (called a deployment stinger) being connected to the wireline. The deployment stinger is raised uphole by operating the winch, and it is replaced by a third tool, such as a firing head, which also includes a third section of a snaplock connector. The third tool suspends by the wireline in the lubricator and it is lowered downhole and attached to the second tool being held by the deployment BOP. The hold by the deployment BOP on the second tool is released, and a resultant tool string of the desired length, consisting of the first tool, the second tool, and the third tool, is lowered downhole for the purpose of performing wellbore operations downhole during one trip into the wellbore. However, another alternate apparatus, and corresponding method, is needed for isolating the formation downhole by means of closing a valve so that wellhead pressure can be bled off for building a long tool string uphole of any desired length and lowering that tool string downhole without a need for snubbing under wellhead pressure for the purpose of performing wellbore operations downhole during a single trip into the wellbore. SUMMARY OF THE INVENTION Accordingly, it is a primary object of the present invention to provide another alternate method and apparatus for building a tool string uphole of any desired length prior to lowering that tool string downhole for the purpose of performing wellbore operations downhole during a single trip into the wellbore. It is a further object of the present invention to provide another alternate method and apparatus for building a tool string uphole of any desired length prior to lowering that tool string downhole for the purpose of performing wellbore operations downhole during a single trip into the wellbore, the alterate apparatus including a valve, such as a ball valve, initially disposed in an open position adapted to be changed from the open position to a closed position when a shifting tool is run through the center of the valve; and a hydraulic section including a rupture disc assembly and a pair of chambers separated by an oil metering orifice, responsive to the closure of the valve by the shifting tool, and further responsive to the further running of the shifting tool through the center of the hydraulic section for changing the valve back from the closed position to the open position thereby reopening the valve in response to a predetermined internal tubing pressure that is greater than a predetermined threshold pressure value. In accordance with these and other objects of the present invention, the formation isolation valve of the present invention can be used for building a tool string uphole of any desired length for the purpose of performing wellbore operations downhole during one trip into the wellbore. The formation isolation valve having a full bore includes a valve, such as a ball valve, assumed to be initially disposed in the open condition and a hydraulic section. A shifting tool, run at the end of the perforating guns, is pulled out through the full bore of the valve of the formation isolation valve after the guns are fired and the well is perforated. An outer periphery of the shifting tool hooks onto the end of a collet finger that is connected to the valve. As the shifting tool comes up through the full bore of the valve, the periphery of the shifting tool forces the end of the collet finger to move in a direction which effectively closes the valve. After the valve is closed, a pressure existing in the area above the valve can now be bled off. When the pressure in the area above the valve is bled off, the tool string (perforating gun and shifting tool) can be retrieved to the surface with the well shut-in downhole and with wellhead pressure bled off. When the shifting tool is retrieved to the surface, the shifting tool continues its run up through the center of the formation isolation valve, and, as a result, the outer periphery of the shifting tool hooks onto the end of another collet finger of an isolation latch assembly thereby pulling a first port into alignment with another, second entry port. At this point, before operating the hydraulics section, the shifting tool can be re-run down through the formation isolation valve thereby re-opening the valve and it can be re-run up through the formation isolation valve thereby re-closing the valve. Since the hydraulics section has not yet been operated, the rupture discs of the hydraulics section have not yet been ruptured. Whenever the shifting tool is run down through the formation isolation valve, the valve opens and whenever the shifting tool is pulled out of the formation isolation valve, the valve is re-closed. Now, when another tool string of any desired length (e.g., a tool string which is longer in length than the length of a wellhead lubricator) is disposed inside the area above the valve, it is now necessary to lower that tool string downhole for the purpose of performing wellbore operations. At this point, it is necessary to reopen the valve so that the tool string can be lowered downhole for performing the wellbore operations. In order to reopen the valve, since the rupture discs of the hydraulics section have not yet been ruptured, it is necessary to initiate the operation of the hydraulics section and rupture the rupture discs. The hydraulics section can be used only once; therefore, it should not be operated until the tool string of any desired length must be lowered downhole. Recall that, when the shifting tool continued its run up through the center of the formation isolation valve, the outer periphery of the shifting tool hooked onto the end of another collet finger of an isolation latch assembly thereby pulling a first port into alignment with another, second entry port. In order for the shifting tool to initiate the operation of the hydraulics section, since the two ports have fallen into alignment with one another, an internal tubing pressure enters the ports and that pressure is exerted against a rupture disc. When the internal tubing pressure is greater than or equal to a predetermined threshold pressure value associated with that rupture disc, the rupture disc will rupture. When the rupture disc ruptures, a piston begins to move downwardly in response to the internal tubing pressure thereby forcing an oil in a first oil chamber to move through an oil metering orifice to a second chamber. When all of the oil meters through the orifice to the second chamber, the piston bottoms out. When the piston bottoms out, the valve has been reopened. When the valve is reopened, the tool string of any desired length, which is disposed inside the area above the valve, can now move through the valve to an area below the valve in the wellbore for performing the wellbore operations in the area below the valve. The wellbore operations are performed during a single trip into the wellbore. In addition, when the piston bottoms out, the piston cannot be moved upwardly because the pressure existing on the top side of the piston is greater than the pressure existing on the bottom side of the piston. As a result, in order to allow the piston to be moved upwardly when it bottoms out, a second rupture disc, located on a side opposite the first rupture disc, will rupture. When the second rupture disc ruptures, the pressure existing on the bottom side of the piston becomes equal to the pressure existing on the top side of the piston. When the two pressures existing on the top side and the bottom side of the piston are equal, the piston can now be moved upwardly for reclosing the valve. To be more specific, the formation isolation valve (FIV) of the present invention consists of a ball valve, upper and lower ball valve supports, a ball valve seal, a ball valve operator, and a spring. The ball valve is rotated to the closed position by moving the ball operator down. The ball valve operator is connected to a latch assembly. The latch assembly consists of two sets of collets, an upper collet for closing the ball valve when in the engaged position and a lower collet for opening the ball valve when in the engaged position. Each collet consists of multiple fingers which move radially inwardly when passed through a small inner diameter and then return back to its natural free position when in open space. A certain force is required to move the collet from the unlatched to the latched position. A hydraulic section consists of an upper and a lower oil chamber which are interconnected together by an oil metering orifice. The orifice provides a time delay. A first pressure isolation device (first rupture disc) is fitted in a power piston for the purpose of connecting pressures in both oil chambers at the end of the operator mandrel downstroke. A pressure transfer section consists of a housing, rupture disc, and an isolation latch assembly, similar to the latch mandrel assembly. The rupture disc prevents the tubing pressure from acting on the power piston until the rupture disc is ruptured. The isolation latch assembly prevents the tubing pressure from acting on the rupture disc until the isolation latch assembly is shifted up and the pressure port is exposed to tubing pressure. The purpose of the isolation latch assembly is to protect the rupture disc from premature rupturing due to high pressure spikes generated during firing of the perforating guns. A shifting tool consists of a mandrel and a collet. The collet of the shifting tool consists of multiple fingers which move radially inwardly when passed through a restriction and then move back to its natural position when removed from the restriction. Two types of collets are used: a collet with ledges on both sides of a groove for opening and closing the ball valve, and a collet with a ledge only on the top side for opening the ball valve. The shifting tool is decoupled from the gun string, and is free to move and rotate. The purpose of decoupling is to minimize the wear on the collet fingers. An upper centralizer is fixed to the gun string and it takes wear due to the weight of the horizontal gun and tubing string. The load does not transfer to the shifting tool collet fingers. The functional operation of the formation isolation valve of the present invention is briefly summarized as follows. The formation isolation valve (FIV) is run into the wellbore in an open position. A perforating gun is run through the full bore of the FIV and the wellbore is perforated. When the perforating gun is fired, the inner diameter of the FIV is filled with wellbore fluid. After firing the perforating gun, the tubing is snubbed out under wellhead pressure and the perforating gun is raised uphole until the collet on the shifting tool connected to the perforating gun latches onto the upper collet fingers of the latch assembly. An upward 2000 pound pull is applied in order to disengage the fingers of the lower collet. As a result, the latch assembly and the ball valve operator move up thereby closing the ball valve. The shifting tool is disengaged from the upper collet fingers when the fingers move radially outward and into the groove in the latch housing inner diameter. Then, the tubing pressure is bled off and the ball valve seal is pressure tested with shut in pressure from below (500 psi higher than tubing pressure in this case). It can also be pressure tested from above since the ball valve holds pressure from both directions. During the time when the guns and the shifting tool are pulled out, the shifting tool collet will engage with the isolation latch assembly and move it upwardly thereby uncovering the pressure port. The first rupture disc is now exposed to the tubing pressure. The tubing and guns are retrieved to the surface with the tubing pressure bled off. At some time later, in order to reopen the ball valve and flow the well, the tubing pressure is increased to rupture the first rupture disc. When the first rupture disc is ruptured, the operator mandrel starts to move down with time delay. Oil starts to meter from the oil chamber to the atmospheric chamber through the oil metering orifice. After five minutes of time delay, the time delay device is disabled (oil no longer meters slowly through the oil metering orifice) and the operator mandrel moves down at a rapid rate. This five minutes of time delay is enough time to bleed off the tubing pressure to prevent formation damage when the ball valve opens. At the end of the time delayed stroke, the operator mandrel engages with the latch assembly and the ball operator and pushes it down. The ball valve is now open and the latch assembly is locked in place. At the end of the stroke, the power piston bottoms out on the oil housing which creates a differential pressure across the second rupture disc (atmospheric pressure on the oil chamber side and tubing pressure on the other side), and this differential pressure ruptures the second rupture disc. This disables the function of the piston mandrel (same pressure on both sides of the piston mandrel). A further application of a high pull will push the collet fingers on the shifting tool radially inwardly thereby disengaging the shifting tool from the latch assembly in the event the shifting tool cannot be unlatched from the latch assembly with the application of a normal pull. This feature allows the shifting tool to be removed in the event of a downhole tool malfunction. Further scope of applicability of the present invention will become apparent from the detailed description presented hereinafter. It should be understood, however, that the detailed description and the specific examples, while representing a preferred embodiment of the present invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become obvious to one skilled in the art from a reading of the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS A full understanding of the present invention will be obtained from the detailed description of the preferred embodiment presented hereinbelow, and the accompanying drawings, which are given by way of illustration only and are not intended to be limitative of the present invention, and wherein: FIG. 1 illustrates a wellbore including a shifting tool and a formation isolation valve (FIV) of the present invention; FIGS. 2-4 illustrate the FIV in a run-in open position, a closed position, and an open (i.e., re-opened) position; FIGS. 5a and 5b illustrate the shifting tool used in conjunction with the FIV of FIGS. 1-4; FIG. 6 illustrates a cross section of the shifting tool of FIG. 5b taken along section lines 6--6 of FIG. 5b; FIG. 7 illustrates a cross section of the shifting tool of FIG. 5b taken along section lines 7--7 of FIG. 5b; FIG. 8 illustrates a cross section of the shifting tool of FIG. 5a taken along section lines 8--8 of FIG. 5a; FIGS. 9a-9d illustrate a more detailed construction of the FIV of FIGS. 1 and 2-4; and FIGS. 10a and 10b illustrate the groove 17 of the collet 16d1 shown in FIG. 5b of the drawings. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT Referring to FIG. 1, a wellbore is illustrated in which the formation isolation valve (FIV) and the shifting tool of the present invention is illustrated. In FIG. 1, a perforating gun 10 connected to the end of a tubing string 14, or to the end of a coiled tubing 14, is disposed in a horizontal or deviated wellbore 12. A shifting tool 16, part of the present invention, is connected to a bottom part of the perforating gun 10. In addition, a formation isolation valve (FIV) 18 surrounds the tubing string or coiled tubing 14 in FIG. 1. The FIV 18 includes a valve 18a. When the perforating gun 10 is raised uphole, the FIV 18 surrounds the shifting tool 16 in FIG. 1 (that is, when the perforating gun 10 is raised uphole, the shifting tool 16 is enclosed by the FIV). The FIV 18 is part of the formation or casing when the perforating gun 10 suspends from a tubing string, the FIV 18 being part of the tubing string when the perforating gun 10 suspends from a coiled tubing. In operation, referring to FIG. 1, the perforating gun 10 perforates the formation 20 penetrated by the wellbore 12. Then, the perforating gun 10 is raised uphole following the perforating operation. The perforating gun 10 eventually passes through the FIV 18 in FIG. 1, and then the shifting tool 16 passes through and is enclosed by the FIV 18 in FIG. 1. Assuming that the valve 18a is initially disposed in the open position, when the shifting tool 16 passes through the FIV 18, the shifting tool 16 closes the valve 18a of the FIV 18 thereby changing the valve 18a from the open position to the closed position. The shifting tool 16 in the FIV 18 remains stationary. Now that the valve 18a is closed, the area 22 above the closed valve 18a in the wellbore 12 can be used to build a tool string of any desired length. Assuming that a new tool string is built in the area 22 with the valve 18a closed, it is time to lower that new tool string downhole for performing a new wellbore operation. Before the new tool string can be lowered downhole, the valve 18a must be reopened. Recalling that the shifting tool 16 remained stationary in the FIV 18, in order to reopen the valve 18a, the shifting tool 16 is raised uphole once again. When the shifting tool 16 is raised uphole, an internal tubing pressure, inside the coiled tubing or tubing string 14, is increased. When the internal tubing pressure is increased beyond a predetermined threshold pressure value, and after a period of time elapses following the increase of the internal tubing pressure beyond the threshold pressure value, the valve 18a will reopen. Now, the new tool string may be lowered downhole for performing the new wellbore operation. Alternatively, the FIV 18 and associated shifting tool 16 may be used to simply open and close the valve 18a for purposes of conducting a simple drill stem test. Referring to FIGS. 2-4, a simplified construction of the formation isolation valve (FIV) 18 of the present invention is illustrated. FIG. 2 illustrates the FIV 18 in its initial run-in position, FIG. 3 illustrating the FIV 18 in its closed position, and FIG. 4 illustrating the FIV 18 in its reopened position. In FIG. 2, the valve 18a of the FIV 18 of the present invention is actually a ball valve 18a that is connected to a ball operator 18b. The ball operator 18b includes a pair of grooves 18b1 in which a detent 18b3 is disposed. An upward longitudinal movement of the ball operator 18b will cause the detent 18b3 to move out of one groove and fall into the other groove of the pair of grooves 18b1 and then the ball operator 18b will rotate the ball valve 18a from the run-in open position shown in FIG. 2 to the closed position shown in FIG. 3. In addition, an operator mandrel 18c includes a piston 18c1, and the piston 18c1 includes a second rupture disc. A fluid communication channel 18d is interconnected between a first rupture disc, which is responsive to a fluid pressure inside the internal full bore of the FIV, and the piston 18c1. The fluid pressure inside the internal full bore of the formation isolation valve exerts itself against the first rupture disc. When the fluid pressure inside the full bore of the FIV 18 is greater than or equal to a predetermined threshold pressure value established by the first rupture disc, the first rupture disc ruptures and the fluid pressure inside the internal full bore of the FIV will travel through channel 18d and will be exerted against the piston 18c1. Below the piston 18c1, an oil chamber 18e fluidly communicates with an atmospheric chamber 18f via an oil metering orifice 18g. When the fluid pressure inside the full bore of the FIV 18 is exerted against the piston 18c1, the piston 18c1 and the operator mandrel 18c will move, and, in response to movement of the piston 18c1, the oil in the oil chamber 18e will start to meter slowly through the oil metering orifice 18g and into the atmospheric chamber 18f, this metering of the oil through the orifice 18g establishing a five minute time delay period (that is, it takes 5 minutes for the oil in the oil chamber 18e to meter through the orifice 18g and into the atmospheric chamber 18f). When this five minute period has elapsed, the operator mandrel 18c will have moved longitudinally from its uppermost position shown in FIG. 3 to its lowermost position shown in FIG. 4. The downward movement of the operator mandrel 18c will also cause the ball operator 18b to move downwardly from its position shown in FIG. 3 to its position shown in FIG. 4. When the ball operator 18b moves to its position shown in FIG. 4, the ball valve 18a will have rotated thereby changing from the closed position shown in FIG. 3 to the open position shown in FIG. 4. A more detailed construction of the formation isolation valve 18 and the shifting tool 16 of the present invention will be set forth in the following paragraphs with reference to FIGS. 5a through 9d of the drawings. Referring to FIGS. 5a, 5b, 6, 7, and 8 of the drawings, the shifting tool 16, which comprises a part of the present invention, is illustrated. In FIG. 5b, the shifting tool 16 includes a collet mandrel 16a, a locking nut 16b secured to the collet mandrel 16a, an end cap 16c, which functions as a centralizer, also secured to the collet mandrel 16a, a collet member 16d threadedly secured to the locking nut 16b, and an opening/closing collet 16d1 integrally connected to the collet member 16d, the opening/closing collet 16d1 including a groove 17 disposed circumferentially around the outer periphery of the collet 16d1. In FIG. 5b, a split nut 16e, which functions as a decoupler, is secured to the collet mandrel 16a, and a top sub 16f is secured to the split nut 16e. In FIG. 5a, the end of the top sub 16f also includes a centralizer 16g. Therefore, the end cap 16c of FIG. 5b includes a centralizer 16c1, and the top sub 16f of FIG. 5a also includes a centralizer 16g. In FIG. 6, a cross sectional view of the end cap 16c is shown. In FIG. 7, a cross sectional view of the collet 16d1 including the groove 17 is illustrated. In FIG. 8, a cross sectional view of the centralizers 16g of the top sub 16f is illustrated. Note that, in the following description, the groove 17 disposed around the outer periphery of the collet 16d1 in FIG. 5b will be used to open and close the ball valve 18a. Referring to FIGS. 9a-9d, a detailed construction of the formation isolation valve (FIV) 18 of the present invention, which utilizes the shifting tool 16 of FIGS. 5a-5b, is illustrated. In FIG. 9c, the FIV 18 includes a ball valve 18a and a ball operator 18b connected to the ball valve 18a. Movement of the ball operator 18b will rotate the ball valve 18a thereby opening and closing the ball valve 18a. The ball operator 18b is also shown in FIG. 9c. In addition, in FIG. 9c, a pair of collet fingers 24 are connected to the ball operator 18b and include a first collet finger and a second collet finger, the first collet finger having a first end 24a, the second collet finger having a second end 24b, the second end 24b being adapted to be disposed in its own detent 24b1 which is shown in FIG. 9c. The pair of collet fingers 24 will move longitudinally when the shifting tool 16 is run through the center of the FIV 18. When the collet fingers 24 move longitudinally in FIG. 9c through the FIV 18, the ball operator 18b is also moved longitudinally in the same direction. Furthermore, in FIG. 9c, an outer housing 26 includes an interior groove 26a which is adapted to receive the first end 24a of the collet finger 24 when the collet finger 24 and the ball operator 18b are moved longitudinally within the FIV 18 (recall the ball valve 18a rotates to either the closed or open position when the ball operator 18b moves longitudinally within the FIV 18). In FIGS. 9a and 9b, starting with FIG. 9b, an operator mandrel 18c includes a piston 18c1 which moves longitudinally when the operator mandrel 18c moves longitudinally within the FIV 18. The piston 18c1 further includes a second rupture disc 28 disposed longitudinally through the piston 18c1. On the other hand, a rupture disc sub 32 in FIG. 9b includes a fluid communication channel 18d disposed longitudinally through the sub 32, the channel 18d being fluidly interconnected between an entry port 36, in FIG. 9a, which is disposed adjacent the internal full bore of the FIV 18 and a first rupture disc 30 in FIG. 9b. Furthermore, in FIG. 9b, the rupture disc sub 32 and the operator mandrel 18c define a fluid chamber 18e filled with a fluid, such as oil. That side of the operator mandrel 18c which is disposed inside the fluid chamber 18e includes a cut 18c2 which has a length "d", as shown in FIG. 9b. In addition, a seal or o-ring 18c3 in FIG. 9b is disposed firmly in contact with said side of the operator mandrel 18c which is disposed inside the oil chamber 18e. When the cut 18c2 is disposed adjacent the o-ring 18c3 in FIG. 9b, the cut 18c2 will allow oil in the oil chamber 18e to quickly flow from the oil chamber 18e to the atmospheric chamber 18f at a more rapid rate. In addition the rupture disc sub 32 and the operator mandrel 18c further define an atmospheric chamber 18f and a fluid metering orifice 18g which is disposed between the fluid chamber 18e and the atmospheric chamber 18f. The fluid metering orifice 18g is designed to meter any fluid from the fluid chamber 18e slowly through the fluid metering orifice 18g to the atmospheric chamber 18f in response to movement of the piston 18c1. Functionally, when the operator mandrel 18c moves, the piston 18c1 also slowly moves. As the piston 18c1 moves, the fluid in the fluid chamber 18e will meter slowly through the fluid metering orifice 18g to the atmospheric chamber 18f. However, when the cut 18c2 in the operator mandrel 18c is disposed adjacent the o-ring 18c3, the operator mandrel 18c and the piston 18c1 will move very rapidly. As a result, when the cut 18c2 is disposed adjacent the o-ring 18c3, the piston 18c1 will very quickly bottom out against one end 18g1 of the fluid metering orifice 18g. In FIG. 9a, a longitudinally movable isolation latch assembly 34 initially blocks the entry port 36. The isolation latch assembly 34 includes a port 38 which is adapted to move into alignment with the entry port 36 in the rupture disc sub 32 when the isolation latch assembly 34 moves longitudinally within the FIV 18. The isolation latch assembly 34 includes a pair of collet fingers, the first collet finger of the isolation latch assembly 34 having a first end 34a, the second collet finger of the isolation latch assembly having a second end 34b, the second end 34b being adapted to be disposed in its own detent 34b1 which is shown in FIG. 9a. The isolation latch assembly 34 will move longitudinally when the shifting tool 16 of FIGS. 5a-5b is run through the center of the FIV 18 and catches the first or second end 34a or 34b of the collet fingers of the isolation latch assembly 34, as discussed below. Referring to FIGS. 10a and 10b, starting with FIG. 10a, the groove 17 of the collet 16d1 of FIG. 5b is illustrated. In FIG. 10a, the groove 17 of collet 16d1 includes a first ledge 17a and a second ledge 17b. However, in FIG. 10b, the groove 17 only includes the first ledge 17a, not the second ledge 17b. In FIG. 10a, the second ledge 17b is used to close the ball valve 18a of FIG. 9b since the second ledge 17b of groove 17 contacts the first end 24a of the collet fingers 24 in FIG. 9c when the shifting tool 16 runs through the center of the FIV of FIG. 9c, the second ledge 17b pushing the first end 24a upwardly and closing the ball valve 18a. The second ledge 17b also contacts the first end 34a of the isolation latch assembly 34 in FIG. 9a thereby moving the port 38 into alignment with the entry port 36 in FIG. 9a (see discussion below). On the other hand, the first ledge 17a of FIG. 10a will contact the second end 34b in FIG. 9a thereby moving the port 38 out of alignment with the entry port 36, and the first ledge 17a will also contact the second end 24b in FIG. 9c thereby reopening the ball valve 18a, as discussed below. In FIG. 10b, since there is no second ledge 17b, there is no second ledge 17b to contact the first end 24a in FIG. 9c for closing the ball valve 18a in FIG. 9d, and there is no second ledge 17b for contacting the first end 34a in FIG. 9a for moving the port 38 into alignment with the entry port 36 in FIG. 9a. A functional description of the operation of the formation isolation valve (FIV) 18 of the present invention, when used in conjunction with the shifting tool 16 of FIGS. 5a-5b, is set forth below with reference to FIGS. 1, 5a, 5b, and 9a through 9d of the drawings. In FIG. 1, the perforating gun 10 and the shifting tool 16 suspend from the tubing string 14 in the wellbore 12. The perforating gun 10 has already perforated the formation penetrated by the wellbore 12, as shown in FIG. 1. The valve 18a is open, and the operator at the wellbore surface is withdrawing the perforating gun 10 to the surface of the wellbore. Since the shifting tool 16 is connected to a bottom of the perforating gun 10, the shifting tool 16 is also being withdrawn to the surface of the wellbore. Eventually, the shifting tool 16, connected to the bottom of the perforating gun 10, enters the formation isolation valve (FIV) 18 in FIG. 1 and runs through the center of the FIV 18. As the collet 16d1 of the shifting tool 16 (of FIG. 5b) enters the FIV 18 and runs through the center thereof, the collet 16d1 of shifting tool 16 will pass through: the ball valve 18a of FIG. 9b, the ball operator 18b of FIG. 9c, and the collet fingers 24 of FIG. 9c. When the collet 16d1 of shifting tool 16 passes through the collet fingers 24 in FIG. 9c, the groove 17 in the collet 16d1 of the shifting tool 16 will surround the first end 24a of the collet fingers 24 in FIG. 9c. As the shifting tool 16 continues to run through the center of the FIV 18, because the groove 17 surrounds the first end 24a of the collet finger 24, the groove 17 of collet 16d1 will force the collet fingers 24 of FIG. 9c to move longitudinally in an upward direction in the FIV 18. When the collet finger 24 moves longitudinally in the upward direction in the FIV, the ball operator 18b of FIG. 9c also moves longitudinally in the upward direction in the FIV 18. Since the ball operator 18b is connected to the ball valve 18a, movement of the ball operator 18b in the upward direction will rotate the ball valve 18a. Since the ball valve 18a was initially disposed in an open position, rotation of the ball valve 18a will close the ball valve 18a. When the ball valve 18a closes in response to a rotation of the ball valve 18a and movement of the ball operator 18b, the first end 24a of the collet finger 24 in FIG. 9c will fall into the interior groove 26a in the outer housing 26. When the first end 24a of collet finger 24 falls into the interior groove 26a of the outer housing 26, the groove 17 of the collet 16d1 of the shifting tool 16 will no longer surround the first end 24a of the collet finger 24. The shifting tool 16 and associated perforating gun 10 is now free to continue its upward movement longitudinally through the interior full bore of the FIV 16. The ball valve 18a, at this point, is closed; however, the collet 16d1 of shifting tool 16 is still disposed adjacent the the interior groove 26a in FIG. 9c. The upward movement of the shifting tool 16 through the center full bore of the FIV 18 of FIGS. 9a, 9b, and 9c continues. As the upward movement of the shifting tool 16 continues, the groove 17 of the collet 16d1 of the shifting tool 16 will now surround the first end 34a of the first collet finger of the isolation latch assembly 34 in FIG. 9a. As a result, any further upward movement of the shifting tool 16 will also force the isolation latch assembly 34 to move upward (because the groove 17 of collet 16d1 of the shifting tool 16 will force the first end 34a of the first collet finger of the assembly 34 to move upward, and the upward movement of the first end 34a in FIG. 9a will cause the isolation latch assembly 34 to move upward). When the isolation latch assembly 34 moves upwardly, the port 38 in the isolation latch assembly 34 will move into alignment with the entry port 36 in the rupture disc sub 32. When the port 38 moves into alignment with the entry port 36, the fluid communication channel 18d in FIG. 9a is open to the fluid pressure existing inside the full bore of the FIV 18 and, since the valve 18a is currently in the closed position, the valve 18a can now be reopened when the full bore fluid pressure is greater than or equal to the threshold pressure value rating of the first rupture disc 30 in FIG. 9b. In the meantime, the perforating gun 10 and shifting tool 16 are withdrawn to the surface of the wellbore, and, as a result, the first end 34a of the first collet finger of the isolation latch assembly 34 falls into the interior groove 32a on the interior of the rupture disc sub 32 while the second end 34b moves radially inwardly since it moves out of its own detent 34b1. Assume that the operator at the wellbore surface notices that the perforating gun 10 did not detonate and there may not be any perforations in the formation 20 penetrated by the wellbore 12. It is necessary to lower another perforating gun downhole to perforate the formation. Another shifting tool 16 is connected to the lower part of another perforating gun 10 and the gun suspends from a tubing string 14. The perforating gun 10 and the shifting tool 16 are lowered into the wellbore, the shifting tool 16 being connected to the lower part of the perforating gun 10. As the perforating gun 10 and the shifting tool 16 is lowered downhole, the groove 17 of the collet 16d1 of the shifting tool 16 surrounds the second end 34b of the second collet finger of the isolation latch assembly 34 in FIG. 9a (recall that the second end 34b is not disposed in its own detent 34b1). As the shifting tool 16 moves downwardly, the groove 17 in collet 16d1 forces the second end 34b to move downwardly. As a result, the port 38 moves out of alignment with the entry port 36. Eventually, the second end 34b falls back into its own detent 34b1 in FIG. 9a and, as a result, the shifting tool 16 may now continue its downward descent into the borehole. During the downward descent of the shifting tool 16, the groove 17 of the collet 16d1 of the shifting tool 16 now begins to surround the second end 24b of the second collet finger 24 in FIG. 9c (recall that the second end 24b is not disposed in its own detent 24b1). The second collet finger 24 is connected to the ball operator 18b. Therefore, as the shifting tool 16 moves downwardly, the groove 17 forces the second end 24b of the collet finger 24 to move downwardly, and, since the collet finger 24 is connected to the ball operator 18b, when the collet finger 24 moves downwardly, the ball operator 18b moves downwardly thereby rotating the ball valve 18a. Since the ball valve 18a is currently closed, any rotation of the ball valve 18a will reopen the ball valve 18a. Eventually, the second end 24b of the collet finger 24 falls back into its own detent 24b1 and, as a result, the perforating gun 10 and the shifting tool 16 can be lowered downhole, through the open valve 18a, for the purpose of perforating the formation 20 penetrated by the wellbore 12. Assume now that the perforating gun 10 did, in fact, perforate the formation 20. It is necessary to withdraw the perforating gun 10 and shifting tool 16 uphole, and reclose the ball valve 18a, so that a tool string of any desired length may be built in the space 22 above the closed ball valve 18a of FIG. 1. In order to reclose the ball valve 18a, the same procedure outlined above is utilized. That is, the perforating gun 10 and shifting tool 16 are withdrawn to the surface of the wellbore 12. The groove 17 in the collet 16d1 of the shifting tool 16 will catch and surround the first end 24a of the collet fingers 24 in FIG. 9c thereby pulling the first end 24a, the collet fingers 24, and the ball operator 18b upwardly to the surface of the wellbore 12. The upward movement of the ball operator 18b will reclose the ball valve 18a. The first end 24a of the collet finger 24 will fall into the interior groove 26a in FIG. 9c, and the groove 17 of the collet 16d1 will be released from the first end 24a and the collet 16d1 will continue its travel uphole. The ball valve 18a is now closed. The groove 17 in the collet 16d1 will catch and surround the first end 34a of the isolation latch assembly 34 in FIG. 9a thereby forcing the first end 34a upwardly, forcing the isolation latch assembly 34 upwardly, and forcing the port 38 in the isolation latch assembly 34 to move into alignment with the entry port 36 in the rupture disc sub 32 of FIG. 9a. The first end 34a falls into the interior groove 32a in the rupture disc sub 32, and the perforating gun 10 and shifting tool 16 are withdrawn to the surface of the wellbore 12. Since the formation 20 was, in fact, perforated as shown in FIG. 1, space 22 in FIG. 1 is now empty, and a tool string of any desired length may now be built inside the space 22 which is disposed above the closed ball valve 18a in FIG. 1. When the tool string of any desired length is built in space 22 of FIG. 1, and when it is necessary to lower such tool string downhole for the purpose of performing a wellbore operation, and recalling that the valve 18a is now closed, it is necessary to reopen the valve 18a. However, the shifting tool 16 is not connected to the tool string. As a result, it is necessary to reopen the ball valve 18a using a different method for opening the valve. Recall that, in FIG. 9a, the port 38 is aligned with the entry port 36 in the rupture disc sub 32. However, the fluid pressure in the FIV 18 (and the rupture disc sub 32) is currently below the threshold pressure value rating of the rupture disc 30 in FIG. 9b. In order to reopen the ball valve 18a, the pressure inside the FIV 18, and inside the fluid channel 18d of FIG. 9b, is increased above the threshold pressure value rating of the rupture disc 30 in FIG. 9b. As a result, the rupture disc 30 in FIG. 9b ruptures. Since the rupture disc 30 has ruptured, the fluid pressure inside the channel 18d is exerted against the piston 18c1 of the operator mandrel 18c in FIG. 9b. As a result, the piston 18c1 starts to move downwardly in FIG. 9b. The oil in the oil chamber 18e starts to meter slowly through the oil metering orifice 18g and into the atmospheric chamber 18f. However, when the cut 18c2 on that side of the operator mandrel 18c inside the oil chamber 18e is disposed adjacent the o-ring 18c3, the cut 18c2 will allow the oil in the oil chamber 18e to move very rapidly into the atmospheric chamber 18f. As a result, when the oil in oil chamber 18e meters slowly through the oil metering orifice 18g and into the atmospheric chamber 18f, a time delay occurs. That is, it takes a predetermined period of time (the time delay) for the oil in the oil chamber 18e to meter slowly through the oil metering orifice 18g into the atmospheric chamber 18f, and during that time, the piston 18c1 moves slowly and the operator mandrel 18c moves slowly. However, when the cut 18c2 in FIG. 9b reaches the o-ring seal 18c3, the oil in the oil chamber 18e moves very rapidly into the atmospheric chamber 18f and, as a result, the piston 18c1 moves very rapidly and it rapidly bottoms out against one end 18g1 of the oil metering orifice 18g. When the piston 18c1 bottoms out against the one end 18g1 of the oil metering orifice 18g, the operator mandrel 18c of FIG. 9b hits the ball operator 18b of FIG. 9c and the ball operator 18b, in turn, rotates the ball valve 18a thereby changing the ball valve 18a from the closed position to the open position. Now, a tool string of any desired length, which is currently disposed inside the space 22 of FIG. 1, can be lowered downhole for the purpose of performing further wellbore operations downhole during one trip into the wellbore. Since a limited tool string length is no longer a problem, it is no longer necessary to continually make up additional tool strings at the wellbore surface, following the performance of an initial wellbore operation by a first tool string, and to sequentially lower the additional tool strings downhole for the purpose of performing additional wellbore operations. Finally, when the piston 18c1 bottoms out against the one side 18g1 of the oil metering orifice 18g, the pressure inside the channel 18d, and inside the first rupture disc 30 which is already ruptured, is increased further to a pressure which exceeds the threshold pressure value rating of the second rupture disc 28 that is disposed inside the piston 18c1. As a result, the second rupture disc 28 ruptures. Now, the pressure existing on one side of the piston 18c1 is equal to the pressure existing on the other side of the piston 18c1. As a result, the operator mandrel 18c can be moved upwardly at any time thereafter because the pressures existing on both sides of the piston 18c1 are approximately equal. The invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications as would be obvious to one skilled in the art are intended to be included within the scope of the following claims.
A formation isolation valve (FIV) method and apparatus is disclosed for building a tool string of any desired length prior to lowering that tool string downhole for the purpose of performing wellbore operations during a single trip into the wellbore. The formation isolation valve apparatus includes a valve, such as a ball valve, initially disposed in an open position and adapted to be changed from the open position to a closed position when a shifting tool is run through the center of the valve; and a hydraulic section including a rupture disc assembly and a pair of chambers separated by an oil metering orifice which is responsive to the previous closure of the valve by the run of the shifting tool through the center of the valve and is further responsive to the further running of the shifting tool through the center of the hydraulic section for changing the valve back from the closed position to the open position thereby reopening the valve when a predetermined internal tubing pressure inside the FIV exceeds a predetermined threshold pressure value rating of the rupture disc assembly.
4
CROSS-REFERENCE TO RELATED APPLICATIONS This application is based on and claims priority under 35 USC 119 from Japanese Patent Application No. 2016-058766 filed Mar. 23, 2016. BACKGROUND Technical Field The present invention relates to a developing device and an image forming apparatus. SUMMARY According to an aspect of the invention, there is provided a developing device including a developer carrier that opposes an image carrier and rotates while carrying developer on a surface thereof; and a container that supports the developer carrier in a rotatable manner and contains the developer, the developer containing toner, first carrier subjected to frictional charging together with the toner, and second carrier having a diameter greater than a diameter of the first carrier and an electrical resistance lower than an electrical resistance of the first carrier. BRIEF DESCRIPTION OF THE DRAWINGS An exemplary embodiment of the present invention will be described in detail based on the following figures, wherein: FIG. 1 illustrates an image forming apparatus according to an exemplary embodiment of the present invention; FIG. 2 illustrates developer according to the exemplary embodiment; FIG. 3 illustrates two-component developer according to the related art; FIG. 4 is a graph showing the experiment result of Experiment Example 1, where the horizontal axis represents the mixing ratio of large-diameter carrier and the vertical axis represents the result of evaluation of an image defect; FIG. 5 is a graph showing the experiment result of Experiment Example 2, where the horizontal axis represents the average carrier particle diameter and the vertical axis represents the grade of image graininess (5 μm≧toner particle diameter); FIGS. 6A and 6B are graphs showing the experiment results of Experiment Example 3, where FIG. 6A is a graph showing the experiment result regarding the resistance of small-diameter carrier and an image quality defect of image loss, and FIG. 6B is a graph showing the experiment result regarding the resistance of the small-diameter carrier and image white spots caused by scattering of carrier; FIG. 7 is a graph showing the experiment result of Experiment Example 4, where the horizontal axis represents the resistance of the large-diameter carrier and the vertical axis represents the grade of image loss; and FIG. 8 is a graph showing the experiment result of Experiment Example 5, where the horizontal axis represents the particle diameter of the large-diameter carrier and the vertical axis represents the grade of transfer failure (5 μm≧toner particle diameter). DETAILED DESCRIPTION An exemplary embodiment of the present invention will be described with reference to the drawings. However, the present invention is not limited to the following exemplary embodiment. To facilitate understanding of the following description, the front-back direction, left-right direction, and up-down direction are defined as the X-axis direction, Y-axis direction, and Z-axis direction, respectively, in each figure. In addition, directions shown by arrows X, −X, Y, −Y, Z, and −Z are defined as forward, backward, rightward, leftward, upward, and downward, respectively, and sides in those directions are defined as the front side, back side, right side, left side, top side, and bottom side, respectively. In the drawings, circles having dots at the center indicate the direction from the far side to the near side in each figure, and circles having the “X” marks therein indicate the direction from near side toward the far side in each figure. In each figure, components other than those necessary for explanation are omitted to facilitate understanding. Exemplary Embodiment FIG. 1 illustrates an image forming apparatus according to an exemplary embodiment of the present invention. In FIG. 1 , a copier U, which is an example of the image forming apparatus according to the exemplary embodiment, includes a printer section U 1 as an example of a recording section as well as an example of an image recording device. A scanner section U 2 , which is an example of a reading section as well as an example of an image reading device, is supported above the printer section U 1 . An automatic feeder U 3 , which is an example of a document transport device, is supported above the scanner section U 2 . The scanner section U 2 according to the exemplary embodiment supports a user interface U 0 , which is an example of an input section. An operator may perform input operation on the user interface U 0 to operate the copier U. A document tray TG 1 , which is an example of a medium container, is disposed in an upper section of the automatic feeder U 3 . The document tray TG 1 is capable of accommodating a stack of document sheets Gi to be copied. A document output tray TG 2 , which is an example of a document output section, is formed below the document tray TG 1 . Document transport rollers U 3 b are arranged along a document transport path U 3 a between the document tray TG 1 and the document output tray TG 2 . A platen glass PG, which is an example of a transparent document table, is disposed on the upper surface of the scanner section U 2 . In the scanner section U 2 according to the exemplary embodiment, a reading optical system A is disposed below the platen glass PG. The reading optical system A according to the exemplary embodiment is supported such that the reading optical system A is movable in the left-right direction along the lower surface of the platen glass PG. Normally, the reading optical system A is stationary at an initial position shown in FIG. 1 . An imaging element CCD, which is an example of an imaging member, is disposed to the right of the reading optical system A. The imaging element CCD is electrically connected to an image processor GS. The image processor GS is electrically connected to a writing circuit DL disposed the printer section U 1 . The writing circuit DL is electrically connected to an exposure device ROS, which is an example of a latent-image forming device. A photoconductor drum PR, which is an example of an image carrier, is disposed in the printer section U 1 . A charging roller CR, which is an example of a charging member, a developing device G, a transfer unit TU, which is an example of a transfer device, and a drum cleaner CLp, which is an example of a cleaning device, are arranged around the photoconductor drum PR. Paper feed trays TR 1 to TR 4 , which are an example of medium containers, are disposed below the transfer unit TU. A transport path SH 1 extends from the paper feed trays TR 1 to TR 4 . Pickup rollers Rp, which are an example medium pickup members, separation rollers Rs, which are an example of separating members, transport rollers Ra, which are an example of transporting members, and registration rollers Rr, which are an example of feeding members, are arranged along the transport path SH 1 . A fixing device F including a heating roller Fh and a pressing roller Fp is disposed to the left of the transfer unit TU. The fixing device F is connected to an output tray TRh by an output path SH 2 . The output path SH 2 is connected to the registration rollers Rr by a reversing path SH 3 . Transport rollers Rb capable of rotating in forward and reverse directions and output rollers Rh are arranged on the output path SH 2 . Description of Image Forming Operation The document sheets Gi accommodated in the document tray TG 1 are successively transported through a document read position on the platen glass PG and output to the document output tray TG 2 . When copying is to be performed by automatically feeding the document sheets by using the automatic feeder U 3 , the document sheets Gi that are successively transported through the read position on the platen glass PG are exposed to light while the reading optical system A is stationary at the initial position. When an operator manually places a document sheet Gi on the platen glass PG to perform copying, the reading optical system A moves in the left-right direction so as to scan the document sheet on the platen glass PG while the document sheet is exposed to light. Reflected light from the document sheet Gi passes through the reading optical system A and is focused on the imaging element CCD. The imaging element CCD converts the reflected light from the document sheet focused on an imaging surface into an electric signal. The image processor GS converts the read signal input from the imaging element CCD into a digital image signal, and outputs the digital image signal to the writing circuit DL of the printer section U 1 . The writing circuit DL outputs a control signal corresponding to the input image write signal to the exposure device ROS. The exposure device ROS emits a laser beam L and forms a latent image on the surface of the photoconductor drum PR charged by the charging roller CR. The latent image on the surface of the photoconductor drum PR is developed into a visible image by the developing device G. The transfer unit TU includes a transfer roller TR that transfers the visible image on the surface of the photoconductor drum PR onto a recording sheet S, which is an example of a medium and which is transported along the transport path SH 1 . The visible image that has been transferred onto the recording sheet S is fixed by the fixing device F. The recording sheet S that has passed through the fixing device F is transported along the reversing path SH 3 when double-sided printing is to be performed, and is discharged by the output rollers Rh when the recording sheet S is to be discharged to the output tray TRh. Description of Developer FIG. 2 illustrates developer according to the exemplary embodiment. The developing device G according to the exemplary embodiment includes a developer container V as an example of a container. A developing roller R 0 , which is an example of a developer carrier, and stirring augers R 1 and R 2 , which are an example of developer transporting members, are rotatably supported in the developer container V. The developer container V contains developer. In the exemplary embodiment, the developer contains toner 1 , small-diameter carrier 2 as an example of first carrier, and large-diameter carrier 3 as an example of second carrier. In the exemplary embodiment, the small-diameter carrier 2 may have a volume average particle diameter of 15 to 25 μm and a volume resistance of 10 9 to 10 11 [Ω]. For example, the volume average particle diameter may be 25 μm, and the volume resistance may be 10 9 [Ω]. In addition, in the exemplary embodiment, the large-diameter carrier 3 may have a volume average particle diameter of 35 to 70 μm and a volume resistance or 10 8 [Ω] or less. For example, the volume average particle diameter may be 35 μm, and the volume resistance may be 10 7 [Ω]. The carriers 2 and 3 may be formed by covering the surfaces of cores made of iron or ferrite, which are an example of a magnetic material, with a resin in which carbon, which is an example of a conductive material, is dispersed. The volume resistance may be adjusted by changing the carbon content. Function of Developing Device G In the developing device G according to the exemplary embodiment having the above-described structure, the developer in the developer container V is transported while being stirred. The toner 1 and the carriers 2 and 3 are charged by friction while being stirred in the developer container V. The toner 1 that has been charged by friction is electrostatically attracted to the carriers 2 and 3 . In addition, the carriers 2 and 3 , which are magnetic, are attracted to the developing roller R 0 by a magnetic force. Therefore, as the developing roller R 0 rotates, the toner 1 and the carriers 2 and 3 are transported to a developing region Q 2 in which the developing roller R 0 and the photoconductor drum PR face each other. In the developing region Q 2 , a developing voltage is applied to the developing roller R 0 so that the toner 1 is moved to the latent image on the photoconductor drum PR and the latent image is developed into a visible image. FIG. 3 illustrates two-component developer according to the related art. Referring to FIG. 3 , when two-component developer containing toner 01 and carrier 02 according to the related art is used, the toner 01 moves to a photoconductor 04 in a developing region 03 to develop a latent image. When the diameter of the carrier 02 is reduced to improve the image quality, as described in Japanese Unexamined Patent Application Publication No. 6-236077, the magnetic force applied between the carrier 02 and the developing roller decreases. This may lead to so-called bead-carry-over (BCO), which is a defect caused when the carrier 02 moves to the photoconductor 04 . To suppress BCO, the developing voltage (for example, negative voltage) may be used to prevent the carrier 02 from moving to the photoconductor 04 by using an electrostatic force. This is achieved by increasing the electrical resistance of the carrier 02 so that the carrier 02 is nearly insulative and natural discharge of the electric charge (for example, positive charge) acquired by the carrier 02 during frictional charging does not easily occur. However, when the electric resistance of the carrier 02 increases, the electrostatic force applied between the carrier 02 and the toner 01 also increases. Therefore, there is a risk that the toner 01 that has moved to the photoconductor 04 in the developing process will be attracted to the carrier 02 due to the residual charge thereof and adhere to the carrier 02 again. When the toner 01 adheres to the carrier 02 again, development failures such as a reduction in the density of the developed image or a partial image loss may occur. The inventors of the present invention have experimentally found that, as described in Japanese Unexamined Patent Application Publication No. 6-236077, the development failures such as insufficient density easily occur irrespective of the particle size and shape of the carrier 02 when the resistance is 10 9 [Ω] or more. In contrast, in the exemplary embodiment, small-diameter carrier 2 having a high resistance and large-diameter carrier 3 having a low resistance are contained in the developer. Therefore, the image quality may be improved by using the small-diameter carrier 2 , and the occurrence of BCO in which the small-diameter carrier 2 having a high resistance moves to the photoconductor drum PR is reduced. Furthermore, since the large-diameter carrier 3 having a low resistance is contained, the electric charge easily moves from the small-diameter carrier 2 to the large-diameter carrier 3 . In particular, when the large-diameter carrier 3 is mixed with the small-diameter carrier 2 , hollow spaces are easily formed. Therefore, the small-diameter carrier 2 more easily comes into contact with the large-diameter carrier 3 to form a conductive path than in the case where the large-diameter carrier is not mixed. Therefore, when the toner 1 is separated from the small-diameter carrier 2 , the electric charge of the small-diameter carrier 2 easily flows to the large-diameter carrier 3 having a low resistance, and natural discharge easily occurs. Thus, in the exemplary embodiment, the occurrence of development failures, such as a reduction in the image density, is lower than that in the case of the technology described in Japanese Unexamined Patent Application Publication No. 6-236077. EXAMPLES Experiments are performed to confirm the effects of the exemplary embodiment. Experiment Example 1 An experiment is performed by using a developing device obtained by remodeling DocuCentre-V C-7755 produced by Fuji Xerox Co., Ltd. The carriers 2 and 3 of the developer used in the experiment are the same as those in the exemplary embodiment. In Experiment Example 1, the experiment is performed by changing the mixing ratio of the small-diameter carrier 2 and the large-diameter carrier 3 . In Experiment Example 1, fogging, which is a phenomenon in which excessive toner adheres to the image, is evaluated by sensory evaluation. Lower grades G indicate lower degrees of fogging, and higher grades G indicate higher degrees of fogging. FIG. 4 shows the experiment result. FIG. 4 is a graph showing the experiment result of Experiment Example 1, where the horizontal axis represents the mixing ratio of the large-diameter carrier, and the vertical axis represents the evaluation result of the image defect. FIG. 4 shows that fogging decreases as the amount of large-diameter carrier 3 increases. When the amount of small-diameter carrier 2 decreases, another problem, such as a reduction in resolution, occurs. The result also shows that fogging decreases as the ratio of the large-diameter carrier 3 becomes lower than that of the small-diameter carrier 2 . The allowable range of the grade G depends on, for example, the image quality demanded by the user, the design, and the specifications. When, for example, the allowable range of the grade G is 1 or less, the mixing ratio of the large-diameter carrier 3 may be 25% or less. Experiment Example 2 In Experiment Example 2, an experiment is performed to evaluate the image graininess (image noise and roughness) with respect to the carrier particle diameter. In Experiment Example 2, the experiment is performed by changing the volume average particle diameter of the small-diameter carrier 2 . The image graininess is evaluated by sensory evaluation. The carrier particle diameter is measured by using Coulter Multisizer II produced by Beckman Coulter, Inc. The experiment is similar to that in Experiment Example 1 in other respects. FIG. 5 shows the experiment result. FIG. 5 shows the experiment result of Experiment Example 2, where the horizontal axis represents the average carrier particle diameter and the vertical axis represents the grade of image graininess (toner particle diameter≧5 μm). FIG. 5 shows that as the average particle diameter of the small-diameter carrier 2 increases, the image graininess increases, that is, the image quality is degraded. The graph shows that when, for example, the allowable range of the grade is 4.5 or less, the volume average particle diameter may be 29 μm or less. Experiment Example 3 In Experiment Example 3, an experiment is performed to evaluate the resistance of the small-diameter carrier and the image quality. In Experiment Example 3, the volume resistance of the small-diameter carrier 2 is changed, and an image quality defect of image loss and image white spots caused by scattering of the carrier are evaluated. Carrier having a volume average particle diameter of 25 μm is used as the small-diameter carrier 2 . The image loss is evaluated by sensory evaluation, and image white spots caused by scattering of the carrier is evaluated by counting the number of voids. The electrical resistance of the carrier is measured by using SM-8215 produced by Hioki E.E. Corporation. The experiment is similar to that in Experiment Example 1 in other respects. FIGS. 6A and 6B show the experiment results. FIGS. 6A and 6B show the experiment results of Experiment Example 3. FIG. 6A is a graph showing the experiment result regarding the resistance of the small-diameter carrier and the image quality defect of image loss, and FIG. 6B is a graph showing the experiment result regarding the resistance of the small-diameter carrier and image white spots caused by scattering of the carrier. FIG. 6A shows that the occurrence of image loss increases as the volume resistance of the small-diameter carrier increases. FIG. 6B shows that the occurrence of voids increases as the volume resistance of the small-diameter carrier decreases. Therefore, when, for example, the allowable range of the grade of the image loss is 3.5 or less and the allowable range of the number of voids is 20 or less, the volume resistance is preferably in the range of 10 8 to 10 11 [Ω], and more preferably in the range of 10 9 to 10 11 [Ω]. Experiment Example 4 In Experiment Example 4, an experiment is performed to evaluate the resistance of the large-diameter carrier and the image quality. In Experiment Example 4, the volume resistance of the large-diameter carrier 3 is changed, and the image quality defect of image loss is evaluated. Carrier having a volume average particle diameter of 40 μm is used as the large-diameter carrier 3 . The image loss is evaluated as in Experiment Example 3. The electrical resistance of the carrier is measured by using SM-8215 produced by Hioki E.E. Corporation. The experiment is similar to that in Experiment Example 1 in other respects. FIG. 7 shows the experiment result. FIG. 7 shows the experiment result of Experiment Example 4, where the horizontal axis represents the resistance of the large-diameter carrier and the vertical axis represents the grade of the image loss. FIG. 7 shows that the occurrence of image loss increases as the volume resistance of the large-diameter carrier increases. Therefore, when, for example, the allowable range of the grade of the image loss is 3.5 or less, the volume resistance of the large-diameter carrier 3 is preferably 10 8 [Ω] or less, and more preferably 10 7 [Ω] or less. Experiment Example 5 In Experiment Example 5, an experiment is performed to evaluate the volume average particle diameter of the large-diameter carrier and the image quality. In Experiment Example 5, the volume average particle diameter of the large-diameter carrier 3 is changed, and an image quality defect due to transfer failure caused by stress on the toner is evaluated. The transfer failure is evaluated by sensory evaluation. The carrier particle diameter is measured as in Experiment Example 2. The experiment is similar to that in Experiment Example 1 in other respects. FIG. 8 shows the experiment result. FIG. 8 shows the experiment result of Experiment Example 5, where the horizontal axis represents the particle diameter of the large-diameter carrier and the vertical axis represents the grade of the transfer failure (toner particle diameter≧5 μm). FIG. 8 shows that the occurrence of transfer failure increases as the volume average particle diameter of the large-diameter carrier increases. When, for example, the allowable range of the grade is 2.5 or less, the volume average particle diameter of the large-diameter carrier 3 is preferably 73 μm or less, more preferably, 70 μm or less. MODIFICATIONS Although an exemplary embodiment of the present invention is described above, the present invention is not limited to the above-described exemplary embodiment, and various modifications are possible within the gist of the present invention described in the claims. An exemplary modification (H01) of the present invention will now be described. (H01) In the above-described exemplary embodiment, the copier U is described as an example of an image forming apparatus. However, the image forming apparatus is not limited to this, and may instead be a printer, a facsimile machine, or a multifunction machine having the functions of these apparatuses. Also, the image forming apparatus is not limited to a monochrome developing image forming apparatus, and may instead be a color image forming apparatus. The foregoing description of the exemplary embodiment of the present invention has been provided for the purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise forms disclosed. Obviously, many modifications and variations will be apparent to practitioners skilled in the art. The embodiment was chosen and described in order to best explain the principles of the invention and its practical applications, thereby enabling others skilled in the art to understand the invention for various embodiments and with the various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the following claims and their equivalents.
A developing device includes a developer carrier that opposes an image carrier and rotates while carrying developer on a surface thereof; and a container that supports the developer carrier in a rotatable manner and contains the developer, the developer containing toner, first carrier subjected to frictional charging together with the toner, and second carrier having a diameter greater than a diameter of the first carrier and an electrical resistance lower than an electrical resistance of the first carrier.
6
CROSS REFERENCE TO RELATED APPLICATIONS [0001] This application claims the benefit of U.S. Provisional Application No. 60/483,904, filed Jul. 2, 2003, entitled CYCLOPROPYL GROUP SUBSTITUTED OXAZOLIDINONE ANTIBIOTICS AND DERIVATIVES THEREOF, and U.S. Provisional Application 60/546,984, filed Feb. 24, 2004, entitled CYCLOPROPYL GROUP SUBSTITUTED OXAZOLIDINONE ANTIBIOTICS AND DERIVATIVES THEREOF, which are hereby incorporated herein by reference it their entirety. BACKGROUND OF THE INVENTION [0002] Oxazolidinones represent the first new class of antibacterials to be developed since the quinolones. The oxazolidinones are synthetic antibacterial compounds that are orally or intravenously active against problematic multidrug resistant Gram positive organisms and are not cross-resistant with other antibiotics. See Riedl et al, Recent Developments with Oxazolidinone Antibiotics, Exp. Opin. Ther. Patents (1999) 9(5), Ford et al., Oxazolidinones: New Antibacterial Agents, Trends in Microbiology 196 Vol. 5, No. 5, May 1997 and WO 96/35691. See also WO 03/063862, WO 01/81350, WO 01/94342, WO 03/072553, EP 0352781 and U.S. Pat. Nos. 5,565,571 and 4,053,593. [0003] This invention relates to new oxazolidinones having a cyclopropyl moiety, which are effective against aerobic and anerobic pathogens such as multi-resistant staphylococci, streptococci and enterococci, Bacteroides spp., Clostridia spp. species, as well as acid-fast organisms such as Mycobacterium tuberculosis and other mycobacterial species. SUMMARY OF THE INVENTION [0004] The present invention relates to compounds of formula I: its enantiomer, diastereomer, or pharmaceutically acceptable salt, hydrate or prodrug thereof wherein: R 1 represents i) hydrogen, ii) (CH 2 ) n NR 5 R 6 , iii) CR 7 R 8 R 9 , C(R) 2 OR 14 , CH 2 NHR 14 , iv) C(═O)R 13 , C(═NOH)H, C(═NOR 13 )H, C(═NOR 13 )R 13 , C(═NOH)R 13 , C(═O)N(R 13 ) 2 , C(═NOH)N(R 13 ) 2 , NHC(═X 1 )N(R 13 ) 2 , NRCO 2 R, (C═NH)R 7 , N(R 13 )C(═X 1 )N(R 13 ) 2 , COOR 13 , SO 2 R 14 , N(R 13 )SO 2 R 14 , N(R 13 )COR 14 , v) (C 1-6 alkyl)CN, CN, CH═C(R) 2 , (CH 2 ) p OH, C(═O)CHR 13 , C(═NR 13 )R 13 , NR 10 C(═X 1 )R 13 ; or vi) C 5-10 heterocycle optionally substituted with 1-3 groups of R 7 , which may be attached through either a carbon or a heteroatom; X represents or a C 5-10 heteroaryl represented by which represents an optionally substituted aromatic heterocyclic group containing 1 to 4 nitrogen atoms and at least one double bond, and which is connected through a bond on any nitrogen said heteroaryl optionally substituted with 1 to 3 substitutents selected from R 7 Y represents NR*, O, CN, or S(O)p; represents aryl or heteroaryl, heterocycle, heterocyclyl or heterocyclic; R x represents hydrogen or C 1-6 alkyl; R 3 represent NR(C═X 2 )R 12 , NR*R 12 , C 6-10 aryl, or —(O) n C 5-10 heterocyclyl which may be attached through either a carbon or a heteroatom; said aryl and heterocyclyl optionally substituted with 1-3 groups of R 7 , R 4 , R 4a , R 4b , and R 4c independently represent i) hydrogen, ii) halogen, iii) C 1-6 alkoxy, or iv) C 1-6 alkyl; r and s independently are 1-3, with the provision that when (R 4a ) s and (R 4 ) r or (R 4b ) and (R 4c ) s are attached to an Ar or HAr ring the sum of r and s is less than or equal to 4; R 5 and R 6 independently represent i) hydrogen, ii) C 1-6 alkyl optionally substituted with 1-3 groups of halogen, CN, OH, C 1-6 alkoxy, amino, imino, hydroxyamino, alkoxyamino, C 1-6 acyloxy, C 1-6 alkylsulfenyl, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, aminosulfonyl, C 1-6 alkylaminosulfonyl, C 1-6 dialkylaminosulfonyl, 4-morpholinylsulfonyl, phenyl, pyridine, 5-isoxazolyl, ethylenyloxy, or ethynyl, said phenyl and pyridine optionally substituted with 1-3 halogen, CN, OH, CF 3 , C 1-6 alkyl or C 1-6 alkoxy; iii) C 1-6 acyl optionally substituted with 1-3 groups of halogen, OH, SH, C 1-6 alkoxy, naphthalenoxy, phenoxy, amino, C 1-6 acylamino, hydroxylamino, alkoxylamino, C 1-6 acyloxy, aralkyloxy, phenyl, pyridine, C 1-6 alkylcarbonyl, C 1-6 alkylamino, C 1-6 dialkylamino, C 1-6 hydroxyacyloxy, C 1-6 alkylsulfenyl, phthalimido, maleimido, succinimido, said phenoxy, phenyl and pyridine optionally substituted with 1-3 groups of halo, OH, CN, C 1-6 alkoxy, amino, C 1-6 acylamino, CF 3 or C 1-6 alkyl; iv) C 1-6 alkylsulfonyl optionally substituted with 1-3 groups of halogen, OH, C 1-6 alkoxy, amino, hydroxylamino, alkoxylamino, C 1-6 acyloxy, or phenyl; said phenyl optionally substituted with 1-3 groups of halo, OH, C 1-6 alkoxy, amino, C 1-6 acylamino, CF 3 or C 1-6 alkyl; v) arylsulfonyl optionally substituted with 1-3 of halogen, C 1-6 alkoxy, OH or C 1-6 alkyl; vi) C 1-6 alkoxycarbonyl optionally substituted with 1-3 of halogen, OH, C 1-6 alkoxy, C 1-6 acyloxy, or phenyl, said phenyl optionally substituted with 1-3 groups of halo, OH, C 1-6 alkoxy, amino, C 1-6 acylamino, CF 3 or C 1-6 alkyl; vii) aminocarbonyl, C 1-6 alkylaminocarbonyl or C 1-6 dialkylaminocarbonyl, said alkyl groups optionally substituted with 1-3 groups of halogen, OH, C 1-6 alkoxy or phenyl viii) five to six membered heterocycles optionally substituted with 1-3 groups of halogen, OH, CN, amino, C 1-6 acylamino, C 1-6 alkylsulfonylamino, C 1-6 alkoxycarbonylamino, C 1-6 alkoxy, C 1-6 acyloxy or C 1-6 alkyl, said alkyl optionally substituted with 1-3 groups of halogen, or C 1-6 alkoxy; ix) C 3-6 cycloalkylcarbonyl optionally substituted with 1-3 groups of halogen, OH, C 1-6 alkoxy or CN; x) benzoyl optionally substituted with 1-3 groups of halogen, OH, C 1-6 alkoxy, C 1-6 alkyl, CF 3 , C 1-6 alkanoyl, amino or C 1-6 acylamino; xi) pyrrolylcarbonyl optionally substituted with 1-3 of C 1-6 alkyl; xii) C 1-2 acyloxyacetyl where the acyl is optionally substituted with amino, C 1-6 alkylamino, C 1-6 dialkylamino, 4-morpholino, 4-aminophenyl, 4-(dialkylamino)phenyl, 4-(glycylamino)phenyl; or R 5 and R 6 taken together with any intervening atoms can form a 3 to 7 membered heterocyclic ring containing carbon atoms and 1-2 heteroatoms independently chosen from O, S, SO, SO 2 , N, or NR 8 ; R 7 represent i) hydrogen, halogen, (CH 2 ) p C 5-10 heterocyclyl, CN, CO 2 R, CON(R) 2 , CHO, (CH 2 ) 0-3 NHAc, C(═NOR), OH, C 1-6 alkoxy, C 1-6 alkyl, alkenyl, hydroxy C 1-6 alkyl, (CH 2 ) 1-3 NHC(O)C 1-6 alkyl, (CH 2 ) 0-3 N(C 1-6 alkyl) 2 , NHCO 2 R, —OCOC 1-6 alkyl; ii) (CH 2 ) n amino, (CH 2 ) n C1-6 alkylamino, C 1-6 acylamino, C 1-6 dialkylamino, hydroxylamino or C 1-2 alkoxyamino all of which can be optionally substituted on the nitrogen with C 1-6 acyl, C 1-6 alkylsulfonyl or C 1-6 alkoxycarbonyl, said acyl and alkylsulfonyl optionally substituted with 1-2 of halogen or OH; R 8 and R 9 independently represent i) H, CN, ii) C 1-6 alkyl optionally substituted with 1-3 halogen, CN, OH, C 1-6 alkoxy, C 1-6 acyloxy, or amino, iii) phenyl optionally substituted with 1-3 groups of halogen, OH, C 1-6 alkoxy; or R 7 and R 8 taken together can form a 3-7 membered carbon ring optionally interrupted with 1-2 heteroatoms chosen from O, S, SO, SO 2 , NH, and NR 8 ; X 1 represents O, S or NR 13 , NCN, NCO 2 R 16 , or NSO 2 R 14 X 2 represents O, S, NH or NSO 2 R 14 ; R 10 represents hydrogen, C 1-6 alkyl or CO 2 R 15 ; R 12 represents hydrogen, C 1-6 alkyl, NH 2 , OR, CHF 2 , CHCl 2 , C(R) 2 Cl, (CH 2 ) n SR, (CH 2 ) n CN, (CH 2 ) n SO 2 R, (CH 2 ) n S(O)R, C 1-6 alkylamino, C 3-6 cycloalkyl, C 5-10 heterocyclyl or C 1-6 dialkylamino, where said alkyl, and cycloalkyl may be substituted with 1-3 groups of halo, CN, OH or C 1-6 alkoxy, said heterocyclyl optionally substituted with 1-3 groups of R 7 ; Each R 13 represents independently hydrogen, C 1-6 alkyl, C 6-10 aryl, NR 5 R 6 , SR 8 , S(O)R 8 , S(O) 2 R 8 , CN, OH, C 1-6 alkylS(O)R, C 1-6 alkoxycarbonyl, hydroxycarbonyl, —OCOaryl, C 1-6 acyl, C 3-7 membered carbon ring optionally interrupted with 1-4 heteroatoms chosen from O, S, SO, SO 2 , NH and NR 8 where said C 1-6 alkyl, aryl or C 1-6 acyl groups may be independently substituted with 0-3 halogens, hydroxy, N(R) 2 , CO 2 R, C 6-10 aryl, C 5-10 heteroaryl, or C 1-6 alkoxy groups; When two R 13 groups are attached to the same atom or two adjacent atoms they may be taken together to form a 3-7 membered carbon ring optionally interrupted with 1-2 heteroatoms chosen from O, S, SO, SO 2 , NH, and NR 8 ; R represents hydrogen or C 1-6 alkyl; R* represents hydrogen, CN, C(═O)R 14 , (CH 2 ) p CO 2 C 1-6 alkyl, (CH 2 ) p C 5-10 heterocyclyl, or C 1-6 alkyl, said alkyl and heterocyclyl optionally substituted with 1 to 3 groups of R 7 ; R 14 represents amino, C 1-6 alkyl, C 3-6 cycloalkyl, (CH 2 ) p C 5-10 heterocyclyl, C 1-6 haloalkyl, phenyl, said alkyl, cycloalkyl, phenyl, heterocyclyl optionally substituted with 1-3 group of R 7 , when R 7 is an amino or hydroxyl group or a nitrogen that forms part of the heterocycle, said amino and hydroxy optionally protected with an amino or hydroxy protecting group; R 15 is C 1-6 alkyl or benzyl said benzyl optionally substituted with 1-3 groups of halo, OH, C 1-6 alkoxy, amino, C 1-6 acylamino, or C 1-6 alkyl; R 16 is hydrogen, C 5-10 heteroaryl, C 6-10 aryl, said heteroaryl and aryl optionally substituted with 1-3 groups of R 7 ; p represents 0-2 and m, n and q independently represent 0-1. [0057] Another aspect of the invention is concerned with the use of the novel antibiotic compositions in the treatment of bacterial infections. DETAILED DESCRIPTION OF THE INVENTION [0058] The invention is described herein in detail using the terms defined below unless otherwise specified. [0059] The compounds of the present invention may have asymmetric centers, chiral axes and chiral planes, and occur as racemates, racemic mixtures, and as individual diastereomers, with all possible isomers, including optical isomers, being included in the present invention. (See E. L. Eliel and S. H. Wilen Stereochemistry of Carbon Compounds (John Wiley and Sons, New York 1994, in particular pages 1119-1190). [0060] When any variable (e.g. aryl, heterocycle, R 5 , R 6 etc.) occurs more than once, its definition on each occurrence is independent at every other occurrence. Also combinations of substituents/or variables are permissible only if such combinations result in stable compounds. [0061] The term “alkyl” refers to a monovalent alkane (hydrocarbon) derived radical containing from 1 to 15 carbon atoms unless otherwise defined. It may be straight or branched. Preferred alkyl groups include lower alkyls which have from 1 to 6 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl and t-butyl. When substituted, alkyl groups may be substituted with up to 3 substituent groups, selected from the groups as herein defined, at any available point of attachment. When the alkyl group is said to be substituted with an alkyl group, this is used interchangeably with “branched alkyl group”. [0062] Cycloalkyl is a species of alkyl containing from 3 to 15 carbon atoms, without alternating or resonating double bonds between carbon atoms. It may contain from 1 to 4 rings which are fused. Preferred cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. When substituted, cycloalkyl groups may be substituted with up to 3 substituents which are defined herein by the definition of alkyl. [0063] Alkanoyl refers to a group derived from an aliphatic carboxylic acid of 2 to 4 carbon atoms. Examples are acetyl, propionyl, butyryl and the like. [0064] The term “alkoxy” refers to those groups of the designated length in either a straight or branched configuration and if two or more carbon atoms in length, they may include a double or a triple bond. Exemplary of such alkoxy groups are methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tertiary butoxy, pentoxy, isopentoxy, hexoxy, isohexoxy allyloxy, propargyloxy, and the like. refers to aryl or heteroaryl, heterocycle, Het, heterocyclyl or heterocyclic as described immediately below. [0065] Aryl refers to any stable monocyclic or bicyclic carbon ring of up to 7 atoms in each ring, wherein at least one ring is aromatic. Examples of such aryl elements include phenyl, napthyl, tetrahydronaphthyl, indanyl, indanonyl, biphenyl, tetralilnyl, tetralonyl, fluorenonyl, phenanthryl, anthryl, acenaphthyl, and the like substituted phenyl and the like. Aryl groups may likewise be substituted as defined. Preferred substituted aryls include phenyl and naphthyl. [0066] The term heterocycle, heteroaryl, Het, heterocyclyl or heterocyclic, as used herein except where noted, represents a stable 5- to 7-membered mono- or bicyclic or stable 8- to 11-membered bicyclic heterocyclic ring system, any ring of which may be saturated or unsaturated, and which consists of carbon atoms and from one to four heteroatoms selected from the group consisting of N, O and S, and wherein the nitrogen and sulfur heteroatoms may optionally be oxidized, and the nitrogen heteroatom may optionally be quaternized (in which case it is properly balanced by a counterion), and including any bicyclic group in which any of the above-defined heterocyclic rings is fused to a benzene ring. The heterocyclic ring may be attached at any heteroatom or carbon atom, which results in the creation of a stable structure. The term heterocycle or heterocyclic includes heteroaryl moieties. “Heterocycle” or “heterocyclyl” therefore includes the above mentioned heteroaryls, as well as dihydro and tetrahydro analogs thereof. The heterocycle, heteroaryl, Het or heterocyclic may be substituted with 1-3 groups of R 7 . Examples of such heterocyclic elements include, but are not limited to the following: piperidinyl, piperazinyl, 2-oxopiperazinyl, 2-oxopiperidinyl, 2-oxopyrrolodinyl, 2-oxoazepinyl, azepinyl, pyrrolyl, 4-piperidonyl, pyrrolidinyl, pyrazolyl, pyrazolidinyl, imidazolyl, imidazolinyl, imidazolidinyl, pyridyl, pyrazinyl, pyrimidinyl, pyrimidonyl, pyridinonyl, pyridazinyl, oxazolyl, oxazolidinyl, isoxazolyl, isoxazolidinyl, morpholinyl, thiazolyl, thiazolidinyl, isothiazolyl, quinuclidinyl, isothiazolidinyl, indolyl, quinolinyl, isoquinolinyl, benzimidazolyl, thiadiazoyl, benzopyranyl, benzothiazolyl, benzoxazolyl, furyl, tetrahydrofuryl, tetrahydropyranyl, thiophenyl, imidazopyridinyl, triazolyl, tetrazolyl, triazinyl, thienyl, benzothienyl, thiamorpholinyl sulfoxide, thiamorpholinyl sulfone, naphthpyridinyl, dihydropyrimidinyl, dihydropyrrolyl, dihydroquinolinyl, dihydrotetrazolyl, dihydrotriazolyl, dihydrothienyl, dihydrooxazolyl, dihydrobenzothiophenyl, dihydrofuranyl, benzothiazolyl, benzothienyl, benzoimidazolyl, benzopyranyl, benzothiofuranyl, carbolinyl, chromanyl, cinnolinyl, benzopyrazolyl, benzodioxolyl and oxadiazolyl. Additional examples of heteroaryls are illustrated by formulas a, b, c and d: wherein R 16 and R 17 are independently selected from hydrogen, halogen, C 1-6 alkyl, C 2-4 alkanoyl, C 1-6 alkoxy; and R 18 represents hydrogen, C 1-6 alkyl, C 2-4 alkanoyl, C 1-6 alkoxycarbonyl and carbamoyl. [0067] The term “alkenyl” refers to a hydrocarbon radical straight, branched or cyclic containing from 2 to 10 carbon atoms and at least one carbon to carbon double bond. Preferred alkenyl groups include ethenyl, propenyl, butenyl and cyclohexenyl. [0068] The terms “quaternary nitrogen” and “positive charge” refer to tetravalent, positively charged nitrogen atoms (balanced as needed by a counterion known in the art) including, e.g., the positively charged nitrogen in a tetraalkylammonium group (e. g. tetramethylammonium), heteroarylium, (e.g., N-methyl-pyridinium), basic nitrogens which are protonated at physiological pH, and the like. Cationic groups thus encompass positively charged nitrogen-containing groups, as well as basic nitrogens which are protonated at physiologic pH. [0069] The term “heteroatom” means O, S or N, selected on an independent basis. [0070] The term “prodrug” refers to compounds which are drug precursors which, following administration and absorption, release the drug in vivo via some metabolic process. Exemplary prodrugs include acyl amides of the amino compounds of this invention such as amides of alkanoic(C 1-6 )acids, amides of aryl acids (e.g., benzoic acid) and alkane(C 1-6 )dioic acids. [0071] Halogen and “halo” refer to bromine, chlorine, fluorine and iodine. [0072] When a group is termed “substituted”, unless otherwise indicated, this means that the group contains from 1 to 3 substituents thereon. [0073] When a functional group is termed “protected”, this means that the group is in modified form to preclude undesired side reactions at the protected site. Suitable protecting groups for the compounds of the present invention will be recognized from the present application taking into account the level of skill in the art, and with reference to standard textbooks, such as Greene, T. W. et al. Protective Groups in Organic Synthesis Wiley, New York (1991). Examples of suitable protecting groups are contained throughout the specification. [0074] Examples of suitable hydroxyl and amino protecting groups are: trimethylsilyl, triethylsilyl, o-nitrobenzyloxycarbonyl, p-nitrobenzyloxycarbonyl, t-butyldiphenylsilyl, t-butyldimethylsilyl, benzyloxycarbonyl, t-butyloxycarbonyl, 2,2,2-trichloroethyloxycarbonyl, allyloxycarbonyl and the like. Examples of suitable carboxyl protecting groups are benzhydryl, o-nitrobenzyl, p-nitrobenzyl, 2-naphthylmethyl, allyl, 2-chloroallyl, benzyl, 2,2,2-trichloroethyl, trimethylsilyl, t-butyldimethylsilyl, t-butldiphenylsilyl, 2-(trimethylsilyl)ethyl, phenacyl, p-methoxybenzyl, acetonyl, p-methoxyphenyl, 4-pyridylmethyl, t-butyl and the like. [0075] The cyclopropyl containing oxazolidinone compounds of the present invention are useful per se and in their pharmaceutically acceptable salt and ester forms for the treatment of bacterial infections in animal and human subjects. The tern “pharmaceutically acceptable ester, salt or hydrate,” refers to those salts, esters and hydrated forms of the compounds of the present invention which would be apparent to the pharmaceutical chemist. i.e., those which are substantially non-toxic and which may favorably affect the pharmacokinetic properties of said compounds, such as palatability, absorption, distribution, metabolism and excretion. Other factors, more practical in nature, which are also important in the selection, are cost of the raw materials, ease of crystallization, yield, stability, solubility, hygroscopicity and flowability of the resulting bulk drug. Conveniently, pharmaceutical compositions may be prepared from the active ingredients in combination with pharmaceutically acceptable carriers. Thus, the present invention is also concerned with pharmaceutical compositions and methods of treating bacterial infections utilizing as an active ingredient the novel cyclopropyl containing oxazolidinone compounds. [0076] The pharmaceutically acceptable salts referred to above also include acid addition salts. Thus, when the Formula I compounds are basic, salts may be prepared from pharmaceutically acceptable non-toxic acids, including inorganic or organic acids. Included among such acid salts are the following: acetate, adipate, alginate, aspartate, benzoate, benzenesulfonate, bisulfate, butyrate, citrate, camphorate, camphorsulfonate, cyclopentanepropionate, digluconate, dodecylsulfate, ethanesulfonate, fumarate, glucoheptanoate, glycerophosphate, hemisulfate, heptanoate, hexanoate, hydrochloride, hydrobromide, hydroiodide, 2-hydroxyethanesulfonate, isethionic, lactate, maleate, mandelic, malic, maleic, methanesulfonate, mucic, 2-naphthalenesulfonate, nicotinate, nitric oxalate, pamoate, pectinate, persulfate, 3-phenylpropionate, picrate, pivalate, propionate, phosphate, pantothenic, pamoic, sulfate, succinate, tartrate, thiocyanate, tosylate and undecanoate. [0077] When the compound of the present invention is acidic, suitable “pharmaceutically acceptable salts” refers to salts prepared from pharmaceutically acceptable non-toxic bases including inorganic bases and organic bases. Salts derived from inorganic bases include aluminum, ammonium, calcium, copper, ferric, ferrous, lithium, magnesium, manganic salts, manganous, potassium, sodium zinc and the like. Particularly preferred are the ammonium, calcium, magnesium, potassium and sodium salts. Salts derived from pharmaceutically acceptable inorganic non-toxic bases include salts of primary, secondary and teritary amines, substituted amines including naturally occurring substituted amines, cyclic amines and basic ion exchange resins, such as arginine, betaine caffeine, choline, N,N 1 -dibenzylethylenediamine, diethylamine, 2-diethylaminoethanol, 2-dimethylaminoethanol, ethanolamine, ethylenediamine, N-ethylmorpholine, N-ethylpiperidine, glucamine, glucosamine, histidine, hydrabamine, isopropylamine, lysine, methylglucamine, morpholine, piperazine, piperidine, polyamine resins, procaine, purines, theobromine, triethylamine, trimethylamine tripropylamine, tromethamine and the like. [0078] The pharmaceutically acceptable esters are such as would be readily apparent to a medicinal chemist, and include those which are hydrolyzed under physiological conditions, such as “biolabile esters”, pivaloyloxymethyl, acetoxymethyl, phthalidyl, indanyl and methoxymethyl, and others. [0079] Biolabile esters are biologically hydrolizable, and may be suitable for oral administration, due to good absorption through the stomach or intenstinal mucosa, resistance to gastric acid degradation and other factors. Examples of biolabile esters include compounds. [0080] An embodiment of this invention is realized when R 1 independently represent H, NR 5 R 6 , CN, OH, or CR 7 R 8 R 9 and all other variables are as described herein. [0081] Another embodiment of this invention is realized when independently are phenyl, pyridyl, pyrimidinyl, or piperidinyl and all other variables are as described herein. [0082] Another embodiment of this invention is realized when R 1 is CN and all other variables are as described herein. [0083] An embodiment of this invention is realized when Y is NR* and all other variables are as described herein. [0084] Another embodiment of this invention is realized when X is C 5-10 heteroaryl represented by which represents an optionally substituted aromatic heterocyclic group containing 1 to 4 nitrogen atoms and at least one double bond, and which is connected through a bond on any nitrogen. Exemplary groups are 1,2,3-triazole, 1,2,4-triazole, 1,2,5-triazole, tetrazole, pyrazole, and imidazole, any of which may contain 1 to 3 substitutents selected from R 7 . [0085] Another embodiment of this invention is realized when X is and all other variables are as described herein. A sub-embodiment of this invention is realized when Y is NR* and R 1 is CN or NH 2 . [0086] Another embodiment of this invention is realized when R 3 is C 5-10 heteroaryl, said heteroaryl optionally substituted with 1-3 groups of R 7 and all other variables are as described herein. [0087] Another embodiment of this invention is realized when R 3 is a C 5-10 heteroaryl represented by which represents an optionally substituted aromatic heterocyclic group containing 1 to 4 nitrogen atoms and at least one double bond, and which is connected through a bond on any nitrogen. Exemplary groups are 1,2,3-triazole, 1,2,4-triazole, 1,2,5-triazole, tetrazole, pyrazole, and imidazole, any of which may contain 1 to 3 substitutents selected from R 7 . [0088] Still another embodiment of this invention is realized when R 5 and R 6 independently are: i) H, ii) C 1-6 alkyl optionally substituted with 1-3 groups of halogen, CN, OH, C 1-6 alkoxy, amino, hydroxyamino, alkoxyamino, C 1-6 acyloxy, C 1-6 alkylsulfenyl, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, aminosulfonyl, C 1-6 alkylaminosulfonyl, C 1-6 dialkylaminosulfonyl, 4-morpholinylsulfonyl, phenyl, pyridine, 5-isoxazolyl, ethyenyloxy, or ethynyl, said phenyl and pyridine optionally substituted with 1-3 halogen, CN, OH, CF 3 , C 1-6 alkyl or C 1-6 alkoxy; iii) C 1-6 acyl optionally substituted with 1-3 groups of halogen, OH, SH, C 1-6 alkoxy, naphthalenoxy, phenoxy, amino, C 1-6 acylamino, hydroxylamino, alkoxylamino, C 1-6 acyloxy, phenyl, pyridine, C 1-6 alkylcarbonyl, C 1-6 alkylamino, C 1-6 dialkylamino, C 1-6 hydroxyacyloxy, C 1-6 alkylsulfenyl, phthalimido, maleimido, succinimido, said phenoxy, phenyl and pyridine optionally substituted with 1-3 groups of halo, OH, CN, C 1-6 alkoxy, amino, C 1-6 acylamino, CF 3 or C 1-6 alkyl; or iv) benzoyl optionally substituted with 1-3 groups of halogen, OH, C 1-6 alkoxy, C 1-6 alkyl, CF 3 , C 1-6 alkanoyl, amino or C 1-6 acylamino and all other variables are as described herein. [0093] Yet another embodiment of this invention is realized when X 1 represents O and all other variables are as described herein. [0094] A preferred embodiment of this invention is realized when the structural formula is III: wherein R 4 , R 4a , and R 3 are as described herein and is 1,2,3-triazole, 1,2,4-triazole, 1,2,5-triazole, tetrazole, pyrazole, or imidazole, any of which may contain 1 to 3 substitutents selected from R 7 . [0095] A subembodiment of this invention is realized when R 3 is a C 5-10 heteroaryl represented by which represents an optionally substituted aromatic heterocyclic group containing 1 to 4 nitrogen atoms and at least one double bond, and which is connected through a bond on any nitrogen. [0096] Another preferred embodiment of this invention is realized when the structural formula is IV: wherein R 1 , R 4 , R 4a , Y and R 3 are as described herein. A subembodiment of this invention is realized when R3 is a C 5-10 heteroaryl represented by which represents an optionally substituted aromatic heterocyclic group containing 1 to 4 nitrogen atoms and at least one double bond, and which is connected through a bond on any nitrogen. [0097] Preferred compounds of this invention are: 1-[5(R)-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole hydrochloride, 1-[5(R)-3-[4-[4-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3-fluorophenyl]phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[4-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3-fluorophenyl]phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole hydrochloride, 1-[5(R)-3-[4-[4-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3-fluorophenyl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[4-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3-fluorophenyl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole hydrochloride, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole hydrochloride, N-[5(S)-3-[4-[4-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0hexan-6-yl]-3-fluorophenyl]phenyl]-2-oxooxazolidin-5-ylmethyl]acetamide, N-[5(S)-3-[4-[4-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3-fluorophenyl]phenyl]-2-oxooxazolidin-5-ylmethyl]acetamide hydrochloride, N-[5(S)-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]phenyl]-2-oxooxazolidin-5-ylmethyl]acetamide, N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]phenyl]-2-oxooxazolidin-5-ylmethyl]acetamide hydrochloride, N-[5(S)-3-[4-[4-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3-fluorophenyl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide, N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3-fluorophenyl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide hydrochloride, N-[5(S)-3-[4-[4-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide, N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide hydrochloride, N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-t-butoxycarbonylamino-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide, N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-amino-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-t-butoxycarbonylamino-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-amino-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, N-[5(S)-3-[4-[4-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-t-butoxycarbonylamino-3-oxabicyclo[3.1.0hexan-6-yl]pyridin-5-yl]phenyl]-2-oxooxazolidin-5-ylmethyl]acetamide, N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-amino-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]phenyl]-2-oxooxazolidin-5-ylmethyl]acetamide, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-t-butoxycarbonylamino-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-amino-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, N-[5(S)-3-[4-[4-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]phenyl]-2-oxooxazolidin-5-ylmethyl]acetamide, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[3-Fluoro-4-[2-(1-methyltetrazol-5-yl)pyridin-5-yl]phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[3,5-Difluoro-4-[2-(1-methyltetrazol-5-yl)pyridin-5-yl]phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[4-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexane-6-yl]-3,5-difluorophenyl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[4-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3,5-difluorophenyl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, N-[5(S)-3-[4-[4-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide, N-[5(S)-3-[4-[4-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide hydrochloride, N-[5(S)-3-[4-[4-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3,5-difluorophenyl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide, N-[5(S)-3-[4-[4-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3,5-difluorophenyl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide hydrochloride, N-[5(S)-3-[4-[4-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]phenyl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide, N-[5(S)-3-[4-[4-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]phenyl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide, N-[5(S)-3-[4-[4-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3-fluorophenyl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide, N-[5(S)-3-[4-[4-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3-fluorophenyl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide, 1-[5(R)-3-[4-[4-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3-fluorophenyl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[4-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3-fluorophenyl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole hydrochloride, 1-[5(R)-3-[4-[4-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexen-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[4-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole 1-[5(R)-3-[4-[4-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]phenyl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[4-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]phenyl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-t-butoxycarbonylamino-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-amino-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-t-butoxycarbonylamino-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide, N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-amino-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide, N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide, N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide S-oxide, N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-thiabicyclo[3.1.0]hexan-6-yl]-pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide S,S-dioxide, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-thiabicyclo[3.1.0]hexan-6-yl]-pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole S-oxide, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole S,S-dioxide, 4-[5(R)-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,4-triazole, 4-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,4-triazole, 5(R)-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-5-[(isoxazol-3-yl)oxy]methyloxazolidin-2-one, 5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6]pyridin-5-yl]-3-fluorophenyl]-5-[(isoxazol-3-yl)oxy]methyloxazolidin-2-one, 5(R)-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-5-[N-(t-butoxycarbonyl)-N-(isoxazol-3-yl)]aminomethyloxazolidin-2-one, 5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-5-[N-(isoxazol-3-yl)]aminomethyloxazolidin-2-one, 5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-5-[(isoxazol-3-yl)oxy]methyloxazolidin-2-one, 5(R)-5-[N-(t-butoxycarbonyl)-N-(isoxazol-3-yl)]aminomethyl-3-[4-[2-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]oxazolidin-2-one, 5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-5-[N-(isoxazol-3-yl)]aminomethyloxazolidin-2-one, N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]propionanide, N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]hexan-6-yl]-pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]difluoroacetamide, N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]hexan-6-yl]-pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]cyclopropanecarboxamide, N-[5(S)-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]propionamide, N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]propionamide, N-[5(S)-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]-hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]cyclopropanecarboxamide, N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]cyclopropanecarboxamide, N-[5(S)-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0.]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]difluoroacetamide, N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]difluoroacetamide, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-methyl-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-3,6-dicyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-3-[(1-t-butoxycarbonylaminocyclopropan-1-yl)carbonyl]-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-3-[(1-aminocyclopropan-1-yl)carbonyl]-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-[2-(phthalimid-2-yl)ethyl]-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-3-(2-aminoethyl)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-[2-(1,2,4-triazol-4-yl)ethyl]-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-3-bromoacetyl-6-cyano-3-azabicyclo[3.1.0]hexane-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-(morpholin-4-yl)acetyl-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-(5-cyanopyridin-2-yl)-3-azabicyclo[3.1.0]hexane-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-(1,3-dihydroxypropan-2-yl)-3-azabicyclo[3.1.0]hexane-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-3-[((2S)-1-t-butoxycabonylpyrrolidin-2-yl)carbonyl]-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-[((2S)-pyrrolidin-2-yl)carbonyl]-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-3-[((2S,4R)-1-t-butoxycabonyl-4-hydroxypyrrolidin-2-yl)carbonyl]-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-[((2S,4R)-4-hydroxypyrrolidin-2-yl)carbonyl]-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-3-[((2S,4S)-1-t-butoxycabonyl-4-fluoropyrrolidin-2-yl)carbonyl]-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-[((2S,4S)-4-fluoropyrrolidin-2-yl)carbonyl]-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[4-[(1α,5α,6β)-3-t-butoxycarbonyl-6-(t-butoxycarbonyl)amino-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[4-[(1α,5α,6β)-6-amino-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole dihydrochloride, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-3-acetoxyacetyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-hydroxyacetyl-3-azabicyclo[3.1.0]hexan-6-yl]-pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, N-[5(S)-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-(2,2-dichlorocyclopropane)-1-carboxamide, N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-(2,2-dichlorocyclopropane)-1-carboxamide, N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-(2,2-dichlorocyclopropane)-1-carboxamide, N-[5(S)-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-(2,2-difluorocyclopropane)-1-carboxamide, N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-(2,2-difluorocyclopropane)-1-carboxamide, N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-(2,2-difluorocyclopropane)-1-carboxamide, O-methyl-N-[5(S)-3-[4-[2-[(1α,5α,β6)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]carbamate, O-methyl-N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]carbamate, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-3,6-dicyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-methyl-3-azabicyclo[3.1.0]hexan-6-yl]-pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[3-fluoro-4-[2-[(1α,5α,6β)-6-hydroxymethyl-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-4-fluoro-1,2,3-triazole, 1-[5(R)-3-[4-[4-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-4-fluoro-1,2,3-triazole, 1-[5(R)-3-[4-[4-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-4-fluoro-1,2,3-triazole, 1-[5(R)-3-[4-[4-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-5-fluoro-1,2,3-triazole, 1-[5(R)-3-[4-[4-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-5-fluoro-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-3-(4-t-butoxycarbonylpiperazin-1-yl)acetyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-(piperazin-1-yl)acetyl-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole dihydrochloride, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]hexan-6-yl]thiophen-4-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-(piperidin-1-yl)acetyl-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-(pyrrolidin-1-yl)acetyl-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-(4-dimethylaminopiperidin-1-yl)acetyl-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-3-[((2S)-1-t-butoxycabonylpyrrolidin-2-yl)carbonyl]-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-[((2S)-pyrrolidin-2-yl)carbonyl]-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-[((2S,4R)-4-hydroxypyrrolidin-2-yl)carbonyl]-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl[-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole hydrochloride, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-3-[((2S,4R)-1-t-butoxycabonyl-4-hydroxypyrrolidin-2-yl)carbonyl]-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-3-[((2S,4S)-1-t-butoxycabonyl-4-fluoropyrrolidin-2-yl)carbonyl]-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-[((2S,4S)-4-fluoropyrrolidin-2-yl)carbonyl]-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-t-butoxycarbonylamino-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-amino-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-t-butoxycarbonylamino-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole S-oxide, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-amino-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole S-oxide, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-t-butoxycarbonylamino-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole S,S-dioxide, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-amino-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole S,S-dioxide, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-t-butoxycarbonylamino-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-amino-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-t-butoxycarbonylamino-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole S-oxide, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-amino-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole S-oxide, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-t-butoxycarbonylamino-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole S,S-dioxide, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-amino-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole S,S-dioxide, 5(R)-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-5-[(isoxazol-3-yl)oxy]methyloxazolidin-2-one, 5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-5-[(isoxazol-3-yl)oxy]methyloxazolidin-2-one, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-(4-methylpiperazin-1-yl)acetyl-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole S-oxide, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole S,S-dioxide, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole S-oxide, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole S,S-dioxide, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-(1,3-diacetoxypropan-2-yl)-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-3-[(3R,4S)-1-azabicyclo[2.2.1]hepan-3-yl]-carbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-(pyridin-2-yl)-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, 5(R)-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-5-[N-(t-butoxycarbonyl)-N-(isoxazol-3-yl)]aminomethyloxazolidin-2-one, 5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-5-[N-(isoxazol-3-yl)]aminomethyloxazolidin-2-one, 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-(thiatriazol-2-yl)-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole, N-[5(S)-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]thioacetamide, N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]thioacetamide, N-[5(S)-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]isothiocyanate, O-methyl-N-[5(S)-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]thiocarbamate, O-methyl-N-[5(S)-3-[4-[2-[(1α, 5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]thiocarbamate, or their enantiomer, diastereomer, or pharmaceutically acceptable salt, hydrate or prodrug thereof. [0254] Suitable subjects for the administration of the formulation of the present invention include mammals, primates, man, and other animals. In vitro antibacterial activity is predictive of in vivo activity when the compositions are administered to a mammal infected with a susceptible bacterial organism. [0255] Using standard susceptibility tests, the compositions of the invention are determined to be active against MRSA and enterococcal infections. [0256] The compounds of the invention are formulated in pharmaceutical compositions by combining the compounds with a pharmaceutically acceptable carrier. Examples of such carriers are set forth below. [0257] The compounds may be employed in powder or crystalline form, in liquid solution, or in suspension. They may be administered by a variety of means; those of principal interest include: topically, orally and parenterally by injection (intravenously or intramuscularly). [0258] Compositions for injection, a preferred route of delivery, may be prepared in unit dosage form in ampules, or in multidose containers. The injectable compositions may take such forms as suspensions, solutions, or emulsions in oily or aqueous vehicles, and may contain various formulating agents. Alternatively, the active ingredient may be in powder (lyophilized or non-lyophilized) form for reconstitution at the time of delivery with a suitable vehicle, such as sterile water. In injectable compositions, the carrier is typically comprised of sterile water, saline or another injectable liquid, e.g., peanut oil for intramuscular injections. Also, various buffering agents, preservatives and the like can be included. [0259] Topical applications may be formulated in carriers such as hydrophobic or hydrophilic bases to form ointments, creams, lotions, in aqueous, oleaginous or alcoholic liquids to form paints or in dry diluents to form powders. [0260] Oral compositions may take such forms as tablets, capsules, oral suspensions and oral solutions. The oral compositions may utilize carriers such as conventional formulating agents, and may include sustained release properties as well as rapid delivery forms. [0261] The dosage to be administered depends to a large extent upon the condition and size of the subject being-treated, the route and frequency of administration, the sensitivity of the pathogen to the particular compound selected, the virulence of the infection and other factors. Such matters, however, are left to the routine discretion of the physician according to principles of treatment well known in the antibacterial arts. Another factor influencing the precise dosage regimen, apart from the nature of the infection and peculiar identity of the individual being treated, is the molecular weight of the compound. [0262] The novel antibiotic compositions of this invention for human delivery per unit dosage, whether liquid or solid, comprise from about 0.01% to as high as about 99% of the cyclopropyl containing oxazolidinone compounds discussed herein, the preferred range being from about 10-60% and from about 1% to about 99.99% of one or more of other antibiotics such as those discussed herein, preferably from about 40% to about 90%. The composition will generally contain from about 125 mg to about 3.0 g of the cyclopropyl containing oxazolidinone compounds discussed herein; however, in general, it is preferable to employ dosage amounts in the range of from about 250 mg to 1000 mg and from about 200 mg to about 5 g of the other antibiotics discussed herein; preferably from about 250 mg to about 1000 mg. In parenteral administration, the unit dosage will typically include the pure compound in sterile water solution or in the form of a soluble powder intended for solution, which can be adjusted to neutral pH and isotonic. [0263] The invention described herein also includes a method of treating a bacterial infection in a mammal in need of such treatment comprising administering to said mammal the claimed composition in an amount effective to treat said infection. [0264] Oxazolidinones have been known at times to cause side effects such as sideroblastic anemia, peripheral sensory neuropathy, optic neuropathy, seizures, thrombocytopenia, cheilosis, seborrheic dermatitis, hypo-regenerative anemia, megaloblastic anemia or normocytic anemia. The compounds of the invention may be combined with an effective amount of one or more vitamins to prevent or reduce the occurrence of oxazolidinone-associated side effects in patients. The vitamins that can be combined are vitamin B2, vitamin B6, vitamin B12 and folic acid. The vitamins may be administered with the oxazolidinones as separate compositions or the vitamins and oxazolidinones may be present in the same composition. [0265] Thus another aspect of this invention is a method of treating or preventing an oxazolidinone-associated side effect by administering an effective amount of the oxazolidinone of structural formula I and an effective amount of one or more of vitamin B2, vitamin B6, vitamin B12 and folic acid to a patient in need thereof. [0266] A further aspect of this invention relates to a method of treating or preventing oxazolidinone-associated normocyctic anemia or peripheral sensory neuropathy by administering an effective amount of vitamin B2 to a patient in need thereof. [0267] Yet another aspect of this invention relates to a method of treating or preventing oxazolidinone-associated sideroblastic anemia, peripheral sensory neuropathy, optic neuropathy, seizures, thrombocytopenia, cheilosis, and seborrheic dermatitis by administering an effective amount of vitamin B6 to a patient in need thereof. [0268] Still another aspect of this invention relates to a method of treating or preventing oxazolidinone-associated hypo-regenerative anemia, megaloblastic anemia by administering an effective amount of vitamin B12 and folic acid to a patient in need thereof. [0269] Still another aspect of this invention relates to a method of treating or preventing bacterial infection by administering an effective amount of a compound of formula I and an effective amount of one or more of the group selected from the group consisting of vitamin B2, vitamin B6, vitamin B12 and folic acid to a patient in need thereof. [0270] The preferred methods of administration of the claimed compositions include oral and parenteral, e.g., i.v. infusion, i.v. bolus and i.m. injection formulated so that a unit dosage comprises a therapeutically effective amount of each active component or some submultiple thereof. [0271] For adults, about 5-50 mg/kg of body weight, preferably about 250 mg to about 1000 mg per person of the cyclopropyl containing oxazolidinone antibacterial compound and about 250 mg, to about 1000 mg per person of the other antibiotic(s) given one to four times daily is preferred. More specifically, for mild infections a dose of about 250 mg two or three times daily of the cyclopropyl containing oxazolidinone antibacterial compound and about 250 mg two or three times daily of the other antibiotic is recommended. For moderate infections against highly susceptible gram positive organisms a dose of about 500 mg each of the cyclopropyl containing oxazolidinone and the other antibiotics, three or four times daily is recommended. For severe, life-threatening infections against organisms at the upper limits of sensitivity to the antibiotic, a dose of about 500-2000 mg each of the cyclopropyl-containing oxazolidinone compound and the other antibiotics, three to four times daily may be recommended. [0272] For children, a dose of about 5-25 mg/kg of body weight given 2, 3, or 4 times per day is preferred; a dose of 10 mg/kg is typically recommended. [0273] The compounds of the present invention can be prepared according to the procedures of the following scheme and general examples, using appropriate materials, and are further exemplified by the following specific examples. The compounds illustrated in the examples are not, however, to be construed as forming the only genus that is considered as the invention. The following examples further illustrate details for the preparation of compounds of the present invention. Those skilled in the art will readily understand that known variations of the conditions and processes of the following preparative procedures can be used to prepare the compounds of the present invention. All temperatures are in degrees Celsius unless otherwise noted. [0274] The compounds of the present invention can be prepared according to Scheme I, using appropriate materials, and are further exemplified by the following specific examples. The compounds illustrated in the examples are not, however, to be construed as forming the only genus that is considered as the invention. The following examples further illustrate details for the preparation of compounds of the present invention. Those skilled in the art will readily understand that known variations of the conditions and processes of the following preparative procedures can be used to prepare the compounds of the present invention. All temperatures are in degrees Celsius unless otherwise noted. [0275] In step 1 aromatic or heteroaromatic amines are converted to the corresponding 5-hydroxyoxazolidinones by methods well known to those skilled in the art. Typical conditions include acylation of the amine with a benzyloxycarbonyl chloride to afford the corresponding carbamate which is then deprotonated with a suitable strong base such n-butyl lithium, lithium t-butoxide or the like and the resulting anion quenched with the requisite glycidylbutyrate or other suitable glycidyl ester. Upon workup and purification the hydroxymethyloxazolidinone is obtained. It will be recognized to one skilled in the art that the requisite acylation may be catalyzed at the discretion of the experimenter by a number of suitable organic or inorganic bases and that likewise a number of suitable acylating agents can be envisaged for the performance of step 1. Moreover it should also be noted that if step 1 is performed using an R-glycidyl ester then the resulting 5-hydroxymethyl oxazolidinone will the S-configuration while performance of step 1 with an S-glycidyl ester will result in a 5-hydroxymethyl oxazolidinone with the R-configuration. [0276] In step 2 the aromatic ring is halogenated using a suitable electrophilic halogenating agent under appropriate conditions. An example of such a halogenationg agent is iodine monochloride, but one skilled in the art will be quick to recognize that other halogenating agents could be used. One will recognize that if the desired halogen is an iodide, then an iodinating agent will be used but if another halogen is desired, then an appropriate halogenating agent will need to be chosen. These are well known to those of only ordinary skill in the art. [0277] Step 3 describes the modification of the hydroxyl group to the R 3 substituent as described in the specification. It will be recognized that the exact procedures, conditions, and reagents will vary depending on the precise chemical nature of the R 3 substituent desired and representative transformations are described, but not limited to, those in the specific examples. [0278] Step 4 describes the conversion of the aromatic halogen to a suitable boronate or boronic acid which is a suitable precursor for the subsequent coupling to AR or HAr a. These conditions are well known to one skilled in the art and include treatment of the starting halide with bispinacolato diboron or another suitable boron precursor in the presence of an appropriate Pd(II) catalyst such as [bis-(diphenylphosphino)ferrocene]palladium II dichloride methylene chloride complex or the like and a suitable base. [0279] Step 5 describes the coupling of the HAr(or AR)b component with a suitable HAr(or AR)a component as detailed in the specification. This transformation, commonly referred to a Suzuki coupling by this skilled in the art is catalyzed by a palladium (0) species such as tetrakis(triphenylphosphine)palladium (0) in the presence ao a suitable base such as alkali metal carbonate to give the compounds of the present invention. Subsequent chemical transformations, well known to those skilled in the art, can be used to interconvert various members of the broad genus described and delineated as X in the specification. [0280] The invention is further described in connection with the following non-limiting examples. EXAMPLE 1 [0281] 1-[5(R)-3-[4-[4-[(1α,5α,6β)-3-t-Butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3-fluorophenyl]phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0282] The mixture of 1-[5(R)-3-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolyl)phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (20.0 mg), 1-bromo-4-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3-fluorobenzene (19.7 mg) and tetrakis(triphenylphosphine)palladium (0) (6.2 mg) in dioxane (0.5 mL) and 2M sodium carbonate solution (135 μL) was heated at 80° C. for 4 hours. The mixture was diluted with ethyl acetate and washed with saturated sodium hydrogencarbonate solution. The organic extracts were washed with brine, dried over anhydrous magnesium sulfate, and then concentrated in vacuo. Preparative thin-layer chromatography (silica, ethyl acetate:acetone=9:1) of the residue gave title compound 1 (19.4 mg) [0283] MS (FAB + ) m/z: 545 (MH + ). [0284] HRMS (FAB + ) for C 29 H 30 FN 6 O 4 (MH + ): calcd, 545.2313; found, 545.2341. EXAMPLE 2 [0285] 1-[5(R)-3-[4-[4-[(1α,5α,6β)-6-Cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3-fluorophenyl]phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole Hydrochloride [0286] To a solution of 1-[5(R)-3-[4-[4-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3-fluorophenyl]phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (316 mg) in dichloromethane-methanol (10:1) solution (2.5 mL) was added a solution of hydrogen chloride in dioxane (4M, 2.5 mL) was stirred at room temperature for 3.5 hours, then concentrated in vacuo. Treatment with ethanol of the residue gave title compound 2 (236 mg). [0287] MS (FAB + ) m/z: 445 (MH + ) (as free base). [0288] HRMS (FAB + ) for C 24 H 22 FN 6 O 2 (MH + ): calcd, 445.1788; found, 445.1765. EXAMPLE 3 [0289] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-3-t-Butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0290] Title compound 3 (22.3 mg) was prepared from 1-[5(R)-3-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolyl)phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (20.0 mg) and 5-bromo-2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridine (19.7 mg) in the same manner as described for EXAMPLE 1. [0291] MS (FAB + ) m/z: 528 (MH + ). [0292] HRMS (FAB + ) for C 28 H 30 N 7 O 4 (MH + ): calcd, 528.2359; found, 528.2352. EXAMPLE 4 [0293] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0294] To a solution of 1-[5(R)-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (209 mg) in dichloromethane-methanol (10:1) solution (1.7 mL) was added a solution of hydrogen chloride in dioxane (4M, 1.7 mL), the mixture was stirred at room temperature for 2.5 hours, then concentrated in vacuo. After dilution of the residue with dichloromethane-methanol (10:1) solution, the mixture was made to alkaline by the addition of 2 N sodium hydroxide solution. The resulting mixture was extracted with dichloromethane-methanol (10:1) solution. The organic extracts were dried over anhydrous magnesium sulfate, and then concentrated in vacuo. Flash chromatography (silica, dichloromethane:methanol=10:1) of the residue gave title compound 5 (134 mg). EXAMPLE 5 [0295] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole Hydrochloride [0296] To a solution of 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (287 mg) in dichloromethane-methanol (10:1) solution (2.5 mL) was added a solution of hydrogen chloride in dioxane (4M, 168 μL) at 0° C., the mixture was concentrated in vacuo. Treatment of the residue with ethanol gave title compound 5 (292 mg). [0297] MS (EI + ) m/z: 428 (M + ) (as free base). [0298] HRMS (EI + ) for C 23 H 22 N 7 O 2 (M + ): calcd, 428.183 5; found, 428.1848. EXAMPLE 6 [0299] 1-[5(R)-3-[4-[4-[(1α,5α,6β)-3-t-Butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3-fluorophenyl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0300] The title compound 6 was prepared from 1-[5(R)-3-[3-fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolyl)phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (20.0 mg) and 1-bromo-4-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3-fluorobenzene (19.6 mg) in the same manner as described for EXAMPLE 1. [0301] MS (FAB + ) m/z: 563 (MH + ). [0302] HRMS (FAB + ) for C 29 H 29 F 2 N 6 O 4 (MH + ): calcd, 563.2218; found, 563.2222. EXAMPLE 7 [0303] 1-[5(R)-3-[4-[4-[(1α,5α,6β)-6-Cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3-fluorophenyl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole Hydrochloride [0304] Title compound 7 (212 mg) was prepared from 1-[5(R)-3-[4-[4-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3-fluorophenyl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (273 mg) in the same manner as described for EXAMPLE 2. [0305] MS (EI + ) m/z: 462 (M + ) (as free base). [0306] HRMS (EI + ) for C 24 H 20 F 2 N 6 O 2 (M + ): calcd, 462.1616; found, 462.1631. EXAMPLE 8 [0307] 1-[5 (R)-3-[4-[2-[(1α,5α,6β)-3-t-Butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0308] The title compound 8 (15.8 mg) was prepared from 1-[5(R)-3-[3-fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolyl)phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (20.0 mg) and 5-bromo-2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridine (18.8 mg) in the same manner as described for EXAMPLE 1. [0309] MS (FAB + ) m/z: 546 (MH + ). [0310] HRMS (FAB + ) for C 28 H 29 FN 7 O 4 (MH + ): calcd, 546.2265; found, 546.2247. EXAMPLE 9 [0311] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole Hydrochloride [0312] The title compound 9 (278 mg) was prepared from 1-[5(R)-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (500 mg) in the same manner as described for EXAMPLE 2. [0313] MS (FAB + ) m/z: 446 (MH + ) (as free base). [0314] HRMS (FAB + ) for C 23 H 21 FN 7 O 2 (MH + ): calcd, 446.1741; found, 446.1733. EXAMPLE 10 [0315] N-[5(S)-3-[4-[4-[(1α,5α,6β)-3-t-Butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3-fluorophenyl]phenyl]-2-oxooxazolidin-5-ylmethyl]acetamide [0316] The title compound 10 (24.9 mg) was prepared from N-[5(S)-3-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolyl)phenyl]-2-oxooxazolidin-5-ylmethyl]acetamide (18.9 mg) and 1-bromo-4-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3-fluorobenzene (20.0 mg) in the same manner as described for EXAMPLE 1. [0317] MS (FAB + ) m/z: 535 (MH + ). [0318] HRMS (FAB + ) for C 29 H 32 FN 4 O 5 (MH + ): calcd, 535.2357; found, 535.2375. EXAMPLE 11 [0319] N-[5(S)-3-[4-[4-[(1α5α,6β)-6-Cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3-fluorophenyl]phenyl]-2-oxooxazolidin-5-ylmethyl]acetamide Hydrochloride [0320] The title compound 11 (281 mg) was prepared from N-[5(S)-3-[4-[4-[(1α,5α,6β)-3-t-butoxycarboyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3-fluorophenyl]phenyl]-2-oxooxazolidin-5-ylmethyl]acetamide (360 mg) in the same manner as described for EXAMPLE 2. [0321] MS (FAB + ) m/z: 435 (MH + ) (as free base). [0322] HRMS (FAB + ) for C 24 H 24 FN 4 O 3 (MH + ): calcd, 435.1832; found, 435.1821. EXAMPLE 12 [0323] N-[5(S)-3-[4-[2-[(1α,5α,6β)-3-t-Butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]phenyl]-2-oxooxazolidin-5-ylmethyl]acetamide [0324] The title compound 12 (20.3 mg) was prepared from N-[5(S)-3-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolyl)phenyl]-2-oxooxazolidin-5-ylmethyl]acetamide (20.0 mg) and 5-bromo-2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridine (20.2 mg) in the same manner as described for EXAMPLE 1. [0325] MS (FAB + ) m/z: 518 (MH + ). [0326] HRMS (FAB + ) for C 28 H 32 N 5 O 5 (MH + ): calcd, 518.2403; found, 518.2412. EXAMPLE 13 [0327] N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]phenyl]-2-oxooxazolidin-5-ylmethyl]acetamide Hydrochloride [0328] The title compound 13 (254 mg) was prepared from N-[5(S)-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]phenyl]-2-oxooxazolidin-5-ylmethyl]acetamide (366 mg) in the same manner as described for EXAMPLE 2. [0329] MS (FAB + ) m/z: 418 (MH + ) (as free base). [0330] HRMS (FAB + ) for C 23 H 24 N 5 O 3 (MH + ): calcd, 418.1879; found, 418.1885. EXAMPLE 14 [0331] N-[5(S)-3-[4-[4-[(1α,5α,6β)-3-t-Butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3-fluorophenyl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide [0332] The title compound 14 (24.9 mg) was prepared from N-[5(S)-3-[3-fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolyl)phenyl]-2-oxooxazolidin-5-ylmethyl]acetamide (20.0 mg) and 1-bromo-4-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3-fluorobenzene (20.2 mg) in the same manner as described for EXAMPLE 1. [0333] MS (FAB + ) m/z: 553 (MH + ). [0334] HRMS (FAB + ) for C 29 H 31 F 2 N 4 O 5 (MH + ): calcd, 553.2263; found, 553.2250. EXAMPLE 15 [0335] N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3-fluorophenyl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide Hydrochloride [0336] The title compound 15 (290 mg) was prepared from N-[5(S)-3-[4-[4-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3-fluorophenyl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide (367 mg) in the same manner as described for EXAMPLE 2. [0337] MS (FAB + ) m/z: 453 (MH + ) (as free base). [0338] HRMS (FAB + ) for C 24 H 23 F 2 N 4 O 3 (MH + ): calcd, 453.1738; found, 453.1747. EXAMPLE 16 [0339] N-[5(S)-3-[4-[4-[(1α,5α,6β)-3-t-Butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide [0340] The title compound 16 (354 mg) was prepared from N-[5(S)-3-[3-fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolyl)phenyl]-2-oxooxazolidin-5-ylmethyl]acetamide (350 mg) and 5-bromo-2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridine (337 mg) in the same manner as described for EXAMPLE 1. [0341] MS (FAB + ) m/z: 536 (MH + ). [0342] HRMS (FAB + ) for C 28 H 31 FN 5 O 5 (MH + ): calcd, 536.2309; found, 536.2296. EXAMPLE 17 [0343] N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide Hydrochloride [0344] The title compound 17 (259 mg) was prepared from N-[5(S)-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]phenyl]-2-oxooxazolidin-5-ylmethyl]acetamide (400 mg) in the same manner as described for EXAMPLE 2. [0345] MS (FAB + ) m/z: 436 (MH + ) (as free base). [0346] HRMS (FAB + ) for C 23 H 23 FN 5 O 3 (MH + ): calcd, 436.1785; found, 436.1776. EXAMPLE 18 [0347] N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-t-Butoxycarbonylamino-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide [0348] The title compound 18 (62.7 mg) was prepared from N-[5(S)-3-[3-fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolyl)phenyl]-2-oxooxazolidin-5-ylmethyl]acetamide (67.2 mg) and 5-bromo-2-[(1α,5α,6β)-6-t-butoxycarbonylamino-3-oxabicyclo[3.1.0]hexan-6-yl]pyridine (63.1 mg) in the same manner as described for EXAMPLE 1. [0349] MS (FAB + ) m/z: 527 (MH + ). [0350] HRMS (FAB + ) for C 27 H 32 FN 4 O 6 (MH + ): calcd, 527.2306; found, 527.2329. EXAMPLE 19 [0351] N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-Amino-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide [0352] To a solution of N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-t-butoxycarbonylamino-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide (52.0 mg) in dichloromethane (1 mL) was added trifluoroacetic acid (0.5 mL) at 0° C., the mixture was stirred at room temperature for 2 hours. After quenching the reaction by addition of saturated sodium hydrogencarbonate solution, the mixture was extracted with chloroform-methanol (9:1) solution. The organic extracts were dried over anhydrous magnesium sulfate, and then concentrated in vacuo. Flash chromatography (NH silica, dichloromethane:methanol=20:1) of the residue gave title compound 19 (36.7 mg). [0353] MS (EI + ) m/z: 426 (M + ). [0354] HRMS (EI + ) for C 22 H 23 FN 4 O 4 (M + ): calcd, 426.1703; found, 426.1741. EXAMPLE 20 [0355] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-t-Butoxycarbonylamino-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0356] The title compound 20 (71.1 mg) was prepared from 1-[5(R)-3-[3-fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolyl)phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (65.6 mg) and 5-bromo-2-[(1α,5α,6β)-6-t-butoxycarbonylamino-3-oxabicyclo[3.1.0]hexan-6-yl]pyridine (60.0 mg) in the same manner as described for EXAMPLE 1. [0357] MS (FAB + ) m/z: 537 (MH + ). [0358] HRMS (FAB + ) for C 27 H 30 FN 6 O 5 (MH + ): calcd, 537.2262; found, 537.2276. EXAMPLE 21 [0359] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Amino-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0360] The title compound 21 (238 mg) was prepared from 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-t-butoxycarbonylamino-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (433 mg) in the same manner as described for EXAMPLE 18. [0361] MS (FAB + ) m/z: 437 (MH + ). [0362] HRMS (FAB + ) for C 22 H 22 FN 6 O 3 (MH + ): calcd, 437.1737; found, 437.1755. EXAMPLE 22 [0363] N-[5(S)-3-[4-[4-[(1α,5α,6β[)-6-Cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide [0364] The title compound 22 (302 mg) was prepared from N-[5(S)-3-[3-fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolyl)phenyl]-2-oxooxazolidin-5-ylmethyl]acetamide (378 mg) and 5-bromo-2-[(](1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridine (337 mg) in the same manner as described for EXAMPLE 1. [0365] MS (EI + ) m/z: 436 (M + ). [0366] HRMS (EI + ) for C 23 H 21 FN 4 O 4 (M + ): calcd, 436.1547; found, 436.1516. EXAMPLE 23 [0367] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0368] The title compound 23 (353 mg) was prepared from 1-[5(R)-3-[3-fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolyl)phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (388 mg) and 5-bromo-2-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridine (265 mg) in the same manner as described for EXAMPLE 1. [0369] MS (FAB + ) m/z: 447 (MH + ). [0370] HRMS (FAB + ) for C 23 H 20 FN 6 O 3 (MH + ): calcd, 447.1581; found, 447.1589. EXAMPLE 24 [0371] N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-t-Butoxycarbonylamino-3-oxabicyclo[3.1.0]hexan-6-yl]-pyridin-5-yl]phenyl]-2-oxooxazolidin-5-ylmethyl]acetamide [0372] The title compound 24 (387 mg) was prepared from N-[5(S)-3-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolyl)phenyl]-2-oxooxazolidin-5-ylmethyl]acetamide (406 mg) and 5-bromo-2-[(1α,5α,6β)-6-t-butoxycarbonylamino-3-oxabicyclo[3.1.0]hexan-6-yl]pyridine (400 mg) in the same manner as described for EXAMPLE 1. [0373] MS (FAB + ) m/z: 509 (MH + ). [0374] HRMS (FAB + ) for C 27 H 33 N 4 O 6 (MH + ): calcd, 509.2400; found, 509.2384. EXAMPLE 25 [0375] N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-Amino-3-oxabicyclo[3.1.0]hexan-6-yl]-pyridin-5-yl]phenyl]-2-oxooxazolidin-5-ylmethyl]acetamide [0376] The title compound 25 (262 mg) was prepared from N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-t-butoxycarbonylamino-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]phenyl]-2-oxooxazolidin-5-ylmethyl]acetamide (380 mg) in the same manner as described for EXAMPLE 18. [0377] MS (FAB + ) m/z: 409 (MH + ). [0378] HRMS (FAB + ) for C 22 H 25 N 4 O 4 (MH + ): calcd, 409.1876; found, 409.1838. EXAMPLE 26 [0379] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-t-Butoxycarbonylamino-3-oxabicyclo[3.1.0hexan-6-yl]pyridin-5-yl]phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0380] The title compound 26 (313 mg) was prepared from 1-[5(R)-3-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolyl)phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (418 mg) and 5-bromo-2-[(1α,5α,6β)-6-t-butoxycarbonylamino-3-oxabicyclo[3.1.0]hexan-6-yl]pyridine (400 mg) in the same manner as described for EXAMPLE 1. [0381] MS (FAB + ) m/z: 519 (MH + ). [0382] HRMS (FAB + ) for C 27 H 31 N 6 O 5 (MH + ): calcd, 519.2356; found, 519.2382. EXAMPLE 27 [0383] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Amino-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0384] The title compound 27 (210 mg) was prepared from 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-t-butoxycarbonylamino-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (310 mg) in the same manner as described for EXAMPLE 18. [0385] MS (FAB + ) m/z: 419 (MH + ). [0386] HRMS (FAB + ) for C 22 H 23 N 6 O 3 (MH + ): calcd, 419.1832; found, 419.1835. EXAMPLE 28 [0387] N-[5(S)-3-[4-[4-[(1α,5α,6β)-6-Cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]phenyl]-2-oxooxazolidin-5-ylmethyl]acetamide [0388] The title compound 28 (318 mg) was prepared from N-[5(S)-3-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolyl)phenyl]-2-oxooxazolidin-5-ylmethyl]acetamide (360 mg) and 5-bromo-2-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridine (265 mg) in the same manner as described for EXAMPLE 1. [0389] MS (FAB + ) m/z: 419 (MH + ). [0390] HRMS (FAB + ) for C 23 H 23 N 4 O 4 (MH + ): calcd, 419.1719, found, 419.1712. EXAMPLE 29 [0391] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0392] The title compound 29 (344 mg) was prepared from 1-[5(R)-3-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolyl)phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (419 mg) and 5-bromo-2-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridine (300 mg) in the same manner as described for EXAMPLE 1. [0393] MS (FAB + ) m/z: 429 (MH + ). [0394] HRMS (FAB + ) for C 23 H 21 N 6 O 3 (MH + ): calcd, 429.1675; found, 429.1677. EXAMPLE 30 [0395] 1-[5(R)-3-[3-Fluoro-4-[2-(1-methyltetrazol-5-yl)pyridin-5-yl]phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0396] The title compound 30 (480 mg) was prepared from 1-[5(R)-3-[3-fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolyl)phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (500 mg) and 5-bromo-2-(1-methyltetrazol-5-yl)pyridine (309 mg) in the same manner as described for EXAMPLE 1. [0397] MS (FAB + ) m/z: 422 (MH + ). [0398] HRMS (FAB + ) for C 19 H 17 FN 9 O 2 (MH + ): calcd, 422.1489; found, 422.1508. EXAMPLE 31 [0399] 1-[5(R)-3-[3,5-Difluoro-4-[2-(1-methyltetrazol-5-yl)pyridin-5-yl]phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0400] The mixture of 5-bromo-2-(1-methyltetrazol-5-yl)pyridine (312 mg), bis(pinacolato)diboron (363 mg), potassium 2-ethylhexanoate (355 mg) and [1,1′-bis(diphenylphosphino)ferrocene]palladium(II) dichloride-dichloromethane adduct (53.1 mg) in dioxane (13 mL) was stirred at 80° C. for 1.5 hours and concentrated in vacuo. To a solution of the resulting residue in dioxane (29 mL) was added 1-[5(R)-3-[3,5-difluoro-4-(trifluoromethanesulfonyl)oxyphenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (500 mg), tetrakis(triphenylphosphine)palladium (0) (135 mg) and 2M sodium carbonate solution (2.9 mL), the mixture was stirred at 90° C. for 6 hours. Flash chromatography (NH silica, ethyl acetate) of the mixture gave title compound 31 (246 mg). [0401] MS (FAB + ) m/z: 440 (MH + ). [0402] HRMS (FAB + ) for C 19 H 16 F 2 N 9 O 2 (MH + ): calcd, 440.1395; found, 440.1395. EXAMPLE 32 [0403] 1-[5(R)-3-[4-[4-[(1α,5α,6β)-3-t-Butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3,5-difluorophenyl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0404] Title compound 32 (362 mg) was prepared from 1-[5(R)-3-[3-fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolyl)-phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (260 mg) and 1-bromo-4-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3,5-difluorobenzene (267 mg) in the same manner as described for EXAMPLE 1. [0405] MS (FAB + ) m/z: 581 (MH + ). [0406] HRMS (FAB + ) for C 29 H 28 F 3 N 6 O 4 (MH + ): calcd, 581.2124; found, 581.2149. EXAMPLE 33 [0407] 1-[5(R)-3-[4-[4-[(1α,5α,6β)-6-Cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3,5-difluorophenyl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole Hydrochloride [0408] Title Compound 33 (281 mg) was prepared from 1-[5(R)-3-[4-[4-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3,5-difluorophenyl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (360 mg) in the same manner as described for EXAMPLE 2. [0409] MS (FAB + ) m/z: 481 (MH + ) (as free base). [0410] HRMS (FAB + ) for C 24 H 20 F 3 N 6 O 2 (MH + ): calcd, 481.1600; found, 481.1598. EXAMPLE 34 [0411] N-[5(S)-3-[4-[4-[(1α,5α,6β)-3-t-Butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetaimide [0412] Title Compound 34 (15.5 mg) was prepared from N-[5(S)-3-[3,5-difluoro-4-(trifluoromethane-sulfonyl)oxyphenyl]-2-oxooxazolidin-5-ylmethyl]acetamide (19.6 mg) and 5-bromo-2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridine (20.0 mg) in the same manner as described for EXAMPLE 31. [0413] MS (FAB + ) m/z: 554 (MH + ). [0414] HRMS (FAB + ) for C 28 H 30 F 2 N 5 O 5 (MH + ): calcd, 554.2215; found, 554.2201. EXAMPLE 35 [0415] N-[5(S)-3-[4-[4-[(1α,5α,6β)-6-Cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide Hydrochloride [0416] Title Compound 35 (185 mg) was prepared from N-[5(S)-3-[4-[4-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide (235 mg) in the same manner as described for EXAMPLE 2. [0417] MS (FAB + ) m/z: 454 (MH + ) (as free base). [0418] HRMS (FAB + ) for C 23 H 22 F 2 N 5 O 3 (MH + ): calcd, 454.1691; 454.1651. EXAMPLE 36 [0419] N-[5(S)-3-[4-[4-[(1α,5α,6β)-3-t-Butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3,5-difluorophenyl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide [0420] Title Compound 36 (347 mg) was prepared from N-[5(S)-3-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolyl)-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide (300 mg) and 1-bromo-4-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3,5-difluorobenzene (317 mg) in the same manner as described for EXAMPLE 1. [0421] MS (FAB + ) m/z: 571 (MH + ). [0422] HRMS (FAB + ) for C 29 H 30 F 3 N 4 O 5 (MH + ): calcd, 571.2168; found, 571.2159. EXAMPLE 37 [0423] N-[5(S)-3-[4-[4-[(1α,5α,6β)-6-Cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3,5-difluorophenyl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide Hydrochloride [0424] Title Compound 37 (251 mg) was prepared from N-[5(S)-3-[4-[4-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo-[3.1.0]hexan-6-yl]-3,5-difluorophenyl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide (347 mg) in the same manner as described for EXAMPLE 2. [0425] MS (EI + ) m/z: 470 (M + ) (as free base). [0426] HRMS (EI + ) for C 24 H 21 F 3 N 4 O 3 (M + ): calcd, 470.1566; found, 470.1551. EXAMPLE 38 [0427] N-[5(S)-3-[4-[4-[(1α,5α,6β)-3-t-Butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]phenyl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide [0428] Title Compound 38 (274 mg) was prepared from N-[5(S)-3-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolyl)-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide (300 mg) and 1-bromo-4-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]benzene (288 mg) in the same manner as described for EXAMPLE 1. [0429] MS (FAB + ) m/z: 535 (MH + ). [0430] HRMS (FAB + ) for C 29 H 32 FN 4 O 5 (MH + ): calcd, 535.2357; found, 535.2325. EXAMPLE 39 [0431] N-[5(S)-3-[4-[4-[(1α,5α,6β)-6-Cyano-3-azabicyclo[3.1.0]hexan-6-yl]phenyl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide Hydrochloride [0432] Title Compound 39 (212 mg) was prepared from N-[5(S)-3-[4-[4-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]phenyl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide (274 mg) in the same manner as described for EXAMPLE 2. [0433] MS (FAB + ) m/z: 435 (MH + ) (as free base). [0434] HRMS (FAB + ) for C 24 H 24 FN 4 O 3 (MH + ): calcd, 435.1832; found, 435.1818. EXAMPLE 40 [0435] N-[5(S)-3-[4-[4-[(1α,5α,6β)-3-t-Butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3-fluorophenyl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide [0436] Title Compound 40 (427 mg) was prepared from N-[5(S)-3-[3,5-difluoro-4-(trifluoromethanesulfonyl)oxyphenyl]-2-oxooxazolidin-5-ylmethyl]acetamide (641 mg) and 1-bromo-4-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3-fluorobenzene (700 mg) in the same manner as described for EXAMPLE 31. [0437] MS (FAB + ) m/z: 571 (MH + ). [0438] HRMS (FAB + ) for C 29 H 30 F 3 N 4 O 5 (MH + ): calcd, 571.2168; found, 571.2134. EXAMPLE 41 [0439] N-[5(S)-3-[4-[4-[(1α,5α,6β)-6-Cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3-fluorophenyl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide Hydrochloride [0440] Title Compound 41 (340 mg) was prepared from N-[5(S)-3-[4-[4-[(1a,5a,6b)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3-fluorophenyl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide (420 mg) in the same manner as described for EXAMPLE 2. [0441] MS (FAB + ) m/z: 471 (MH + ) (as free base). [0442] HRMS (FAB + ) for C 24 H 22 F 3 N 4 O 3 (MH + ): calcd, 471.1644; found, 471.1611. EXAMPLE 42 [0443] 1-[5(R)-3-[4-[4-[(1α,5α,6β)-3-t-Butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3-fluorophenyl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0444] Title Compound 42 (273 mg) was prepared from 1-[5(R)-3-[3,5-difluoro-4-(trifluoromethanesulfonyl)oxyphenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (561 mg) and 1-bromo-4-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3-fluorobenzene (600 mg) in the same manner as described for EXAMPLE 31. [0445] MS (FAB + ) m/z: 581 (MH + ). [0446] HRMS (FAB + ) for C 29 H 28 F 3 N 6 O 4 (MH + ): calcd, 581.2124; found, 581.2141. EXAMPLE 43 [0447] 1-[5(R)-3-[4-[4-[(1α,5α,6β)-6-Cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3-fluorophenyl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole Hydrochloride [0448] Title Compound 43 1-[5(R)-3-[4-[4-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3-fluorophenyl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole hydrochloride (223 mg) was prepared from (270 mg) in the same manner as described for EXAMPLE 2. [0449] MS (FAB + ) m/z: 481 (MH + ) (as free base). [0450] HRMS (FAB + ) for C 24 H 20 F 3 N 6 O 2 (MH + ): calcd, 481.1600; found, 481.1624. EXAMPLE 44 [0451] 1-[5(R)-3-[4-[4-[(1α,5α,6β)-3-t-Butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0452] Title Compound 44 (14.5 mg) was prepared from 1-[5(R)-3-[3,5-difluoro-4-(trifluoromethanesulfonyl)oxyphenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (19.6 mg) and 5-bromo-2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin (20.0 mg) in the same manner as described for EXAMPLE 31. [0453] MS (FAB + ) m/z: 564 (MH + ). [0454] HRMS (FAB + ) for C 28 H 28 F 2 N 7 O 4 (MH + ): calcd, 564.2171; found, 564.2147. EXAMPLE 45 [0455] 1-[5(R)-3-[4-[4-[(1α,5α,6β)-6-Cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole Hydrochloride [0456] Title Compound 45 (294 mg) was prepared from 1-[5(R)-3-[4-[4-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (360 mg) in the same manner as described for EXAMPLE 2. [0457] MS (FAB + ) m/z: 464 (MH + ) (as free base). [0458] HRMS (FAB + ) for C 23 H 20 F 2 N 7 O 2 (MH + ): calcd, 464.1647; found, 464.1648. EXAMPLE 46 [0459] 1-[5(R)-3-[4-[4-[(1α,5α,6β)-3-t-Butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]phenyl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0460] Title Compound 46 (305 mg) was prepared from 1-[5(R)-3-[3-fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolyl)phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (300 mg) and 1-bromo-4-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]benzene (281 mg) in the same manner as described for EXAMPLE 1. [0461] MS (FAB + ) m/z: 545 (MH 30 ). [0462] HRMS (FAB + ) for C 29 H 30 FN 6 O 4 (MH + ): calcd, 545.2313; found, 545.2318. EXAMPLE 47 [0463] 1-[5(R)-3-[4-[4-[(1α,5α,6β)-6-Cyano-3-azabicyclo[3.1.0]hexan-6-yl]phenyl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole Hydrochloride [0464] Title Compound 47 (265 mg) was prepared from 1-[5(R)-3-[4-[4-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]phenyl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (305 mg) in the same manner as described for EXAMPLE 2. [0465] MS (FAB + ) m/z: 445 (MH + ) (as free base). [0466] HRMS (FAB + ) for C 24 H 22 FN 6 O 2 (MH + ): calcd, 445.1788; found, 445.1826. EXAMPLE 48 [0467] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-t-Butoxycarbonylamino-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0468] Title Compound 48 (482 mg) was prepared from 1-[5(R)-3-[3,5-difluoro-4-(trifluoromethanesulfonyl)oxyphenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (750 mg) and 5-bromo-2-[(1α,5α,6β)-6-t-butoxycarbonylamino-3-oxabicyclo[3.1.0]hexan-6-yl]pyridine (684 mg) in the same manner as described for EXAMPLE 31. [0469] MS (FAB + ) m/z: 555 (MH + ). [0470] HRMS (FAB + ) for C 27 H 29 F 2 N 6 O 5 (MH + ): calcd, 555.2167; found, 555.2159. EXAMPLE 49 [0471] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Amino-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0472] To a solution of 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-t-butoxycarbonylamino-3-oxabicyclo[3.1.0]hexan-6-yl]pyridine-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (465 mg) in dichloromethane was added trifluoroacetic acid (4 mL) at room temperature, the mixture was stirred at the same temperature for 1 hour and concentrated in vacuo. After addition of aqueous sodium hydrogencarbonate solution, the mixture was extracted with dichloromethane-methanol (10:1). The organic extracts were dried over anhydrous magnesium sulfate, filtered, and then concentrated in vacuo. Flash chromatography (NH silica, chloroform:methanol=9:1) of the residue gave 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-amino-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (299 mg). [0473] MS (FAB + ) m/z: 455 (MH + ). [0474] HRMS (FAB + ) for C 22 H 21 F 2 N 6 O 3 (MH + ): calcd, 455.1643; found, 455.1649. EXAMPLE 50 [0475] N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-t-Butoxycarbonylamino-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide [0476] Title Compound 50 (269 mg) was prepared from N-[5(S)-3-[3,5-difluoro-4-(trifluoromethanesulfonyl)oxyphenyl]-2-oxooxazolidin-5-ylmethyl]acetamide (500 mg) and 5-bromo-2-[(1α,5α,6β)-6-t-butoxycarbonylamino-3-oxabicyclo[3.1.0]hexan-6-yl]pyridine (467 mg) in the same manner as described for EXAMPLE 31. [0477] MS (FAB + ) m/z: 545 (MH + ). [0478] HRMS (FAB + ) for C 27 H 31 F 2 N 4 O 6 (MH + ): calcd, 545.2212; found, 545.2224. EXAMPLE 51 [0479] N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-Amino-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide [0480] Title Compound 51 (278 mg) was prepared from N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-t-butoxycarbonylamino-3-oxabicyclo-[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide (442 mg) in the same manner as described for EXAMPLE 49. [0481] MS (FAB + ) m/z: 445 (MH + ). [0482] HRMS (FAB + ) for C 22 H 23 F 2 N 4 O 4 (MH + ): calcd, 445.1687; found, 445.1699. EXAMPLE 52 [0483] N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide [0484] Title Compound 52 (349 mg) was prepared from N-[5(S)-3-[3,5-difluoro-4-(trifluoromethanesulfonyl)oxyphenyl]-2-oxooxazolidin-5-ylmethyl]acetamide (600 mg) and 5-bromo-2-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]-hexan-6-yl]pyridine (419 mg) in the same manner as described for EXAMPLE 31. [0485] MS (FAB + ) m/z: 455 (MH + ). [0486] HRMS (FAB + ) for C 23 H 21 F 2 N 4 O 4 (MH + ): calcd, 455.1531; found, 455.1505. EXAMPLE 53 [0487] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0488] Title Compound 53 (319 mg) was prepared from 1-[5(R)-3-[3,5-difluoro-4-(trifluoromethanesulfonyl)oxyphenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (612 mg) and 5-bromo-2-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]-hexan-6-yl]pyridine (419 mg) in the same manner as described for EXAMPLE 31. [0489] MS (FAB + ) m/z: 465 (MH + ). [0490] HRMS (FAB + ) for C 23 H 19 F 2 N 6 O 3 (MH + ): calcd, 465.1487; found, 465.1460. EXAMPLE 54 [0491] N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide [0492] Title Compound 54 (1.32 g) was prepared from N-[5(S)-3-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolyl)-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide (1.51 g) and 5-bromo-2-[(1α,5α,6β)-6-cyano-3-thiabicyclo-[3.1.0]hexan-6-yl]pyridine (1.13 g) in the same manner as described for EXAMPLE 1. [0493] MS (FAB + ) m/z: 453 (MH + ). [0494] HRMS (FAB + ) for C 23 H 22 FN 4 O 3 S (MH + ): calcd, 453.1397; found, 453.1402. EXAMPLE 55 [0495] N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide S-Oxide [0496] Title Compound 55 (233 mg) was prepared from N-[5(S)-3-[4-[2-[(1α, 5α,6β)-6-cyano-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide (294 mg) in the same manner as described for EXAMPLE 58. [0497] MS (FAB + ) m/z: 469 (MH + ). [0498] HRMS (FAB + ) for C 23 H 22 FN 4 O 4 S (MH + ): calcd, 469.1346; found, 469.1359. EXAMPLE 56 [0499] N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide S,S-Dioxide [0500] Title Compound 56 (292 mg) was prepared from N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]acetamide (317 mg) in the same manner as described for EXAMPLE 59. [0501] MS (FAB + ) m/z: 485 (MH + ). [0502] HRMS (FAB + ) for C 23 H 22 FN 4 O 5 S (MH + ): calcd, 485.1295; found, 485.1282. EXAMPLE 57 [0503] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0504] Title Compound 57 (546 mg) was prepared from 1-[5(R)-3-[3-fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolyl)phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (582 mg) and 5-bromo-2-[(1α,5α,6β)-6-cyano-3-thiabicyclo-[3.1.0]hexan-6-yl]pyridine (422 mg) in the same manner as described for EXAMPLE 1. [0505] MS (FAB + ) m/z: 463 (MH + ). [0506] HRMS (FAB + ) for C 23 H 20 FN 6 O 2 S (MH + ): calcd, 463.1352; found, 463.1355. EXAMPLE 58 [0507] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-thiabicyclo[3.1.0]hexan-6-yl]-pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole S-Oxide [0508] To a solution of 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (118 mg) in dichloromethane-methanol (5:1, 8 mL) was added a solution of m-chloroperoxybenzoic acid (74.5 mg) in dichloromethane-methanol (5:1, 1 mL) at −19° C., the mixture was stirred at 0° C. for 70 minutes. Flash chromatography (NH silica, dichloromethane:tetrahydrofuran=7:3) of the mixture gave 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-thiabicyclo[3.1.0]hexan-6-yl]-pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole S-oxide (111 mg). [0509] MS (FAB + ) m/z: 479 (MH + ). [0510] HRMS (FAB + ) for C 23 H 20 FN 6 O 3 S (MH + ): calcd, 479.1302; found, 479.1306. EXAMPLE 59 [0511] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole S,S-Dioxide [0512] To a solution of 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (254 mg) in dichloromethane-methanol (5:1, 14 mL) was added a solution of m-chloroperoxybenzoic acid (438 mg) in dichloromethane-methanol (5:1, 2.0 mL) at 0° C., the mixture was stirred at room temperature for 1.25 hours. After addition of m-chloroperoxybenzoic acid (146 mg) in dichloromethane-methanol (5:1, 0.7 mL) to the mixture, the mixture was stirred at room temperature for 2 hours. Flash chromatography (NH silica, dichloromethane:tetrahydrofuran=2:1) of the mixture gave 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-thiabicyclo3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole S,S-dioxide (261 mg). [0513] MS (FAB + ) m/z: 495 (MH + ). [0514] HRMS (FAB + ) for C 23 H 20 FN 6 O 4 S (MH + ): calcd, 495.1251; found, 495.1256. EXAMPLE 60 [0515] 4-[5(R)-3-[4-[2-[(1α,5α,6β)-3-t-Butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,4-triazole [0516] Title Compound 60 (64.0 mg) was prepared from 5(S)-aminomethyl-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]oxazolidin-2-one (700 mg) in the same manner as described for EXAMPLE 83. [0517] Rf value (TLC): 0.26 (dichloromethane:methanol=10:1). EXAMPLE 61 [0518] 4-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,4-triazole Hydrochloride [0519] Title Compound 61 (37.9 mg) was prepared from 4-[5(R)-3-[4-[2-[(1a,5a,6b)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,4-triazole (64.0 mg) in the same manner as described for EXAMPLE 2. [0520] MS (FAB + ) m/z: 446 (MH + ) (as free base). [0521] HRMS (FAB + ) for C 23 H 21 FN 7 O 2 (MH + ): calcd, 446.1741; found, 446.1756. EXAMPLE 62 [0522] 5(R)-3-[4-[2-[(1α,5α,6β)-3-t-Butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-5-[(isoxazol-3-yl)oxy]methyloxazolidin-2-one [0523] Title Compound 62 (53.8 mg) was prepared from N-[5(S)-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-5-hydroxymethyloxazolidin-2-one (50.0 mg) in the same manner as described for EXAMPLE 66. [0524] MS (FAB + ) m/z: 562 (MH + ). [0525] HRMS (FAB + ) for C 29 H 29 FN 5 O 6 (MH + ): calcd, 562.2102; found, 562.2074. EXAMPLE 63 [0526] 5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-5-[(isoxazol-3-yl)oxy]methyloxazolidin-2-one Hydrochloride [0527] Title Compound 63 (303 mg) was prepared from 5(R)-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-Azabicyclo-[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-5-[(isoxazol-3-yl)oxy]methyloxazolidin-2-one (400 mg) in the same manner as described for EXAMPLE 2. [0528] MS (FAB + ) m/z: 462 (MH + ) (as free base). [0529] HRMS (FAB + ) for C 24 H 21 FN 5 O 4 (MH + ): calcd, 462.1578; found, 462.1534. EXAMPLE 64 [0530] 5(R)-3-[4-[2-[(1α,5α,6β)-3-t-Butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-5-[N-(t-butoxycarbonyl)-N-(isoxazol-3-yl)]aminomethyloxazolidin-2-one [0531] Title Compound 64 (58.2 mg) was prepared from N-[5(S)-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo-[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-5-hydroxymethyloxazolidin-2-one (50.0 mg) in the same manner as described for EXAMPLE 67. [0532] MS (FAB + ) m/z: 661 (MH + ). [0533] HRMS (FAB + ) for C 34 H 38 FN 6 O 7 (MH + ): calcd, 661.2786; found, 661.2760. EXAMPLE 65 [0534] 5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-5-[N-(isoxazol-3-yl)]aminomethyloxazolidin-2-one Hydrochloride [0535] Title Compound 65 (280 mg) was prepared from 5(R)-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-5-[N-(t-butoxycarbonyl)-N-(isoxazol-3-yl)]aminomethyloxazolidin-2-one (600 mg) in the same manner as described for EXAMPLE 2. [0536] MS (FAB + ) m/z: 461 (MH + ) (as free base). [0537] HRMS (FAB + ) for C 24 H 22 FN 6 O 3 (MH + ): calcd, 461.1737; found, 461.1712. EXAMPLE 66 [0538] 5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-5-[(isoxazol-3-yl)oxy]methyloxazolidin-2-one [0539] To a suspension of N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]hexan-6-yl]-pyridin-5-yl]-3-fluorophenyl]-5-hydroxymethyloxazolidin-2-one (200 mg), 3-hydroxyisoxazole (55.9 mg) and triphenylphosphine (199 mg) in tetrahydrofuran (5 mL) was added diisopropyl azodicarboxylate (133 mg), the mixture was stirred at room temperature for 1 hour, and concentrated in vacuo. After treatment of the residue with ethyl acetate and ether, the resulting residue was dissolved in chloroform, insoluble materials were filtered off, and filtrate was concentrated in vacuo to give 5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]hexan-6-yl]-pyridin-5-yl]-3-fluorophenyl]-5-[(isoxazol-3-yl)oxy]methyloxazolidin-2-one (205 mg). [0540] MS (FAB + ) m/z: 463 (MH + ). [0541] HRMS (FAB + ) for C 24 H 20 FN 4 O 5 (MH + ): calcd, 463.1418; found, 463.1439. EXAMPLE 67 [0542] 5(R)-5-[N-(t-Butoxycarbonyl)-N-(isoxazol-3-yl)]aminomethyl-3-[4-[2-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]oxazolidin-2-one [0543] To a suspension of N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]hexan-6-yl]-pyridin-5-yl]-3-fluorophenyl]-5-hydroxymethyloxazolidin-2-one (300 mg), 3-N-(t-butoxycarbonyl)aminoisoxazole (168 mg), and tetramethylazodicarboxamide (196 mg) in toluene (7.5 mL) was added tributylphosphine (230 mg), and the mixture was stirred at 50° C. for 2 hours. Flash chromatography (silica, hexane:ethyl acetate=1:1) of the mixture gave 5(R)-5-[N-(t-butoxycarbonyl)-N-(isoxazol-3-yl)]aminomethyl-3-[4-[2-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]oxazolidin-2-one (392 mg). [0544] MS (FAB + ) m/z: 562 (MH + ). [0545] HRMS (FAB + ) for C 29 H 29 FN 5 O 6 (MH + ): calcd, 562.2102; found, 562.2123. EXAMPLE 68 [0546] 5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-5-[N-(isoxazol-3-yl)]aminomethyloxazolidin-2-one [0547] To a solution of 5(R)-5-[N-(t-butoxycarbonyl)-N-(isoxazol-3-yl)]aminomethyl-3-[4-[2-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]oxazolidin-2-one (375 mg) in dichloromethane (4.0 mL) was added trifluoroacetic acid (2.0 mL) at 0° C., the mixture was stirred at room temperature for 2 hours and then concentrated in vacuo. After dilution of the residue with ethyl acetate, the mixture was washed with 5% potassium carbonate solution, dried over anhydrous magnesium sulfate, and then concentrated in vacuo to give 5(R)-3-[4-[2-[(1α,5α,6β)-6-cyan-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-5-[N-(isoxazol-3-yl)]aminomethyloxazolidin-2-one (189 mg). [0548] MS (FAB + ) m/z: 462 (MH + ). [0549] HRMS (FAB + ) for C 24 H 21 FN 5 O 4 (MH + ): calcd, 462.1578; found, 462.1602. EXAMPLE 69 [0550] N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]propionamide [0551] The title Compound 69 (213 mg) was prepared from 5(S)-aminomethyl-3-[4-[2-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]oxazolidin-2-one (200 mg) in the same manner as described for EXAMPLE 70. [0552] MS (FAB + ) m/z: 451 (MH + ). [0553] HRMS (FAB + ) for C 24 H 24 FN 4 O 4 (MH + ): calcd, 451.1782; found, 451.1753. EXAMPLE 70 [0554] N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]difluoroacetamide [0555] To a suspension of 5(S)-aminomethyl-3-[4-[2-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]hexan-6-yl]-pyridin-5-yl]-3-fluorophenyl]oxazolidin-2-one (200 mg) in pyridine (5 mL) was added difluoroacetic anhydride (159 mg) at 0° C., the mixture was stirred at room temperature for 2 hours and then concentrated in vacuo. After dilution of the residue with dichloromethane, the mixture was washed with 3% hydrochloric acid and 5% sodium hydrogencarbonate solution, dried over anhydrous magnesium sulfate, and then concentrated in vacuo. Flash chromatography (silica, dichloromethane:methanol=15:1) of the residue gave N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]difluoroacetamide (230 mg). [0556] MS (FAB + ) m/z: 473 (MH + ). [0557] HRMS (FAB + ) for C 23 H 20 F 3 N 4 O 4 (MH + ): calcd, 473.1437; found, 473.1426. EXAMPLE 71 [0558] N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]cyclopropanecarboxamide [0559] To a solution of 5(S)-aminomethyl-3-[4-[2-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]hexan-6-yl]-pyridin-5-yl]-3-fluorophenyl]oxazolidin-2-one (200 mg) and cyclopropanecarboxylic acid (56.8 mg) in dichloromethane (10 mL) was added 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride (146 mg) at room temperature, the mixture was stirred at the same temperature for 2 hours. The mixture was washed with water and 5% sodium hydrogencarbonate solution, dried over anhydrous magnesium sulfate, and then concentrated in vacuo. Flash chromatography (silica, dichloromethane:methanol=15:1) of the residue gave N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-cyan-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]cyclopropanecarboxamide (167 mg). [0560] MS (FAB + ) m/z: 463 (MH + ). [0561] HRMS (FAB + ) for C 25 H 24 FN 4 O 4 (MH + ): calcd, 463.1782; found, 463.1774. EXAMPLE 72 [0562] N-[5(S)-3-[4-[2-[(1α,5α,6β)-3-t-Butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]propionamide [0563] Title Compound 72 (305 mg) was prepared from 5(S)-aminomethyl-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]oxazolidin-2-one (300 mg) and propionyl chloride (58 μL) in the same manner as described for EXAMPLE 92. [0564] MS (FAB + ) m/z: 550 (MH + ). EXAMPLE 73 [0565] N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]propionamide [0566] Title Compound 73 (165 mg) was prepared from N-[5(S)-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]propionamide (295 mg) in the same manner as described for EXAMPLE 49. [0567] MS (FAB + ) m/z: 450 (MH + ). [0568] HRMS (FAB + ) for C 24 H 25 FN 5 O 3 (MH + ): calcd, 450.1941; found, 450.1905. EXAMPLE 74 [0569] N-[5(S)-3-[4-[2-[(1α,5α,6β)-3-t-Butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]cyclopropanecarboxamide [0570] Title Compound 74 (260 mg) was prepared from 5(S)-aminomethyl-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]oxazolidin-2-one (300 mg) in the same manner as described for EXAMPLE 71. [0571] MS (FAB + ) m/z: 562 (MH + ). EXAMPLE 75 [0572] N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]cyclopropanecarboxamide Hydrochloride [0573] Title Compound 75 (183 mg) was prepared from N-[5(S)-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]cyclopropanecarboxamide (250 mg) in the same manner as described for EXAMPLE 2. [0574] MS (FAB + ) m/z: 462 (MH + ) (as free base). [0575] HRMS (FAB + ) for C 25 H 25 FN 5 O 3 (MH + ): calcd, 462.1941; found, 462.1938. EXAMPLE 76 [0576] N-[5(S)-3-[4-[2-[(1α,5α,6β)-3-t-Butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]difluoroacetamide [0577] Title Compound 76 (258 mg) was prepared from 5(S)-aminomethyl-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]oxazolidin-2-one (300 mg) in the same manner as described for EXAMPLE 70. [0578] MS (FAB + ) m/z: 572 (MH + ). EXAMPLE 77 [0579] N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]difluoroacetamide Hydrochloride [0580] Title Compound 77 (170 mg) was prepared from N-[5(S)-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]difluoroacetamide (250 mg) in the same manner as described for EXAMPLE 2. [0581] MS (FAB + ) m/z: 472 (MH + ) (as free base). [0582] HRMS (FAB + ) for C 23 H 21 F 3 N 5 O 3 (MH + ): calcd, 472.1596; found, 472.1590. EXAMPLE 78 [0583] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-methyl-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0584] To a suspension of 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (20.0 mg) in tetrahydrofuran (0.45 mL) was added acetic acid (5.1 μL), 35% formaldehyde solution (35.6 μL), and sodium triacetoxyborohydride (20.0 mg) at room temperature, the mixture was stirred at the same temperature for 3 hours. After quenching the reaction by addition of saturated sodium hydrogencarbonate solution at 0° C., the mixture was extracted with dichloromethane-methanol (5:1) solution. The organic extracts were washed with brine, dried over anhydrous magnesium sulfate, and then concentrated in vacuo. Preparative thin-layer chromatography (silica, dichloromethane:methanol=10:1) of the residue gave 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-methyl-3-azabicyclo[3.1.0]hexan-6-yl]-pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (15.0 mg). [0585] MS (FAB + ) m/z: 460 (MH + ). [0586] HRMS (FAB + ) for C 24 H 23 FN 7 O 2 (MH + ): calcd, 460.1897; found, 460.1888. EXAMPLE 79 [0587] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-3,6-Dicyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0588] A suspension of 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (300 mg) and sodium acetate (390 mg) in methanol (20 mL) was stirred at room temperature for 30 minutes. To the resulting suspension was added a solution of cyanogens bromide in dichloromethane (5 M, 0.4 mL) at 0° C., the mixture was stirred at the same temperature for 8 hours. After insoluble materials were filtered off, the filtrate was concentrated in vacuo. Treatment of the residue with water and methanol gavel-[5(R)-3-[4-[2-[(1α,5α,6β)-3,6-dicyano-3-azabicyclo[3.1.0]hexan-6-yl]-pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (138 mg). [0589] MS (FAB + ) m/z: 471 (MH + ). [0590] HRMS (FAB + ) for C 24 H 20 FN 8 O 2 (MH + ): calcd, 471.1693; found, 471.1709. EXAMPLE 80 [0591] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-3-[(1-t-Butoxycarbonylaminocyclopropan-1yl)carbonyl]-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0592] A mixture of 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (20.0 mg), 1-(t-butoxycarbonylamino)cyclopropane-1-carboxylic acid (13.6 mg), 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride (12.9 mg), and 4-(dimethylamino)pyridine (8.2 mg) in dichloromethane was stirred at room temperature for 5 hours. After dilution of the mixture with water, the mixture was washed with brine, dried over anhydrous magnesium sulfate, and then concentrated in vacuo. Flash chromatography (silica, dichloromethane:methanol=10:1) of the residue gave title compound 80(28.6 mg). [0593] MS (FAB + ) m/z: 629 (MH + ). [0594] HRMS (FAB + ) for C 32 H 34 FN 8 O 5 (MH + ): calcd, 629.2636; found, 629.2633. EXAMPLE 81 [0595] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-3-[(1-Aminocyclopropan-1-yl)carbonyl]-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole Hydrochloride [0596] Title Compound 81 (18.4 mg) was prepared from 1-[5(R)-3-[4-[2-[(1α,5α,6β)-3-[(1-t-butoxycarbonylaminocyclopropan-1-yl)carbonyl]-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (26.6 mg) in the same manner as described for EXAMPLE 2. [0597] MS (FAB + ) m/z: 529 (MH + ) (as free base). [0598] HRMS (FAB + ) for C 27 H 26 FN 8 O 3 (MH + ): calcd, 529.2112; found, 529.2105. EXAMPLE 82 [0599] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-3-(2-Aminoethyl)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0600] Step 1. [0601] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-[2-(phthalimid-2-yl)ethyl]-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole. [0602] A suspension of 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (20.0 mg), 2-bromoethylphthalimide (11.4 mg) and potassium carbonate (9.3 mg) in acetonitrile (0.2 mL) was heated under reflux for overnight and concentrated in vacuo. Flash chromatography (silica, dichloromethane:methanol=10:1) of the residue gave compound of Step 1 of Example 82 (25.2 mg). [0603] MS (FAB + ) m/z: 619 (MH + ): [0604] HRMS (FAB + ) for C 33 H 28 FN 8 O 4 (MH + ): calcd, 619.2218; found, 619.2214. [0605] Step 2. [0606] Title compound 82 [0607] A mixture of the compound of Step 1 of Example 82 (20.0 mg) and methylhydrazine (34.4 μL) in ethanol was heated under reflux for 2 days. After dilution of the mixture with brine, the mixture was extracted with ethyl acetate. The organic extracts were dried over anhydrous magnesium sulfate, and then concentrated in vacuo. Preparative thin-layer chromatography (NH silica, ethyl acetate:methanol=10:1) of the residue gave title compound 82 (10.8 mg). [0608] MS (FAB + ) m/z: 489 (MH + ). [0609] HRMS (FAB + ) for C 25 H 26 FN 8 O 2 (MH + ): calcd, 489.2163; found, 489.2195. EXAMPLE 83 [0610] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-[2-(1,2,4-triazol-4-yl)ethyl]-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0611] A mixture of 1-[5(R)-3-[4-[2-[(1α,5α,6β)-3-(2-aminoethyl)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (29.7 mg), dimethylformamide azine (8.6 mg) and p-toluenesulfonic acid (0.6 mg) in toluene was heated under reflux for 16 hours and concentrated in vacuo. Preparative thin-layer chromatography (silica, dichloromethane:methanol=10:1) of the residue gave title compound 83 (10.9 mg). [0612] MS (FAB + ) m/z: 541 (MH + ). [0613] HRMS (FAB + ) for C 27 H 26 FN 10 O 2 (MH + ): calcd, 541.2224; found, 541.2203. EXAMPLE 84 [0614] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-(morpholin-4-yl)acetyl-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0615] Step 1. [0616] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-3-Bromoacetyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole. [0617] To a solution of bromoacetyl bromide (9.8 μL) in dichloromethane (0.3 mL) was added a solution of 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (50.0 mg) and triethylamine (15.6 μL) in dichloromethane (1.5 mL) at 0° C., the mixture was stirred at the same temperature for 3 hours, and concentrated in vacuo. After dilution of the residue with dichloromethane-methanol (10:1) solution, the mixture was washed with 2 N hydrochloric acid, dried over anhydrous magnesium sulfate, and then concentrated in vacuo to give compound of Step 1 of example 84 (88.1 mg). [0618] Step 2. [0619] Title compound 84. [0620] To a solution of morpholine (29.3 μL) in acetonitrile (1.0 mL) was added a solution of the crude compound of Step 1 of Example 84 (88.1 mg) in acetonitrile (1.5 mL) at 0° C., the mixture was stirred at the same temperature for 5 hours. After dilution of the residue with water, the mixture was washed with dichloromethane-methanol (10:1) solution. The organic extracts were washed with brine, dried over anhydrous magnesium sulfate, and then concentrated in vacuo. Preparative thin-layer chromatography (silica, dichloromethane:methanol=5:1) of the residue gave title compound 84 (17.5 mg). [0621] MS (FAB + ) m/z: 573 (MH + ). [0622] HRMS (FAB + ) for C 29 H 30 FN 8 O 4 (MH + ): calcd, 573.2374; found, 573.238 1. EXAMPLE 85 [0623] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-(5-cyanopyridin-2-yl)-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0624] To a suspension of 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (20.0 mg) in dimethyl sulfoxide (0.5 mL) was added diisopropylethylamine (78 μL), the mixture was stirred at room temperature for 5 minutes. To the resulting mixture was added 2-bromo-5-cyanopyridine (16.4 mg), the mixture was stirred at 60° C. for 9 hours. After dilution of the mixture with ethyl acetate and water, the mixture was extracted with ethyl acetate. The organic extracts were washed with water and brine, dried over anhydrous magnesium sulfate, filtered, and then concentrated in vacuo. Flash chromatography (silica, dichloromethane:methanol=20:1) of the residue gave title compound 85 (12.8 mg). [0625] MS (FAB + ) m/z: 548 (MH + ). [0626] HRMS (FAB + ) for C 29 H 23 FN 9 O 2 (MH + ): calcd, 548.1959; found, 548.1984. EXAMPLE 86 [0627] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-(1,3-dihydroxypropan-2-yl)-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0628] To a solution of 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]1,2,3-triazole (50.0 mg) in dichloromethane-methanol (10:1, 1.0 mL) was added 1,3-dihydroxyacetone dimmer (60.7 mg), methanol (4.0 mL), acetic acid (0.5 mL), and sodium cyanoborohydride (21.2 mg), the mixture was stirred at room temperature for 7.5 hours. After addition of 2 N hydrochloric acid, the mixture was stirred at room temperature for 1 hour. The mixture was diluted with brine and extracted with dichloromethane-methanol (10:1). The organic extracts were dried over anhydrous potassium carbonate, filtered, and then concentrated in vacuo. Preparative thin-layer chromatography (silica, dichloromethane:methanol=10:1) of the residue gave title compound 86 (13.2 mg). [0629] MS (FAB + ) m/z: 520 (M + ). [0630] HRS (FAB + ) for C 26 H 27 FN 7 O 4 (MH + ): calcd, 520.2109; found, 520.2086. EXAMPLE 87 [0631] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-[((2S)-pyrrolidin-2-yl)carbonyl]-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole Hydrochloride [0632] Step 1. [0633] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-3-[((2S)-1-t-Butoxycarbonylpyrrolidin-2-yl)carbonyl]-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole. [0634] The compound of Step 1 in Example 87 (27.1 mg) was prepared from 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]-hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (20.0 mg) and N-Boc-L-proline (11.6 mg) in the same manner as described for EXAMPLE 71. [0635] MS (FAB + ) m/z: 643 (MH + ). [0636] HRMS (FAB + ) for C 33 H 36 FN 8 O 5 (MH + ): calcd, 643.2793; found, 643.2744. [0637] Step 2. [0638] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-[((2S)-pyrrolidin-2-yl)carbonyl]-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole Hydrochloride. The compound of Step 2 in Example 87 (16.8 mg) was prepared from 1-[5(R)-3-[4-[2-[(1α,5α,6β)-3-[((2S)-1-t-butoxycarbonylpyrrolidin-2-yl)carbonyl]-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (26.9 mg) in the same manner as described for EXAMPLE 2. [0639] MS (FAB + ) m/z: 543 (MH + ) (as free base). [0640] HRMS (FAB + ) for C 28 H 28 FN 8 O 3 (MH + ): calcd, 543.2268; found, 543.2243. EXAMPLE 88 [0641] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-[((2S,4R)-4-hydroxypyrrolidin-2-yl)carbonyl]-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole Hydrochloride [0642] Step 1. [0643] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-3-[((2S,4R)-1-t-Butoxycarbonyl-4-hydroxypyrrolidin-2-yl)carbonyl]-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole. [0644] The compound of Step 1 of Example 88 (28.4 mg) was prepared from 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (20.0 mg) and N-Boc-4-hydroxy-L-proline (12.3 mg) in the same manner as described for EXAMPLE 71. [0645] MS (FAB + ) m/z: 659 (MH + ). [0646] HRMS (FAB + ) for C 33 H 36 FN 8 O 6 (MH + ): calcd, 659.2742; found, 659.2775. [0647] Step 2. [0648] Compound 88 (15.6 mg) was prepared from the compound of Step 1 of Example 88 (27.4 mg) in the same manner as described for EXAMPLE 2. [0649] MS (FAB + ) m/z: 559 (MH + ). [0650] HRMS (FAB + ) for C 28 H 28 FN 8 O 4 (MH + ): calcd, 559.2218; found, 559.2247. EXAMPLE 89 [0651] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-[((2S,4S)-4-fluoropyrrolidin-2-yl)carbonyl]-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole Hydrochloride [0652] Step. 1 [0653] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-3-[((2S,4S)-1-t-Butoxycarbonyl-4-fluoropyrrolidin-2-yl)carbonyl]-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole. [0654] The compound of Step 1 of Example 89 (73.6 mg) was prepared from 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (50.0 mg) and N-Boc-(4S)-fluoro-L-proline (31.5 mg) in the same manner as described for EXAMPLE 71. [0655] MS (FAB + ) m/z: 661 (MH + ). [0656] HRMS (FAB + ) for C 33 H 35 F 2 N 8 O 5 (MH + ): calcd, 661.2698; found, 661.2656. [0657] Step 2. [0658] The compound of Example 89 (44.0 mg) was prepared from the compound of Step 1 of Example 89 (69.3 mg) in the same manner as described for EXAMPLE 2. [0659] MS (FAB + ) m/z: 561 (MH + ). [0660] HRMS (FAB + ) for C 28 H 27 F 2 N 8 O 3 (MH + ): calcd, 561.2174; found, 561.2142. EXAMPLE 90 [0661] 1-[5(R)-3-[4-[4-[(1α,5α,6β)-3-t-Butoxycarbonyl-6-(t-butoxycarbonyl)amino-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0662] Title Compound 90 (473 mg) was prepared from 1-[5(R)-3-[3-fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolyl)-phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (600 mg) and 5-bromo-2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-(t-butoxycarbonyl)amino-3-azabicyclo[3.1.0]hexan-6-yl]pyridine (702 mg) in the same manner as described for EXAMPLE 1. [0663] MS (FAB + ) m/z: 636 (MH + ). [0664] HRMS (FAB + ) for C 32 H 39 FN 7 O 6 (MH + ): calcd, 636.2946; found, 636.2931. EXAMPLE 91 [0665] 1-[5(R)-3-[4-[4-[(1α,5α,6β)-6-Amino-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole Dihydrochloride [0666] Title Compound 91 (305 mg) was prepared from 1-[5(R)-3-[4-[4-[(1α,5α,6β)-3-t-butoxycarbonyl-6-(t-butoxycarbonyl)-amino-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (397 mg) in the same manner as described for EXAMPLE 2. [0667] MS (FAB + ) m/z: 436 (MH + ). [0668] HRMS (FAB + ) for C 22 H 23 FN 7 O 2 (MH + ): calcd, 436.1897; found, 436.1898. EXAMPLE 92 [0669] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-3-Acetoxyacetyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0670] To a suspension of 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (30.0 mg) in dichloromethane (0.7 mL) was added triethylamine (28 μL) and acetoxyacetyl chloride (7.0 μL) at 0° C., the mixture was stirred at the same temperature for 1 hour. After dilution of the mixture with water, the mixture was extracted with dichloromethane. The organic extracts were washed with water and brine, dried over anhydrous sodium sulfate, filtered, and then concentrated in vacuo. Flash chromatography (silica, dichloromethane:methanol=10:1) of the residue gave the title compound of 92 (34.7 mg). [0671] MS (FAB + ) m/z: 546 (MH + ). [0672] HRMS (FAB + ) for C 27 H 25 FN 7 O 5 (MH + ): calcd, 546.1901; found, 546.1888. EXAMPLE 93 [0673] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-hydroxyacetyl-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0674] To a solution of 1-[5(R)-3-[4-[2-[(1α,5α,6β)-3-acetoxyacetyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (255 mg) in methanol (4.5 mL) and tetrahydrofuran (1.3 mL) was added potassium carbonate (130 mg) at room temperature, the mixture was stirred at the same temperature for 2 hours, and concentrated in vacuo. After dilution of the residue with dichloromethane-methanol (5:1) solution, the mixture was washed with brine. The organic extracts were dried over anhydrous magnesium sulfate, filtered, and then concentrated in vacuo. Flash chromatography (silica, dichloromethane:methanol=5:1) of the residue gave the title compound of Example 93 (137 mg). [0675] MS (FAB + ) m/z: 504 (MH + ). [0676] HRMS (FAB + ) for C 25 H 23 FN 7 O 4 (MH + ): calcd, 504.1796; found, 504.1800. EXAMPLE 94 [0677] N-[5(S)-3-[4-[2-[(1α,5α,6β)-3-t-Butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-(2,2-dichlorocyclopropane)-1-carboxamide Diastereomer A and Diastereomer B [0678] Title Compound 94 (diastereomer A: 100 mg, diastereomer B: 76.6 mg) were prepared from 5(S)-aminomethyl-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]oxazolidin-2-one (269 mg) and 2,2-dichlorocyclopropanecarboxylic acid (110 mg) in the same manner as described for EXAMPLE 71. [0679] diastereomer A (less polar): [0680] MS (FAB + ) m/z: 630 (MH + ). [0681] diastereomer B (more polar): [0682] MS (FAB + ) m/z: 630 (MH + ). EXAMPLE 95 [0683] N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-(2,2-dichlorocyclopropane)-1-carboxamide Diastereomer A′ [0684] Title Compound 95 (diastereomer A′: 78.9 mg) was prepared from N-[5(S)-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-(2,2-dichlorocyclopropane)-1-carboxamide (diastereomer A: 97.0 mg) in the same manner as described for EXAMPLE 49. [0685] MS (FAB + ) m/z: 530 (MH + ). [0686] HRMS (FAB + ) for C 25 H 23 Cl 2 FN 5 O 3 (MH + ): calcd, 530.1162; found, 530.1198. EXAMPLE 96 [0687] N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-(2,2-dichlorocyclopropane)-1-carboxamide Diastereomer B′ [0688] Title Compound 96 (diastereomer B′: 57.2 mg) was prepared from N-[5(S)-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-(2,2-dichlorocyclopropane)-1-carboxamide (diastereomer B: 73.0 mg) in the same manner as described for EXAMPLE 49. [0689] MS (FAB + ) m/z: 530 (MH + ). [0690] HRMS (FAB + ) for C 25 H 23 Cl 2 FN 5 O 3 (MH + ): calcd, 530.1162; found, 530.1137. EXAMPLE 97 [0691] N-[5(S)-3-[4-[2-[(1α,5α,6β)-3-t-Butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-(2,2-difluorocyclopropane)-1-carboxamide Diastereomer C and Diastereomer D [0692] Title Compound 97 (diastereomer C: 125 mg, diastereomer D: 125 mg) were prepared from 5(S)-aminomethyl-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]oxazolidin-2-one (300 mg) and 2,2-difluorocyclopropanecarboxylic acid (96.5 mg) in the same manner as described for EXAMPLE 71. EXAMPLE 98 [0693] N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-(2,2-difluorocyclopropane)-1-carboxamide Diastereomer C′ [0694] Title Compound 98 (diastereomer C′: 75.8 mg) was prepared from N-[5(S)-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-(2,2-difluorocyclopropane)-1-carboxamide (diastereomer C: 122 mg) in the same manner as described for EXAMPLE 49. [0695] MS (FAB + ) m/z: 498 (MH + ). [0696] HRMS (FAB + ) for C 25 H 23 F 3 N 5 O 3 (MH + ): calcd, 498.1753; found, 498.1783. EXAMPLE 99 [0697] N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-(2,2-difluorocyclopropane)-1-carboxamide Diastereomer D′ [0698] Title Compound 99 (diastereomer D′: 62.2 mg) was prepared from N-[5(S)-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0.]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-(2,2-difluorocyclopropane)-1-carboxamide (diastereomer D: 122 mg) in the same manner as described for EXAMPLE 49. [0699] MS (FAB + ) m/z: 498 (MH + ). [0700] HRMS (FAB + ) for C 25 H 23 F 3 N 5 O 3 (MH + ): calcd, 498.1753; found, 498.1740. EXAMPLE 100 [0701] O-Methyl-N-[5(S)-3-[4-[2-[(1α,5α,6β)-3-t-Butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]carbamate [0702] Title Compound 100 (53.2 mg) was prepared from 5(S)-aminomethyl-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]oxazolidin-2-one (200 mg) and methyl chloroformate (37 μL) in the same manner as described for EXAMPLE 92. [0703] MS (FAB + ) m/z: 552 (MH + ). EXAMPLE 101 [0704] O-Methyl-N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]carbamate [0705] Title Compound 101 (32.7 mg) was prepared from O-methyl N-[5(S)-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]carbamate (50.0 mg) in the same manner as described for EXAMPLE 49. [0706] MS (FAB + ) m/z: 452 (MH + ). [0707] HRMS (FAB + ) for C 23 H 23 FN 5 O 4 (MH + ): calcd, 452.1734; found, 452.1729. EXAMPLE 102 [0708] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-3,6-Dicyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0709] Title Compound 102 (12.2 mg) was prepared from 1-[5(R)-3-[4-[4-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]-hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (15.0 mg) in the same manner as described for EXAMPLE 79. [0710] MS (FAB + ) m/z: 489 (MH + ). [0711] HRMS (FAB + ) for C 24 H 19 F 2 N 8 O 2 (MH + ): calcd, 489.1599; found, 489.1634. EXAMPLE 103 [0712] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-methyl-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0713] Title Compound 103 (14.8 mg) was prepared from 1-[5(R)-3-[4-[4-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (15.0 mg) in the same manner as described for EXAMPLE 78. [0714] MS (FAB + ) m/z: 478 (MH + ). [0715] HRMS (FAB + ) for C 24 H 22 F 2 N 7 O 2 (MH + ): calcd, 478.1803; found, 478.1825. EXAMPLE 104 [0716] 1-[5(R)-3-[3-Fluoro-4-[2-[(1α,5α,6β)-6-hydroxymethyl-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0717] Title Compound 104 (73.2 mg) was prepared from 1-[5(R)-3-[3-fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolyl)-phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (83.4 mg) and 5-bromo-2-[(1α,5α,6β)-6-hydroxymethyl-3-oxabicyclo[3.1.0]hexan-6-yl]pyridine (58.0 mg) in the same manner as described for EXAMPLE 1. [0718] MS (FAB + ) m/z: 452 (MH + ). [0719] HRMS (FAB + ) for C 23 H 23 FN 5 O 4 (MH + ): calcd, 452.1734; found, 452.1735. EXAMPLE 105 [0720] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-4-fluoro-1,2,3-triazole [0721] Title Compound 105 (101 mg) was prepared from 4-fluoro-1-[5(R)-3-(3-fluoro-4-iodophenyl)-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (125 mg) and 5-bromo-2-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridine (122 mg) in the same manner as described for EXAMPLE 31. [0722] MS (FAB + ) m/z: 465 (MH + ). [0723] HRMS (FAB + ) for C 23 H 19 F 2 N 6 O 3 (MH + ): calcd, 465.1487, found, 465.1514. EXAMPLE 106 [0724] 1-[5(R)-3-[4-[4-[(1α,5α,6β)-3-t-Butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]-hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-4-fluoro-1,2,3-triazole [0725] Title Compound 106 (301 mg) was prepared from 4-fluoro-1-[5(R)-3-[3-fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolyl)phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (370 mg) and 5-bromo-2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin (332 mg) in the same manner as described for EXAMPLE 1. [0726] MS (FAB + ) m/z: 564 (MH + ). [0727] HRMS (FAB + ) for C 28 H 28 F 2 N 7 O 4 (MH + ): calcd, 564.2171; found, 564.2168. EXAMPLE 107 [0728] 1-[5(R)-3-[4-[4-[(1α,5α,6β)-6-Cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-4-fluoro-1,2,3-triazole Hydrochloride [0729] Title Compound 107 (231 mg) was prepared from 1-[5(R)-3-[4-[4-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-4-fluoro-1,2,3-triazole (290 mg) in the same manner as described for EXAMPLE 2. [0730] MS (FAB + ) m/z: 464 (MH + ) (as free base). [0731] HRMS (FAB + ) for C 23 H 20 F 2 N 7 O 2 (MH + ): calcd, 464.1647; found, 464.1645. EXAMPLE 108 [0732] 1-[5(R)-3-[4-[4-[(1α,5α,6β)-3-t-Butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-5-fluoro-1,2,3-triazole [0733] Title Compound 108 (169 mg) was prepared from 1-[5(R)-3-(3-fluoro-4-iodophenyl)-2-oxooxazolidin-5-ylmethyl]-5-fluoro-1,2,3-triazole (150 mg) and 5-bromo-2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo-[3.1.0]hexan-6-yl]pyridine (202 mg) in the same manner as described for EXAMPLE 3 1. [0734] MS (FAB + ) m/z: 564 (MH + ). [0735] HRMS (FAB + ) for C 28 H 28 F 2 N 7 O 4 (MH + ): calcd, 564.2171; found, 564.2189. EXAMPLE 109 [0736] 1-[5(R)-3-[4-[4-[(1α,5α,6β)-6-Cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-5-fluoro-1,2,3-triazole Hydrochloride [0737] Title Compound 109 (118 mg) was prepared from 1-[5(R)-3-[4-[4-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-5-fluoro-1,2,3-triazole (151 mg) in the same manner as described for EXAMPLE 2. [0738] MS (FAB + ) m/z: 464 (MH + ) (as free base). [0739] HRMS (FAB + ) for C 23 H 20 F 2 N 7 O 2 (MH + ): calcd, 464.1647; found, 464.1679. EXAMPLE 110 [0740] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-3-(4-t-Butoxycarbonylpiperazin-1-yl)acetyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0741] Title compound 110 (60.7 mg) was prepared from 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (50.0 mg) and 1-t-butoxycarbonylpiperazine (62.6 mg) in the same manner as described for EXAMPLE 78. [0742] MS (FAB + ) m/z: 672 (MH + ). [0743] HRMS (FAB + ) for C 34 H 39 FN 9 O 5 (MH + ): calcd, 672.3058; found, 672.3040. EXAMPLE 111 [0744] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-(piperazin-1-yl)acetyl-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole Dihydrochloride [0745] Title Compound 111 (57.0 mg) was prepared from 1-[5(R)-3-[4-[2-[(1α,5α,6β)-3-(4-t-butoxycarbonylpiperazin-1-yl)-acetyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (59.7 mg) in the same manner as described for EXAMPLE 2. [0746] MS (FAB + ) m/z: 572 (MH + ) (as free base). [0747] HRMS (FAB + ) for C 29 H 31 FN 9 O 3 (MH + ): calcd, 572.2534; found, 572.2535. EXAMPLE 112 [0748] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-oxabicyclo[3.1.0]hexan-6-yl]thiopen-4-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0749] Title Compound 112 (261 mg) was prepared from 1-[5(R)-3-[3-fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolyl)-phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (388 mg) and 4-bromo-2-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]hexan-6-yl]thiophene (270 mg) in the same manner as described for EXAMPLE 1. [0750] MS (FAB + ) m/z: 452 (MH + ). [0751] HRMS (FAB + ) for C 22 H 19 FN 5 O 3 S (MH + ): calcd, 452.1193; found, 452.1180. EXAMPLE 113 [0752] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-(piperidin-1-yl)acetyl-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0753] Title Compound 113 (15.7 mg) was prepared from 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (20.0 mg) and piperidine (17.8 μL) in the same manner as described for EXAMPLE 84. [0754] MS (FAB + ) m/z: 571 (MH + ). [0755] HRMS (FAB + ) for C 30 H 32 FN 8 O 3 (MH + ): calcd, 571.258 1; found, 571.2579. EXAMPLE 114 [0756] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-(pyrrolidin-1-yl)acetyl-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0757] Title Compound 114 (20.7 mg) was prepared from 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (20.0 mg) and pyrrolidine (15 μL) in the same manner as described for EXAMPLE 84. [0758] MS (FAB + ) m/z: 557 (MH + ). [0759] HRMS (FAB + ) for C 30 H 32 FN 8 O 3 (MH + ): calcd, 557.2425; found, 557.2467. EXAMPLE 115 [0760] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-(4-dimethylaminopiperidin-1-yl)acetyl-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0761] Title Compound 115 (22.0 mg) was prepared from 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (20.0 mg) and 4-dimethylaminopiperidine dihydrochloride (36.2 mg) in the same manner as described for EXAMPLE 84. [0762] MS (FAB + ) m/z: 614 (MH + ). [0763] HRMS (FAB + ) for C 32 H 37 FN 9 O 3 (MH + ): calcd, 614.3003; found, 614.3049. EXAMPLE 116 [0764] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-[((2S)-pyrrolidin-2-yl)carbonyl]-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole Hydrochloride [0765] Step 1. [0766] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-3-[((2S)-1-t-Butoxycarbonylpyrrolidin-2-yl)carbonyl]-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole. [0767] The compound of Step 1 of Example 116 (13.3 mg) was prepared from 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]-hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (10.0 mg) and N-Boc-L-proline (5.6 mg) in the same manner as described for EXAMPLE 71 [0768] MS (FAB + ) m/z: 661 (MH + ). [0769] HRMS (FAB + ) for C 33 H 35 F 2 N 8 O 5 (MH + ): calcd, 661.2698; found, 661.2691. [0770] Step 2. [0771] Title Compound 116 (8.4 mg) was prepared from the compound of Step 1 of title Example 116 (13.3 mg) in the same manner as described for and EXAMPLE 2. [0772] MS (FAB + ) m/z: 561 (MH + ) (as free base). [0773] HRMS (FAB + ) for C 28 H 27 F 2 N 8 O 3 (MH + ): calcd, 561.2174; found, 561.2220. EXAMPLE 117 [0774] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-[((2S,4R)-4-hydroxypyrrolidin-2-yl)carbonyl]-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole Hydrochloride [0775] Step 1. [0776] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-3-[((2S,4R)-1-t-Butoxycarbonyl-4-hydroxypyrrolidin-2-yl)carbonyl]-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole. [0777] The compound of Step 1 of Example 117 (12.9 mg) was prepared from 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (10.0 mg) and N-Boc-4-hydroxy-L-proline (6.0 mg) in the same manner as described for EXAMPLE 71. [0778] MS (FAB + ) m/z: 677 (MH + ). [0779] HRMS (FAB + ) for C 33 H 35 F 2 N 8 O 6 (MH + ): calcd, 677.2698; found, 677.2691. [0780] Step 2. [0781] Title Compound 117 (2.7 mg) was prepared from the compound of Step 1 of Example 117 (11.7 mg) in the same manner as described for EXAMPLE 2. [0782] MS (FAB + ) m/z: 577 (MH + ) (as free base). [0783] HRMS (FAB + ) for C 28 H 27 F 2 N 8 O 4 (MH + ): calcd, 577.2123; found, 577.2123. EXAMPLE 118 [0784] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-[((2S,4S)-4-fluoropyrrolidin-2-yl)carbonyl]-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-y]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole Hydrochloride [0785] Step 1. [0786] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-3-[((2S,4S)-1-t-Butoxycarbonyl-4-fluoropyrrolidin-2-yl)carbonyl]-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole. [0787] The compound of Step 1 of Example 118 (12.8 mg) was prepared from 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (10.0 mg) and N-Boc-(4S)-fluoro-L-proline (6.0 mg) in the same manner as described for EXAMPLE 71 [0788] MS (FAB + ) m/z: 679 (MH + ). [0789] HRMS (FAB + ) for C 33 H 34 F 3 N 8 O 5 (MH + ): calcd, 679.2604; found, 679.2625. [0790] Step 2. [0791] Title Compound 118 (8.8 mg) was prepared from the compound of Step 1 of Example 118 (12.6 mg) EXAMPLE 2. [0792] MS (FAB + ) m/z: 579 (MH + ) (as free base). [0793] HRMS (FAB + ) for C 28 H 26 F 3 N 8 O 3 (MH + ): calcd, 579.2080; found, 579.2055. EXAMPLE 119 [0794] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Amino-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0795] Step 1. [0796] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-t-Butoxycarbonylamino-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole. [0797] The compound of Step 1 of Example 119 (9.8 mg) was prepared from 1-[5(R)-3-[3-fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolyl)phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (22.3 mg) and 5-bromo-2-[(1α,5α,6β)-6-t-butoxycarbonylamino-3-thiabicyclo[3.1.0]hexan-6-yl]pyridine (18.4 mg) in the same manner as described for EXAMPLE 1. [0798] MS (FAB + ) m/z: 553 (MH + ). [0799] HRMS (FAB + ) for C 27 H 30 FN 6 O 4 S (MH + ): calcd, 553.2033; found, 553.2039. [0800] Step 2. [0801] Title Compound 119 (1.2 mg) was prepared from the compound of Step 1 of Example 119 (4.0 mg) in the same manner as described for EXAMPLE 49. [0802] MS (FAB + ) m/z: 453 (MH + ). [0803] HRMS (FAB + ) for C 22 H 22 FN 6 O 2 S (MH + ): calcd, 453.1509; found, 453.1520. EXAMPLE 120 [0804] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Amino-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole S-Oxide Diastereomer E′ and Diastereomer F′ [0805] Step 1. [0806] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-t-Butoxycarbonylamino-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole S-Oxide Diastereomer E and Diastereomer F. [0807] The compound of Step 1 of Example 120 diastereomer E (4.8 mg) and diastereomer F (10.2 mg) was prepared from 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-t-butoxycarbonylamino-3-thiabicyclo[3.1.0]hexan-6-yl]-pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (20.0 mg) in the same manner as described for EXAMPLE 58. [0808] Diastereomer E (less polar): [0809] MS (FAB + ) m/z: 569 (MH + ). [0810] HRMS (FAB + ) for C 27 H 30 FN 6 O 5 S (MH + ): calcd, 569.1982; found, 569.1945. [0811] Diastereomer F (more polar): [0812] MS (FAB + ) m/z: 569 (MH + ). [0813] HRMS (FAB + ) for C 27 H 30 FN 6 O 5 S (MH + ): calcd, 569.1982; found, 569.1947. [0814] Step 2. [0815] Title Compound 120 diastereomer E′(2.4 mg) was prepared from the compound of Step 1 of Example 120 diastereomer E (3.7 mg) in the same manner as described for EXAMPLE 49. [0816] MS (FAB + ) m/z: 469 (MH + ). [0817] HRMS (FAB + ) for C 23 H 20 FN 6 O 2 S (MH + ): calcd, 469.1458; found, 469.1411. EXAMPLE 121 [0818] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Amino-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole S,S-Dioxide [0819] Step 1. [0820] 1 -[5(R)-3-[4-[2-[(1α,5α,6β)-6-t-Butoxycarbonylamino-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole S,S-Dioxide. [0821] The compound of Step 1 of Example 121 (10.6 mg) was prepared from 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-t-butoxycarbonylamino-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (20.0 mg) in the same manner as described for EXAMPLE 59. [0822] MS (FAB + ) m/z: 585 (MH + ). [0823] HRMS (FAB + ) for C 27 H 30 FN 6 O 6 S (MH + ): calcd, 585.1932; found, 585.1923. [0824] Step 2. [0825] Title Compound 121 (2.3 mg) was prepared from the compound of Step 1 of Example 121 (3.0 mg) in the same manner as described for EXAMPLE 49. [0826] MS (FAB + ) m/z: 485 (MH + ). [0827] HRMS (FAB + ) for C 22 H 22 FN 6 O 4 S (MH + ): calcd, 485.1407; found, 485.1397. EXAMPLE 122 [0828] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Amino-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0829] Step 1. [0830] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-t-Butoxycarbonylamino-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole. [0831] The compound of Step 1 of Example 122 (141 mg) was prepared from 1-[5(R)-3-(3,5-difluoro-4-iodophenyl)-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (188 mg) and 5-bromo-2-[(1α,5α,6β)-6-t-butoxycarbonylamino-3-thiabicyclo[3.1.0]hexan-6-yl]pyridine (200 mg) in the same manner as described for EXAMPLE 31. [0832] MS (FAB + ) m/z: 571 (MH + ). [0833] HRMS (FAB + ) for C 27 H 29 F 2 N 6 O 4 S (MH + ): calcd, 571.1939; found, 571.1899. [0834] Step 2. [0835] Title Compound 122 (4.2 mg) was prepared from 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-t-butoxycarbonylamino-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (10.0 mg) in the same manner as described for EXAMPLE 49. [0836] MS (FAB + ) m/z: 471 (MH + ). [0837] HRMS (FAB + ) for C 22 H 21 F 2 N 6 O 2 S (MH + ): calcd, 471.1415; found, 471.1436. EXAMPLE 123 [0838] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Amino-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole S-Oxide Diastereomer G′ and Diastereomer H′ [0839] Step 1. [0840] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-t-Butoxycarbonylamino-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole S-Oxide Diastereomer G and Diastereomer H. [0841] The compound of Step 1 of Example 123 diastereomer G (10.2 mg) and diastereomer H (18.6 mg) was prepared from 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-t-butoxycarbonylamino-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (30.0 mg) in the same manner as described for EXAMPLE 58. [0842] Diastereomer G (less polar): [0843] MS (FAB + ) m/z: 587 (MH + ). [0844] HRMS (FAB + ) for C 27 H 29 F 2 N 6 O 5 S (MH + ): calcd, 587.1888; found, 587.1860. [0845] Diastereomer H (more polar): [0846] MS (FAB + ) m/z: 587 (MH + ). [0847] HRMS (FAB + ) for C 27 H 29 F 2 N 6 O 5 S (MH + ): calcd, 587.1888; found, 587.1921. [0848] Step 2. [0849] Title Compound 123 diastereomer G′ (0.8 mg) was prepared from 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-t-butoxycarbonylamino-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole diastereomer G (2.2 mg) in the same manner as described for EXAMPLE 49. [0850] MS (FAB + ) m/z: 487 (MH + ). [0851] HRMS (FAB + ) for C 22 H 21 F 2 N 6 O 3 S (MH + ): calcd, 487.1364; found, 487.1348. EXAMPLE 124 [0852] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Amino-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole S,S-Dioxide [0853] Step 1. [0854] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-t-Butoxycarbonylamino-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole S,S-Dioxide. [0855] The compound of Step 1 of Example 124 (19.2 mg) was prepared from 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-t-butoxycarbonylamino-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (20.0 mg) in the same manner as described for EXAMPLE 59. [0856] MS (FAB + ) m/z: 603 (MH + ). [0857] HRMS (FAB + ) for C 27 H 29 F 2 N 6 O 6 S (MH + ): calcd, 603.1837; found, 603.1873. [0858] Step 2. [0859] Title Compound 124 (2.7 mg) was prepared from the compound of Step 1 of Example 124 (4.0 mg) in the same manner as described for EXAMPLE 49. [0860] MS (FAB + ) m/z: 503 (MH + ). [0861] HRMS (FAB + ) for C 22 H 21 F 2 N 6 O 4 S (MH + ): calcd, 503.1313; found, 503.1306. EXAMPLE 125 [0862] 5(R)-3-[4-[2-[(1α,5α,6β)-3-t-Butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-5-[(isoxazol-3-yl)oxy]methyloxazolidin-2-one [0863] Title Compound 125 (47.8 mg) was prepared from N-[5(S)-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-5-hydroxymethyloxazolidin-2-one (50.0 mg) in-the same manner as described for EXAMPLE 66. [0864] MS (FAB + ) m/z: 580 (MH + ). [0865] HRMS (FAB + ) for C 29 H 28 F 2 N 5 O 6 (MH + ): calcd, 580.2008; found, 580.1965. EXAMPLE 126 [0866] 5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-5-[(isoxazol-3-yl)oxy]methyloxazolidin-2-one Hydrochloride [0867] Title Compound 126 (26.5 mg) was prepared from 5(R)-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-5-[(isoxazol-3-yl)oxy]methyloxazolidin-2-one (47.0 mg) in the same manner as described for EXAMPLE 2. [0868] MS (FAB + ) m/z: 480 (MH + ) (as free base). [0869] HRMS (FAB + ) for C 24 H 20 F 2 N 5 O 4 (MH + ): calcd, 480.1483; found, 480.1449. EXAMPLE 127 [0870] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-(4-methylpiperazin-1-yl)acetyl-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0871] Title Compound 127 (17.9 mg) was prepared from 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (20.0 mg) and N-methylpiperazine (20 μL) in the same manner as described for EXAMPLE 84. [0872] MS (FAB + ) m/z: 586 (MH + ). [0873] HRMS (FAB + ) for C 30 H 33 FN 9 O 3 (MH + ): calcd, 586.2690; found, 586.2642. EXAMPLE 128 [0874] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0875] Title Compound 128 (201 mg) was prepared from 1-[5(R)-3-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolyl)phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (263 mg) and 5-bromo-2-[(1α,5α,6β)-6-cyano-3-thiabicyclo-[3.1.0]hexan-6-yl]pyridine (200 mg) in the same manner as described for EXAMPLE 1. [0876] MS (FAB + ) m/z: 445 (MH + ). [0877] HRMS (FAB + ) for C 23 H 21 N 6 O 2 S (MH + ): calcd, 445.1447; found, 445.1434. EXAMPLE 129 [0878] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole S-Oxide [0879] Title Compound 129 (21.9 mg) was prepared from 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (22.3 mg) in the same manner as described for EXAMPLE 58. [0880] MS (FAB + ) m/z: 461 (MH + ). [0881] HRMS (FAB + ) for C 23 H 21 N 6 O 3 S (MH + ): calcd, 461.1396; found, 461.1390. EXAMPLE 130 [0882] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole S,S-Dioxide [0883] Title Compound 130 (18.2 mg) was prepared from 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (22.3 mg) in the same manner as described for EXAMPLE 58. [0884] MS (FAB + ) m/z: 477 (MH + ). [0885] HRMS (FAB + ) for C 23 H 21 N 6 O 4 S (MH + ): calcd, 477.1345; found, 477.1329. EXAMPLE 131 [0886] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0887] Title Compound 131 (142 mg) was prepared from 1-[5(R)-3-[3,5-difluoro-4(trifluoromethanesulfonyl)-oxyphenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (254 mg) and 5-bromo-2-[(1α,5α,6β)-6-cyano-3-thiabicyclo[3.1.0]hexan-6-yl]pyridine (200 mg) in the same manner as described for EXAMPLE 31. [0888] MS (FAB + ) m/z: 481 (MH + ). [0889] HRMS (FAB + ) for C 23 H 19 F 2 N 6 O 2 S(MH + ): calcd, 481.1258; found, 481.1241. EXAMPLE 132 [0890] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole S-Oxide [0891] Title Compound 132 (18.5 mg) was prepared from 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (20.0 mg) in the same manner as described for EXAMPLE 58. [0892] MS (FAB + ) m/z: 497 (MH + ). [0893] HRMS (FAB + ) for C 23 H 19 F 2 N 6 O 3 S (MH + ): calcd, 497.1207; found, 497.1251. EXAMPLE 133 [0894] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole S,S-Dioxide [0895] Title Compound 133 (18.9 mg) was prepared from 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-thiabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (20.0 mg) in the same manner as described for EXAMPLE 58. [0896] MS (FAB + ) m/z: 513 (MH + ). [0897] HRMS (FAB + ) for C 23 H 19 F 2 N 6 O 4 S (MH + ): calcd, 513.1157; found, 513.1181. EXAMPLE 134 [0898] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-(1,3-diacetoxypropan-2-yl)-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0899] To a solution of 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-(1,3-dihydroxypropan-2-yl)-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (7.7 mg) in dichloromethane (0.2 mL) was added acetic anhydride at room temperature, the mixture was stirred at the same temperature for 5 hours. To the mixture was added 4-(dimethylamino)pyridine (9.0 mg), the mixture was stirred at room temperature for 1 hour and concentrated in vacuo. Preparative thin-layer chromatography (silica, dichloromethane:methanol=10:1) of the residue gave title compound 134 (5.8 mg). [0900] MS (FAB + ) m/z: 604 (MH + ). [0901] HRMS (FAB + ) for C 30 H 31 FN 7 O 6 (MH + ): calcd, 604.2320; found, 604.2300. EXAMPLE 135 [0902] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-3-[(3R,4S)-1-Azabicyclo[2.2.1]hepan-3-yl]carbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0903] Title Compound 135 (3.9 mg) was prepared from 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (20.0 mg) and (3R,4S)-1-azabicycloheptane-3-carboxylic acid hydrochloride (9.5 mg) in the same manner as described for EXAMPLE 71. [0904] MS (FAB + ) m/z: 569 (MH + ). [0905] HRMS (FAB + ) for C 30 H 30 FN 8 O 3 (MH + ): calcd, 569.2425; found, 569.2380. EXAMPLE 136 [0906] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-(pyridin-2-yl)-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0907] A suspension of 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (50.0 mg) and 2-pyridyl trifluoromethnesulfonate (0.86 mL) in diisopropylethylamine (0.2 mL) was stirred at 90° C. for 44 hours. Flash chromatography (silica, ethyl acetate:methanol=5:1) of the mixture gave title compound 136 (18.6 mg). [0908] MS (FAB + ) m/z: 523 (MH + ). [0909] HRMS (FAB + ) for C 28 H 24 FN 8 O 2 (MH + ): calcd, 523.2006; found, 523.1978. EXAMPLE 137 [0910] 5(R)-3-[4-[2-[(1α,5α,6β)-3-t-Butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-5-[N-(t-butoxycarbonyl)-N-(isoxazol-3-yl)]aminomethyloxazolidin-2-one [0911] Title Compound 137 (54.9 mg) was prepared from N-[5(S)-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-5-hydroxymethyloxazolidin-2-one (50.0 mg) in the same manner as described for EXAMPLE 67. [0912] MS (FAB + ) m/z: 679 (MH + ). [0913] HRMS (FAB + ) for C 34 H 37 F 2 N 6 O 7 (MH + ): calcd, 679.2692; found, 679.2672. EXAMPLE 138 [0914] 5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-5-[N-(isoxazol-3-yl)]aminomethyloxazolidin-2-one Hydrochloride [0915] Title Compound 138 (20.7 mg) was prepared from 5(R)-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3,5-difluorophenyl]-5-[N-(t-butoxycarbonyl)-N-(isoxazol-3-yl)]aminomethyloxazolidin-2-one (51.8 mg) in the same manner as described for EXAMPLE 2. [0916] 1 H NMR (DMSO-d6) δ 3.03-3.09 (m, 2H), 3.40-3.47 (m, 4H), 3.85 (dd, J=9.2 Hz, 6.1 Hz, 1H), 3.90-4.00 (m, 2H), 4.20 (t, J=9.2 Hz, 1H), 4.90-4.98 (m, 1H), 6.00 (d, J=1.8 Hz, 1H), 6.57 (t, J=6.1 Hz, 1H), 7.45-7.53 (m, 2H), 7.72 (d, J=7.9 Hz, 1H), 8.01 (d, J=7.9 Hz, 1H), 8.39 (d, J=1.8 Hz, 1H), 8.64 (s, 1H). EXAMPLE 139 [0917] 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-(thiatriazol-2-yl)-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0918] To a solution of 1,1′-thiocarbonyldiimidazole (21.6 mg) in acetonitrile (1.0 mL) was added 1-[5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (50.0 mg) at room temperature, the mixture was stirred at the same temperature for 1 hour. To the mixture was added iodomethane (67.9 μL), the mixture was stirred at room temperature for overnight, and concentrated in vacuo. A suspension of the residue and sodium azide (21.3 mg) in acetonitrile (1.0 mL) was stirred at room temperature for overnight. After dilution of the mixture with water, the insoluble materials were collected by filtration. Preparative thin-layer chromatography (silica, dichloromethane:methanol=10:1 ) of the insoluble materials title compound 139 (13.7 mg). [0919] MS (FAB + ) m/z: 531 (MH + ). [0920] HRMS (FAB + ) for C 24 H 20 FN 10 O 2 S (MH + ): calcd, 531.1475; found, 531.1466. EXAMPLE 140 [0921] N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]thioacetamide [0922] Step 1. [0923] N-[5(S)-3-[4-[2-[(1α,5α,6β)-3-t-Butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]thioacetamide. [0924] A mixture of 5(S)-aminomethyl-3-[4-[2-[(1α,5α, 6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]oxazolidin-2-one (100 mg), ethyl dithioacetate (28.0 μL), triethylamine (62.2 μL), and tetrahydrofuran (3 mL) was stirred at room temperature for overnight and concentrated in vacuo Flash chromatography (silica, dichloromethane:methanol=10:1) of the residue gave N-[5(S)-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]thioacetamide (82.0 mg). [0925] MS (FAB + ) m/z: 552 (MH + ). [0926] Step 2. [0927] Title Compound 140 (46.2 mg) was prepared from the compound of Step 1 of Example 140 (77.0 mg) in the same manner as described for EXAMPLE 49. [0928] MS (FAB + ) m/z: 452 (MH + ). [0929] HRMS (FAB + ) for C 23 H 23 FN 5 O 2 S (MH + ): calcd, 452.1557; found, 452.1531. EXAMPLE 141 [0930] O-Methyl N-[5(S)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]thiocarbamate [0931] Step 1. [0932] N-[5(S)-3-[4-[2-[(1α,5α,6β)-3-t-Butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]isothiocyanate. [0933] To a solution of 5(S)-aminomethyl-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]oxazolidin-2-one (150 mg) in tetrahydrofuran (2.0 mL) was added carbon disulfide (36.6 μL) and triethylamine (42.4 μL) at 0° C., the mixture was stirred at the same temperature for 4 hours. To the mixture was added ethyl chloroformate (29.1 μL) at 0° C., the mixture was stirred at the same temperature for 30 minutes and concentrated in vacuo. Treatment of the residue with water gave crude product. A solution of the crude product in dichloromethane was dried over anhydrous sodium sulfate, filtered, and then concentrated in vacuo. Flash chromatography (silica, ethyl acetate) of the residue gave the compound of Step 1 of Example 141 (125 mg). [0934] MS (FAB + ) m/z: 536 (MH + ). [0935] Step 2. [0936] O-Methyl N-[5(S)-3-[4-[2-[(1α,5α,6β)-3-t-Butoxy,carbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-2-oxooxazolidin-5-ylmethyl]thiocarbamate. [0937] To a solution of sodium methoxide in methanol (prepared from sodium hydride (26.5 mg) and methanol (1.0 mL)) was added a suspension of the compound of Step 1 of Example 141 (119 mg) in methanol (1.0 mL) at 0° C., the mixture was stirred at room temperature for 5 hours and concentrated in vacuo. After dilution of the residue with water, the mixture was extracted with dichloromethane-methanol (10:1). The organic extracts were dried over anhydrous sodium sulfate, filtered, and then concentrated in vacuo. Flash chromatography (silica, dichloromethane:ethyl acetate=1:1) of the residue gave the compound of Step 2 of Example 141 (93.5 mg). [0938] MS (FAB + ) m/z: 568 (MH + ). [0939] Step 3. [0940] Title Compound 141 (43.6 mg) was prepared from the compound of Step 2 of Example 141 (85.0 mg) in the same manner as described for EXAMPLE 49. [0941] MS (FAB + ) m/z: 468 (MH + ). [0942] HRMS (FAB + ) for C 23 H 23 FN 5 O 3 S (MH + ): calcd, 468.1506; found, 468.1524. REFERENCE EXAMPLE 1 N-[5(S)-3-[3-Fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolyl)phenyl]-2-oxooxazolidin-5-ylmethyl]acetamide [0943] The mixture of N-[5(S)-3-(3-fluoro-4-iodophenyl)-2-oxooxazolidin-5-ylmethyl]acetamide (2.00 g), bis(pinacolato)diboron (1.61 g), potassium acetate (1.56 g) and [1,1′-bis(diphenylphosphino)ferrocene]palladium(II) dichloride-dichloromethane adduct (432 mg) in dimethyl sulfoxide (50 mL) was heated at 80° C. for 1 hour. The mixture was diluted with water and extracted with ethyl acetate. The organic extracts were washed with brine, dried over anhydrous magnesium sulfate, and then concentrated in vacuo. Flash chromatography (silica, ethyl acetate:acetone=9:1) of the residue gave N-[5(S)-3-[3-fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolyl)phenyl]-2-oxooxazolidin-5-ylmethyl]acetamide (889 mg). [0944] MS (EI + ) m/z: 378 (M + ). [0945] HRMS (EI + ) for C 18 H 24 BFN 2 O 5 (M + ): calcd, 378.1762; found, 378.1779. REFERENCE EXAMPLE 2 N-[5(S)-3-[4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolyl)phenyl]-2-oxooxazolidin-5-ylmethyl]acetamide [0946] Reference Example 2 (92.5 mg) was prepared from N-[5(S)-3-(4-iodophenyl)-2-oxooxazolidin-5-ylmethyl]acetamide (108 mg) and bis(pinacolato)diboron (855 mg) in the same manner as described for REFERENCE EXAMPLE 1. [0947] MS (EI + ) m/z: 360 (M + ). [0948] HRMS (EI + ) for C 18 H 25 BN 2 O 5 (M + ): calcd, 360.1857; found, 360.1875. REFERENCE EXAMPLE 3 1-[5(R)-3-[3-Fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolyl)phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0949] Reference Example 3 (1.53 g) was prepared from 1-[5(R)-3-(3-fluoro-4-iodophenyl)-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (2.69 g) and bis(pinacolato)diboron (1.86 g) in the same manner as described for REFERENCE EXAMPLE 1. [0950] MS (EI + ) m/z: 388 (M + ). [0951] HRMS (EI + ) for C 18 H 22 BFN 4 O 4 (M + ): calcd, 388.1718; found, 388.1752. REFERENCE EXAMPLE 4 1-[5(R)-3-[4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolyl)phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0952] Reference Example 4 (147 mg) was prepared from 1-[5(R)-3-(4-iodophenyl)-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (200 mg) and bis(pinacolato)diboron (151 mg) in the same manner as described for REFERENCE EXAMPLE 1. [0953] MS (EI + ) m/z: 370 (M + ). [0954] HRMS (EI + ) for C 18 H 23 BN 4 O 4 (M + ): calcd, 370.1812; found, 370.1814. REFERENCE EXAMPLE 5 5(R)-5-(t-Butyidimethylsilyloxy)methyl-3-(3-fluoro-4-iodophenyl)oxazolidin-2-one [0955] To a solution of 5(R)-3-(3-fluoro-4-iodophenyl)-5-hydroxymethyloxazolidin-2-one (3.00 g) in dichloromethane (30 mL) was added imidazole (1.33 g) and t-butyidimethylsilyl chloride (1.48 g) at 0° C., the mixture was stirred at room temperature for 2 hours. The mixture was washed with water, 2N hydrochloric acid, saturated sodium hydrogencarbonate solution and brine, dried over anhydrous magnesium sulfate, and then concentrated in vacuo to give Reference Example 5 (3.66 g). [0956] MS (EI + ) m/z: 451 (M + ). [0957] HRMS (EI + ) for C 16 H 23 FINO 3 Si (M + ): calcd, 451.0476; found, 451.0511. REFERENCE EXAMPLE 6 5(R)-5-(t-Butyldimethylsilyloxy)methyl-3-[3-fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolyl)phenyl]oxazolidin-2-one [0958] Reference Example 6 (64.4 mg) was prepared from 5(R)-5-(t-butyldimethylsilyloxy)methyl-3-(3-fluoro-4-iodophenyl)oxazolidin-2-one (100 mg) and bis(pinacolato)diboron (67.0 mg) in the same manner as described for Reference Example 1. [0959] MS (CI + ) m/z: 452 (MH + ). [0960] HRMS (CI + ) for C 22 H 36 BFNO 5 Si (MH + ): calcd, 452.2440; found, 452.2394. REFERENCE EXAMPLE 7 3,5-Difluoro-4-(methoxymethyl)oxynitrobenzene [0961] To a solution of 2,6-difluoro-4-nitrophenol (35.0 g) in dichloromethane (300 mL) was added diisopropylethylamine (50.2 mL) and methoxymethyl chloride (17.5 mL) at 0° C., the mixture was stirred at room temperature for 2 hours. The mixture was washed with water, 5% sodium hydrogencarbonate solution and brine, dried over anhydrous magnesium sulfate, and then concentrated in vacuo. Flash chromatography (silica, hexane:ethyl acetate=9:1) of the residue gave Reference Example 7(35.2 g). [0962] 1 H NMR (CDCl 3 ) δ 3.59 (d, J=1.5 Hz, 3H), 5.30 (s, 2H), 7.83-7.91 (m, 2H). REFERENCE EXAMPLE 8 4-Benzyloxycarbonylamino-2,6-difluoro-1-(methoxymethyl)oxybenzene [0963] A suspension of 3,5-difluoro-4-(methoxymethyl)oxynitrobenzene (35.0 g) and palladium catalyst (10% on charcoal, 3.00 g) in methanol (250 mL)) was hydrogenated at 1 atm for 2 hours at room temperature. After filtration of the catalyst, the filtrate was concentrated in vacuo to give 4-amino-2,6-difluoro-1-(methoxymethyl)oxybenzene. This was used in the next step without further purification. To a solution of crude 4-amino-2,6-difluoro-1-(methoxymethyl)oxybenzene thus obtained in tetrahydrofuran (500 mL) was successively added sodium hydrogencarbonate (17.4 g), water (100 mL) and benzyl chloroformate (30.0 g) at 0° C., and the mixture was stirred at room temperature for 15 minutes. The mixture was diluted with saturated sodium hydrogencarbonate solution and extracted with ethyl acetate. The organic extracts were washed with brine, dried over anhydrous magnesium sulfate, and then concentrated in vacuo. Flash chromatography (silica, hexane:ethyl acetate=6:1) of the residue gave Reference Example 8 (49.10 g). [0964] MS (EI + ) m/z: 323 (M + ). [0965] HRMS (EI + ) for C 16 H 15 F 2 NO 4 (M + ): calcd, 323.0969; found, 323.0963. REFERENCE EXAMPLE 9 5(R)-3-[3,5-Difluoro-4-(methoxymethyl)oxyphenyl]-5-hydroxymethyloxazolidin-2-one [0966] To a solution of 4-benzyloxycarbonylamino-2,6-difluoro-1-(methoxymethyl)oxybenzene (46.3 g) in dry tetrahydrofuran (400 mL) was added a solution of n-butyllithium in hexane (1.6 M, 90.0 mL) at −78° C., and the mixture was stirred at the same temperature for 30 minutes. (R)-Glycidyl butyrate (20.3 mL) was added to the mixture at −78° C. and the mixture was allowed to stand at room temperature for 3 hours. After quenching the reaction with the addition of aqueous ammonium chloride solution, the mixture was extracted with ethyl acetate. The organic extracts were washed with brine, dried over anhydrous magnesium sulfate, filtered, and then concentrated in vacuo. To a solution of the residue in methanol (300 mL) was added potassium carbonate (20.0 g), the mixture was stirred at room temperature for 30 minutes, and then concentrated in vacuo. After dilution of the residue with water, the mixture was extracted with ethyl acetate. The organic extracts were washed with brine, dried over anhydrous magnesium sulfate, filtered, and then concentrated in vacuo. Flash chromatography (silica, hexane:ethyl acetate=1:4) of the residue gave Reference Example 9 (36.1 g). [0967] MS (EI + ) m/z: 289 (M + ). [0968] HRMS (EI + ) for C 12 H 13 F 2 NO 5 (M + ): calcd, 289.0762; found, 289.0743. REFERENCE EXAMPLE 10 N-[5(S)-3-[3,5-Difluoro-4-(methoxymethyl)oxyphenyl]-2-oxooxazolidin-5-ylmethyl]acetamide [0969] To a solution of 5(R)-3-[3,5-difluoro-4-(methoxymethyl)oxyphenyl]-5-hydroxymethyloxazolidin-2-one (5.00 g) in dichloromethane (20 mL) were successively added triethylamine (4.82 mL) and methanesulfonyl chloride (2.53 mL) at 0° C., and the mixture was stirred at the same temperature for 1 hour. The mixture was washed with water, dried over anhydrous magnesium sulfate, filtered, and then concentrated in vacuo to give 5(R)-3-[3,5-difluoro-4-(methoxymethyl)oxyphenyl]-5-methanesulfonyloxymethyloxazolidin-2-one. This was used in the next step without further purification. The mixture of crude 5(R)-3-[3,5-difluoro-4-(methoxymethyl)oxyphenyl]-5-methanesulfonyloxymethyloxazolidin-2-one thus obtained and sodium azide (3.93 g) in N,N-dimethylformamide (20 mL) was heated at 60° C. for 8 hours, and then concentrated in vacuo. The residue was diluted with ethyl acetate and washed with water and brine. The organic extracts were dried over anhydrous magnesium sulfate, filtered, and then concentrated in vacuo to give 5(R)-azidomethyl-3-[3,5-difluoro-4-(methoxymethyl)oxyphenyl]oxazolidin-2-one (5.43 g). This was used in the next step without further purification. A suspension of 5(R)-azidomethyl-3-[3,5-difluoro-4-(methoxymethyl)oxyphenyl]oxazolidin-2-one (3.53 g) and Lindlar catalyst (5% palladium on CaCO3 partially poisoned with lead, 700 mg) in methanol (110 mL) was hydrogenated at 1 atm for 6 hours at room temperature. After filtration of the catalyst, the filtrate was concentrated in vacuo. To a solution of the residue in tetrahydrofuran (15 mL) was added triethylamine (6.30 mL) and acetic anhydride (2.10 mL) at room temperature, and the mixture was stirred at the same temperature for 2 hours. After quenching the reaction by the addition of saturated sodium hydrogencarbonate solution, the mixture was extracted with ethyl acetate. The organic extracts were dried over anhydrous magnesium sulfate, filtered, and then concentrated in vacuo. Flash chromatography (silica, ethyl acetate) of the residue gave Reference Example 10 (3.45 g). [0970] MS (EI + ) m/z: 330 (M + ). [0971] HRMS (EI + ) for C 14 H 16 F 2 N 2 O 5 (M + ): calcd, 330.1027; found, 330.1001. REFERENCE EXAMPLE 11 N-[5(S)-3-(3,5-Difluoro-4-hydroxyphenyl)-2-oxooxazolidin-5-ylmethyl]acetamide [0972] To a solution of N-[5(S)-3-[3,5-difluoro-4-(methoxymethyl)oxyphenyl]-2-oxooxazolidin-5-ylmethyl]acetamide (200 mg) in methanol (5 mL) was added concentrated hydrochloric acid (0.50 mL), the mixture was stirred at room temperature for 1 day, and then concentrated in vacuo. Treatment with water of the residue gave Reference Example 11 (144 mg). [0973] MS (EI + ) m/z: 286 (M + ). [0974] HRMS (EI + ) for C 12 H 12 F 2 N 2 O 4 (M + ): calcd, 286.0765; found, 286.0747. REFERENCE EXAMPLE 12 N-[5(S)-3-[3,5-Difluoro-4-(trifluoromethanesulfonyl)oxyphenyl]-2-oxooxazolidin-5-ylmethyl]acetamide [0975] To a solution of N-[5(S)-3-(3,5-difluoro-4-hydroxyphenyl)-2-oxooxazolidin-5-ylmethyl]acetamide (2.70 g) in pyridine (15 mL) was added triflic anhydride (2.38 mL) at 0° C., the mixture was stirred at room temperature for 12 hours. After dilution of the mixture with water, the mixture was extracted with ethyl acetate. The organic extracts were washed with 5% hydrochloric acid and brine, dried over anhydrous magnesium sulfate, filtered, and then concentrated in vacuo. Flash chromatography (silica, ethyl acetate:methanol=19:1 ) of the residue gave Reference Example 12 (3.48 g). [0976] MS (EI + ) m/z: 418 (M + ). [0977] HRMS (EI + ) for C 13 H 11 F 5 N 2 O 6 S (M + ): calcd, 418.0258; found, 418.0210. REFERENCE EXAMPLE 13 1-[5(R)-3-(3-Fluoro-4-iodophenyl)-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0978] Step 1. 5(R)-Acetoxymethyl-3-(3-fluorophenyl)oxazolidin-2-one [0979] To a solution of 5(R)-3-(3-fluorophenyl)-5-hydroxymethyloxazolidin-2-one (5.28 g) in tetrahydrofuran (53 mL) was added triethylamine (3.83 mL), acetic anhydride (2.55 mL) and (4-dimethylamino)pyridine (152 mg), and the mixture was stirred at room temperature for 1 hour. After quenching the reaction by the addition of 1 N hydrochloric acid, the mixture was extracted with ethyl acetate. The organic extracts were washed with brine, dried over anhydrous sodium sulfate, filtered, and then concentrated in vacuo to give crude 5(R)-acetoxymethyl-3-(3-fluorophenyl)oxazolidin-2-one (6.33 g). [0980] Step 2. 5(R)-Acetoxymethyl-3-(3-fluoro-4-iodophenyl)oxazolidin-2-one [0981] To a solution of 5(R)-acetoxymethyl-3-(3-fluorophenyl)oxazolidin-2-one (6.33 g) in acetic acid (40 mL) was added iodine monochloride (1.91 mL), the mixture was stirred at room temperature for 18 hours, and then concentrated in vacuo. The resulting residue was dissolved with ethyl acetate, the mixture was washed with aqueous sodium hydrogencarbonate solution, 20% sodium sulfite solution and brine, dried over anhydrous sodium sulfate, filtered, and then concentrated in vacuo to give crude 5(R)-acetoxymethyl-3-(3-fluoro-4-iodophenyl)oxazolidin-2-one (9.48 g). [0982] Step 3. 5(R)-3-(3-Fluoro-4-iodophenyl)-5-hydroxymethyloxazolidin-2-one [0983] To a solution of crude 5(R)-acetoxymethyl-3-(3-fluoro-4-iodophenyl)oxazolidin-2-one (9.48 g) in methanol (95 mL) was added potassium carbonate (6.91 g), and the mixture was stirred at room temperature for 2.5 hours. After insoluble materials were filtered off, the filtrate was concentrated in vacuo. The residue was dissolved with ethyl acetate, the mixture was washed with brine, dried over anhydrous sodium sulfate, filtered, and then concentrated in vacuo. After treating of the residue with isopropanol, the resulting precipitates were collected by filtration to give 5(R)-3-(3-fluoro-4-iodophenyl)-5-hydroxymethyloxazolidin-2-one, and the filtrate was concentrated in vacuo. Flash chromatography (silica, ethyl acetate) of the residue gave further amount of the product (total 6.24 g). [0984] MS (EI + ) m/z: 337 (M + ). [0985] 1 H NMR (CDCl 3 ) δ 2.15 (t, J=6.4 Hz, 1H), 3.74-4.80 (m, 5H), 7.07 (dd, J=8.8, 2.4 Hz, 1H), 7.48 (dd, J=10.3, 2.4 Hz, 1H), 7.70 (dd, J=8.8, 6.8 Hz, 1H). [0986] Step 4. 5(R)-Azidomethyl-3-(3-fluoro-4-iodophenyl)oxazolidin-2-one [0987] To a solution of 5(R)-3-(3-fluoro-4-iodophenyl)-5-hydroxymethyloxazolidin-2-one (2.00 g) in dichloromethane (30 mL) was added triethylamine (1.24 mL) and methanesulfonyl chloride (551 μL) at 0° C., the mixture was stirred at the same temperature for 30 minutes. The mixture was washed with ice water, dried over anhydrous magnesium sulfate, filtered, and then concentrated in vacuo. [0988] The mixture of the residue and sodium azide (964 mg) in N,N-dimethylformamide (30 mL) was stirred at 80° C. for 2 hours and concentrated in vacuo. After dilution of the residue with water, the mixture was extracted with ethyl acetate. The organic extracts were dried over anhydrous magnesium sulfate, filtered, and then concentrated in vacuo to give 5(R)-azidomethyl-3-(3-fluoro-4-iodophenyl)oxazolidin-2-one (2.18 g). [0989] MS (EI + ) m/z: 361 (M + ). [0990] HRMS (EI + ) for C 10 H 8 FIN 4 O 2 (M + ): calcd, 361.9676; found, 361.9698. [0991] Step 5. 1-[5(R)-3-(3-Fluoro-4-iodophenyl)-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0992] The mixture of 5(R)-azidomethyl-3-(3-fluoro-4-iodophenyl)oxazolidin-2-one (2.18 g) and 2,5-norbornadiene (6.40 mL) in dioxane (45.6 mL) was stirred at 80° C. for 2 hours, 110° C. for 4 hours, and then concentrated in vacuo to give Reference Example 13 (1.70 g). [0993] MS (EI + ) m/z: 388 (M + ). [0994] HRMS (EI + ) for C 12 H 10 FIN 4 O 2 (M + ): calcd, 387.9833; found, 387.9835. REFERENCE EXAMPLE 14 5(R)-Azidomethyl-3-(4-iodophenyl)oxazolidin-2-one [0995] Reference Example 14 (75.3 g) was prepared from 5(R)-3-(4-iodophenyl)-5-hydroxymethyloxazolidin-2-one (70.0 g) in the same manner as described for REFERENCE EXAMPLE 13. [0996] MS (EI + ) m/z: 344 (M + ). [0997] HRMS (EI + ) for C 10 H 9 IN 4 O 2 (M + ): calcd, 343.9770; found, 343.9740. REFERENCE EXAMPLE 15 1-[5(R)-3-(4-Iodophenyl)-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [0998] Reference Example 15 (62.5 mg) was prepared from 5(R)-azidomethyl-3-(4-iodophenyl)oxazolidin-2-one (100 mg) in the same manner as described for REFERENCE EXAMPLE 13. [0999] MS (EI + ) m/z: 370 (M + ). [1000] HRMS (EI + ) for C 12 H 11 IN 4 O 2 (M + ): calcd, 369.9927; found, 369.9919. REFERENCE EXAMPLE 16 5(R)-5-(t-Butyldimethylsilyloxy)methyl-3-(4-iodophenyl)oxazolidin-2-one [1001] Reference Example 16 (2.66 g) was prepared from 5(R)-3-(4-iodophenyl)-5-hydroxymethyloxazolidin-2-one (2.00 g) in the same manner as described for REFERENCE EXAMPLE 5. [1002] MS (EI + ) m/z: 433 (M + ). [1003] HRMS (EI + ) for C 16 H 24 INO 3 Si (M + ): calcd, 433.0570; found, 433.0544. REFERENCE EXAMPLE 17 cis-N-t-Butoxycarbonylpyrrolidine-3,4-diol [1004] To a solution of N-t-butoxycarbonyl-3-pyrroline (69.3 g) and NMO (72.2 g) in tetrahydrofuran (340 mL), t-butanol (210 mL) and water (100 mL) was added OsO4 (2.5% solution in t-butanol, 4.8 mL), the mixture was heated under reflux for 2.5 hours, and then concentrated in vacuo. After dilution of the residue with brine, the mixture was extracted with ethyl acetate. The organic extracts were concentrated in vacuo. Flash chromatography (silica, hexane:ethyl acetate=1:1) of the residue gave Reference Example 17 (55.0 g). [1005] MS (FAB + ) m/z: 204 (MH + ). [1006] HRMS (FAB + ) for C 9 H 18 NO 4 (MH + ): calcd, 204.1236; found, 204.1240. REFERENCE EXAMPLE 18 cis-N-t-Butoxycarbonylpyrrolidine-3,4-cyclic Sulfate [1007] To a solution of cis-N-t-butoxycarbonylpyrrolidine-3,4-diol (406 mg) and triethylamine (1.1 mL) in dichloromethane (10 mL) was added thionyl chloride (220 μL) at 0° C., the mixture was stirred at the same temperature for 10 minutes. After quenching the reaction by addition of water (1 mL), the mixture was diluted hexane and water. The organic extracts were washed with water, saturated sodium hydrogencarbonate solution and brine, dried over anhydrous magnesium sulfate, filtered, and then concentrated in vacuo to give crude cyclic sulfite (482 mg). To a solution of the crude cyclic sulfite (482 mg) in carbon tetrachloride (6 mL), acetonitrile (6 mL), and water (9 mL) was added ruthenium(III) chloride hydrate (6.0 mg) and sodium periodate (856 mg) at 0° C., the mixture was stirred at the same temperature for 2 hours. After dilution of the mixture with hexane and ether, the mixture was extracted with hexane. The organic extracts were washed with brine, dried over anhydrous magnesium sulfate, filtered, and then concentrated in vacuo. Flash chromatography (silica, hexane:ethyl acetate=1:1) of the residue gave Reference Example 18 (438 mg). [1008] MS (FAB + ) m/z: 266 (MH + ). [1009] HRMS (FAB + ) for C 9 H 16 NO 6 S (MH + ): calcd, 266.0698; found, 266.0730. REFERENCE EXAMPLE 19 5-Bromo-2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridine [1010] To a suspension of sodium hydride (60% oil dispersion, 2.24 g) in dimethoxyethane (110 mL) was added a solution of 5-bromo-2-pyridylacetonitrile (5.0 g) in dimethoxyethane (20 mL) and a solution of cis-N-t-butoxycarbonylpyrrolidine-3,4-cyclic sulfate (7.41 g) in dimethoxyethane (20 mL) at 0° C., the mixture was stirred at room temperature for 3 hours. After dilution of the mixture with brine, the mixture was extracted with ethyl acetate. The organic extracts were dried over anhydrous magnesium sulfate, filtered, and then concentrated in vacuo. Flash chromatography (silica, hexane:ethyl acetate=4:1) of the residue gave Reference Example 19 (7.50 g). [1011] MS (EI + ) m/z: 363 (M + ). [1012] HRMS (EI + ) for C 16 H 18 BrN 3 O 2 (M + ): calcd, 363.0582; found, 363.0582. REFERENCE EXAMPLE 20 1-Bromo-4-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3-fluorobenzene [1013] Reference Example 20 (334 mg) was prepared from 4-bromo-2-fluorophenylacetonitrile (214 mg) and cis-N-t-butoxycarbonylpyrrolidine-3,4-cyclic sulfate (292 mg) in the same manner as described for REFERENCE EXAMPLE 19. [1014] MS (FAB + ) m/z: 381 (MH + ). [1015] HRMS (FAB + ) for C 17 H 19 BrFN 2 O 2 (MH + ): calcd, 381.0614; found, 381.0622. REFERENCE EXAMPLE 21 5-Bromo-2-chloro-3-fluoropyridine [1016] A suspension of 5-bromo-3-fluoro-2-hydroxypyridine (10.0 g) in phosphoryl chloride (50 mL) was heated at 150° C. for 4 hours. The mixture was poured into ice, the resulting mixture was adjusted to pH 10 by addition of potassium carbonate and extracted with dichloromethane. The organic extracts were dried over anhydrous magnesium sulfate, filtered, and then concentrated in vacuo to give Reference Example 21 (10.9 g). [1017] MS (EI + ) m/z: 209 (M + ). [1018] HRMS (EI + ) for C 5 H 2 BrClFN (M + ): calcd, 208.9043; found, 208.9064. REFERENCE EXAMPLE 22 5-Bromo-3-fluoro-2-pyridineacetonitrile [1019] The mixture of 5-bromo-2-chloro-3-fluoropyridine (700 mg) and potassium fluoride (773 mg) in dimethyl sulfoxide (14 mL) was heated at 150° C. for 12 hours. To the resulting mixture was added a solution of sodium anion of t-butyl cyanoacetate [prepared from t-butyl cyanoacetate (1.27 g) and sodium hydride (346 mg) in dimethyl sulfoxide (14 mL)] in dimethyl sulfoxide (14 mL), the mixture was stirred at room temperature for 2.5 days. After dilution of the mixture with saturated ammonium chloride solution, the mixture was extracted with ethyl acetate. The organic extracts were washed with brine, dried over anhydrous magnesium sulfate, filtered, and then concentrated in vacuo. Flash chromatography (silica, hexane:ethyl acetate=5:1) of the residue gave-crude t-butyl 5-bromo-3-fluoro-2-pyridinecyanoacetate. To a solution of the crude t-butyl 5-bromo-3-fluoro-2-pyridinecyanoacetate in acetonitrile (5 mL) was added trifluoroacetic acid (5 mL) at 0° C., the mixture was stirred at room temperature for 2 hours, and poured into ice water and potassium carbonate. The mixture was extracted with ethyl acetate. The organic extracts were washed with brine, dried over anhydrous magnesium sulfate, filtered, and then concentrated in vacuo. Flash chromatography (silica, hexane:ethyl acetate=4:1) of the residue gave Reference Example 22 (179 mg). [1020] MS (EI + ) m/z: 214 (M + ). [1021] HRMS (EI + ) for C 7 H 4 BrFN 2 (M + ): calcd, 213.9542; found, 213.9558. REFERENCE EXAMPLE 23 5-Bromo-2-pyrimidineacetonitrile [1022] To a suspension of sodium hydride (3.76 g) in dimethyl sulfoxide (200 mL) was added t-butyl cyanoacetate (13.9 mL) at 10° C., the mixture was stirred at room temperature for 1 hour. To the mixture was added 5-bromo-2-chloropyrimidine (7.00 g), the mixture was stirred at room temperature for 2 hours, and poured into ice water and ammonium chloride. The mixture was extracted with ethyl acetate. The organic extracts were dried over anhydrous magnesium sulfate, filtered, and then concentrated in vacuo to give crude t-butyl 5-bromo-2-pyrimidinecyanoacetate. To a suspension of the crude t-butyl 5-bromo-2-pyrimidinecyanoacetate (3.9 g) in dichloromethane (75 mL) was added trifluoroacetic acid (75 mL) at 0° C., the mixture was stirred at room temperature for 18 hours, and concentrated in vacuo. After dilution of the residue with saturated sodium hydrogencarbonate solution, the mixture was extracted with ethyl acetate. The organic extracts were dried over anhydrous magnesium sulfate, filtered, and then concentrated in vacuo. Flash chromatography (silica, hexane:ethyl acetate=2:1) of the residue gave Reference Example 23 (3.71 g). [1023] MS (EI + ) m/z: 197 (M + ). [1024] HRMS (EI + ) for C 6 H 4 BrN 3 (M + ): calcd, 196.9589; found, 196.9572. REFERENCE EXAMPLE 24 1-[5(R)-3-(3,5-Difluoro-4-iodophenyl)-2-oxooxazolidin-5-ylmethyl]-4-methyl-1,2,3-triazole [1025] To a solution of 5(R)-aminomethyl-3-(3,5-difluoro-4-iodophenyl)oxazolidin-2-one (100 mg) in methanol (2 mL) was added diisopropylethylamine (262 μL) and asym-dichloroacetone tosylhydrazone (108 mg) at 0° C., the mixture was stirred at room temperature for 20 hours, and concentrated in vacuo. Flash chromatography (silica, ethyl acetate) of the residue gave Reference Example 24 (110 mg). [1026] MS (EI + ) m/z: 420 (M + ). [1027] HRMS (EI + ) for C 13 H 11 F 2 IN 4 O 2 (M + ): calcd, 420.9895; found, 420.9904. REFERENCE EXAMPLE 25 cis-Tetrahydrofuran-3,4-cyclic Sulfate [1028] To a suspension of 1,4-anhydroerythritol (5.00 g) in carbon tetrachloride (48 mL) was added thionyl chloride (4.2 mL), the mixture was heated under reflux for 1 hour. The mixture was cooled to 0° C., and diluted with acetonitrile (48 mL). The mixture was added sodium periodate (15.4 g), ruthenium trichloride n-hydrate (49.8 mg), and then water at 0° C., the mixture stirred at room temperature for 3 hours. After dilution of the mixture with ether, the mixture was washed with water. The organic extracts were washed with water, dried over anhydrous magnesium sulfate, filtered, and then concentrated in vacuo. Flash chromatography (silica, hexane:ethyl acetate=1:1) of the residue gave Reference Example 25 (6.70 g). [1029] MS (CI + ) m/z: 167 (MH + ). [1030] HRMS (CI + ) for C 4 H 7 O 5 S (MH + ): calcd, 167.0014; found, 166.9993. REFERENCE EXAMPLE 26 5-Bromo-2-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridine [1031] Reference Example 26 (187 mg) was prepared from 5-bromo-2-pyridylacetonitrile (197 mg) and cis-tetrahydrofuran-3,4-cyclic sulfate (183 mg) in the same manner as described for REFERENCE EXAMPLE 19. [1032] MS (CI + ) m/z: 265 (MH + ). [1033] HRMS (CI + ) for C 11 H 10 BrN 2 O (MH + ): calcd, 264.9976; found, 264.9981. REFERENCE EXAMPLE 27 6-(5-Bromopyridin-2-yl)-(1α,5α,6β)-3-oxabicyclo[3.1.0]hexane-6-carboxamide [1034] The mixture of 5-bromo-2-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridine (4.00 g) and 25% sodium hydroxide solution (66 mL) in ethanol (200 mL) was heated under reflux for 6 hours and concentrated in vacuo. Treatment of the residue with water gave Reference Example 27 (4.20 g). [1035] MS (EI + ) m/z: 282 (M + ). [1036] HRMS (EI + ) for C 11 H 11 BrN 2 O 2 (M + ): calcd, 282.0004; found, 281.9966. REFERENCE EXAMPLE 28 5-Bromo-2-[(1α,5α,6β)-6-t-butoxycarbonylamino-3-oxabicyclo[3.1.0]hexan-6-yl]pyridine [1037] The mixture of 6-(5-bromopyridin-2-yl)-(1α,5α,6β)-3-oxabicyclo[3.1.0]hexane-6-carboxamide (2.50 g) and lead tetraacetate (7.83 g) in t-butanol (125 mL) was heated under reflux for 8 hours. After quenching the reaction by addition of saturated sodium hydrogencarbonate solution, the mixture was diluted with ethyl acetate. After the insoluble materials were filtered off, the filtrate was extracted with ethyl acetate. The organic extracts were washed with brine, dried over anhydrous magnesium sulfate, filtered, and then concentrated in vacuo. Flash chromatography (NH silica, hexane:ethyl acetate=7:3) of the residue gave Reference Example 28 (2.10 g). [1038] MS (FAB + ) m/z: 355 (MH + ). [1039] HRMS (FAB + ) for C 15 H 20 BrN 2 O 3 (MH + ): calcd, 355.0657; found, 355.0656. REFERENCE EXAMPLE 29 1-Bromo-4-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3,5-difluorobenzene [1040] Reference Example 29 (1.06 g) was prepared from 4-bromo-3,5-difluorophenylacetonitrile (1.50 g) and cis-N-t-butoxycarbonylpyrrolidine-3,4-cyclic sulfate (1.89 g) in the same manner as described for Reference Example 19. [1041] MS (FAB + ) m/z: 399 (MH + ). [1042] HRMS (FAB + ) for C 17 H 18 BrF 2 N 2 O 2 (MH + ): calcd, 399.0520; found, 399.0522. REFERENCE EXAMPLE 30 1-Bromo-4-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]benzene [1043] Reference Example 30 (809 mg) was prepared from 4-bromophenylacetonitrile (1.00 g) and cis-N-t-butoxycarbonylpyrrolidine-3,4-cyclic sulfate (1.49 g) in the same manner as described for Reference Example 19. [1044] MS (FAB + ) m/z: 363 (MH + ). [1045] HRMS (FAB + ) for C 17 H 20 BrN 2 O 2 (MH + ): calcd, 363.0708; found, 363.0730. REFERENCE EXAMPLE 31 5-Bromo-2-[(1α,5α,6β)-6-cyano-3-thiabicyclo[3.1.0]hexan-6-yl]pyridine [1046] Reference Example 31 (5.5 mg) was prepared from 5-bromo-2-pyridylacetonitrile (32.3 mg) and cis-tetrahydrothiophene-3,4-cyclic sulfate (32.9 mg) in the same manner as described for Reference Example 19. [1047] MS (FAB + ) m/z: 281 (MH + ). [1048] HRMS (FAB + ) for C 11 H 10 BrN 2 S (MH + ): calcd; 280.9748; found, 280.9743. REFERENCE EXAMPLE 32 cis-Tetrahydrothiophene-3,4-cyclic sulfate [1049] To a solution of cis-tetrahydrothiophene-3,4-diol (48.8 mg) and triethylamine (22.6 μL) in dichloromethane (2 mL) was added a solution of sulfuryl chloride (48.9 μL) in dichloromethane (0.4 mL) at −78° C., the mixture was stirred at the same temperature for 1.5 hours. After quenching the reaction by addition of ice, the mixture was extracted with ethyl acetate. The organic extracts were washed with brine, dried over anhydrous sodium sulfate, filtered, and then concentrated in vacuo. Flash chromatography (silica, ethyl acetate) of the residue gave Reference Example 32 (14.6 mg). [1050] MS (EI + ) m/z: 182 (M + ). [1051] HRMS (EI + ) for C 4 H 6 O 4 S 2 (M + ): calcd, 182.0582; found, 182.0582. REFERENCE EXAMPLE 33 [1052] Step 1. 5-Bromo-2-[(1α,5α,6β)-6-carboxyl-3-oxabicyclo[3.1.0]hexan-6-yl]pyridine [1053] To a solution of 6-(5-bromopyridin-2-yl)-(1α,5α,6β)-3-oxabicyclo[3.1.0]hexane-6-carboxamide (100 mg) in concentrated sulfuric acid (1.0 mL) and water (0.5 mL) was added sodium nitrite (73.1 mg) at 0° C., the mixture was stirred at room temperature for 30 minutes. After addition of ice water (1.5 mL), the mixture was stirred at room temperature for 30 minutes. The mixture was adjusted to pH 7 by the addition of potassium carbonate at 0° C. The mixture was adjusted to pH 4 by the addition of 5% hydrochloric acid, the mixture was extracted with chloroform. The organic extracts were dried over anhydrous magnesium sulfate, filtered, and then concentrated in vacuo to give 5-bromo-2-[(1α,5α,6β)-6-carboxyl-3-oxabicyclo[3.1.0]hexan-6-yl]pyridine (87.9 mg). [1054] MS (EI + ) m/z: 283 (M + ). [1055] HRMS (EI + ) for C 11 H 10 BrNO 3 (M + ): calcd, 282.9844; found, 282.9874. [1056] Step 2. 5-Bromo-2-[(1α,5α,6β)-6-hydroxymethyl-3-oxabicyclo[3.1.0]hexan-6-yl]pyridine [1057] To a solution of 5-bromo-2-[(1α,5α,6β)-6-carboxyl-3-oxabicyclo[3.1.0]hexan-6-yl]pyridine (150 mg) in tetrahydrofuran (5.3 mL) was added a solution of diisobutylalminum hydride in toluene (1.0 M, 1.32 mL) at 0° C., the mixture was stirred at room temperature for 1 hour, and stirred at 60° C. for 1 hour. After quenching the reaction by addition of saturated ammonium chloride solution, the mixture was stirred at room temperature for 30 minutes. The mixture was extracted with ethyl acetate. The organic extracts were dried over anhydrous magnesium sulfate, filtered, and then concentrated in vacuo. Flash chromatography (silica, hexane:ethyl acetate=1:3) of the residue gave 5-bromo-2-[(1α,5α,6β)-6-hydroxymethyl-3-oxabicyclo[3.1.0]hexan-6-yl]pyridine (62.3 mg). [1058] MS (EI + ) m/z: 269 (M + ). [1059] HRMS (EI + ) for C 11 H 12 BrNO 2 (M + ): calcd, 269.0051; found, 269.0045. REFERENCE EXAMPLE 34 4-Bromo-2-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]hexan-6-yl]thiophene [1060] Reference Example 34 (104 mg) was prepared from 4-bromo-2-thiopheneacetonitrile (100 mg) and cis-tetrahydrofuran-3,4-cyclic sulfate (90.4 mg) in the same manner as described for Reference Example 26. [1061] MS (EI + ) m/z: 269 (M + ). [1062] HRMS (EI + ) for C 10 H 8 BrNOS (M + ): calcd, 268.9510; found, 268.9519. REFERENCE EXAMPLE 35 5-Bromo-2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-(t-butoxycarbonyl)amino-3-azabicyclo[3.1.0hexane-6-yl]pyridine [1063] Step 1. 5-Bromo-2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-carbamoyl-3-azabicyclo[3.1.0]hexan-6-yl]pyridine [1064] A mixture of 5-bromo-2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridine (4.00 g) and 25% sodium hydroxide solution (70 mL) in ethanol (210 mL) was heated under reflux for 8 hours and concentrated in vacuo. Treatment of the residue with ice water gave the compound of Step 1 of Reference Example 35 (3.88 g). [1065] MS (FAB + ) m/z: 382 (MH + ). [1066] HRMS (FAB + ) for C 16 H 21 BrN 3 O 3 (MH + ): calcd, 382.0766; found, 382.0776. [1067] Step 2. [1068] Reference Example 35 (2.42 g) was prepared from the compound of Step 1 of Reference Example 35 (3.50 g) in the same manner as described for Reference Example 28. [1069] MS (FAB + ) m/z: 454 (MH + ). [1070] HRMS (FAB + ) for C 20 H 29 BrN 3 O 4 (MH + ): calcd, 454.1341; found, 454.1323. REFERENCE EXAMPLE 36 5(R)-5-(t-Butyldimethylsilyloxy)methyl-3-[4-[2-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]oxazolidin-2-one [1071] Reference Example 36 (5.42 g) was prepared from 5(R)-5-(t-butyldimethylsilyloxy)methyl-3-[3-fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolyl)phenyl]oxazolidin-2-one (5.00 g) and 5-bromo-2-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridine (2.94 g) in the same manner as described for EXAMPLE 1. [1072] MS (FAB + ) m/z: 510 (MH + ). [1073] HRMS (FAB + ) for C 27 H 33 FN 3 O 4 Si (MH + ): calcd, 510.2224; found, 510.2204. REFERENCE EXAMPLE 37 5(R)-3-[4-[2-[(1α,5α,6β)-6-Cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5yl]-3-fluorophenyl]-5-hydroxymethyloxazolidin-2-one [1074] To a solution of 5(R)-5-(t-butyldimethylsilyloxy)methyl-3-[4-[2-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]oxazolidin-2-one (4.75 g) in tetrahydrofuran (93 mL) was added a solution of tetrabutylammonium fluoride in tetrahydrofuran (1.0 M, 11.2 mL) at 0° C., the mixture was stirred at room temperature for 1 hour. After quenching the reaction by addition of saturated ammonium chloride solution, the mixture was extracted with ethyl acetate. The organic extracts were washed with brine, dried over anhydrous magnesium sulfate, filtered, and then concentrated in vacuo. Treatment of the residue with ether gave 5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-5-hydroxymethyloxazolidin-2-one (3.07 g). [1075] MS (EI + ) m/z: 395 (M + ). [1076] HRMS (EI + ) for C 21 H 18 FN 3 O 4 (M + ): calcd, 395.1281; found, 395.1261. REFERENCE EXAMPLE 38 5(R)-Azidomethyl-3-[4-[2-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]oxazolidin-2-one [1077] Reference Example 38 (1.72 g) was prepared from 5(R)-3-[4-[2-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]-5-hydroxymethyloxazolidin-2-one (1.90 g) in the same manner as described for Reference Example 13. [1078] MS (FAB + ) m/z: 421 (MH + ). [1079] HRMS (FAB + ) for C 21 H 18 FN 6 O 3 (MH + ): calcd, 421.1424; found, 421.1431. REFERENCE EXAMPLE 39 5(S)-Aminomethyl-3-[4-[2-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]oxazolidin-2-one [1080] Reference Example 39 (1.40 g) was prepared from 5(R)-azidomethyl-3-[4-[2-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]oxazolidin-2-one (1.60 g) in the same manner as described for Reference Example 10. [1081] MS (FAB + ) m/z: 395 (MH + ). [1082] HRMS (FAB + ) for C 21 H 20 FN 4 O 3 (MH + ): calcd, 395.1519, found, 395.1513. REFERENCE EXAMPLE 40 5(R)-5-(t-Butyldimethylsilyloxy)methyl-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]oxazolidin-2-one [1083] Reference Example 40 (109 mg) was prepared from 5(R)-5-(t-butyldimethylsilyloxy)methyl-3-[3-fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolyl)phenyl]oxazolidin-2-one (100 mg) and 5-bromo-2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridine (80.9 mg) in the same manner as described for EXAMPLE 1. [1084] MS (FAB + ) m/z: 609 (MH + ). [1085] HRMS (FAB + ) for C 32 H 42 FN 4 O 5 Si (MH + ): calcd, 609.2909; found, 609.2886. REFERENCE EXAMPLE 41 5(R)-3-[4-[2-[(1α,5α,6β)-3-t-Butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3-fluorophenyl]-5-hydroxymethyloxazolidin-2-one [1086] Reference Example 41 (3.21 g) was prepared from 5(R)-5-(t-butyldimethylsilyloxy)methyl-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]oxazolidin-2-one (4.24 g) in the same manner as described for Reference Example 36. [1087] MS (FAB + ) m/z: 495 (MH + ). [1088] HRMS (FAB + ) for C 26 H 28 FN 4 O 5 (MH + ): calcd, 495.2044; found, 495.2048. REFERENCE EXAMPLE 42 5(R)-Azidomethyl-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3-fluorophenyl]oxazolidin-2-one [1089] Reference Example 42 (1.88 g) was prepared from 5(R)-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3-fluorophenyl]-5-hydroxymethyloxazolidin-2-one (2.00 g) in the same manner as described for Reference Example 13. [1090] MS (FAB + ) m/z: 520 (MH + ). [1091] HRMS (FAB + ) for C 26 H 27 FN 7 O 4 (MH + ): calcd, 520.2109; found, 520.2137. REFERENCE EXAMPLE 43 5(S)-Aminomethyl-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]pyridin-5-yl]-3-fluorophenyl]oxazolidin-2-one [1092] Reference Example 43 (48.0 mg) was prepared from 5(R)-azidomethyl-3-[4-[2-[(1α,5α,6β)-3-t-butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3-fluorophenyl]oxazolidin-2-one (100 mg) in the same manner as described for Reference Example 10. [1093] MS (FAB + ) m/z: 494 (MH + ). [1094] HRMS (FAB + ) for C 26 H 29 FN 5 O 4 (MH + ): calcd, 494.2204; found, 494.2197. REFERENCE EXAMPLE 44 5-Bromo-2-(4-cyanotetrahydropyran-4-yl)pyridine [1095] A mixture of 5-bromo-2-pyridineacetonitrile (400 mg), triethylbenzylammonium chloride (462 mg), bis(2-bromoethyl)ether (281 μL), and 50% sodium hydroxide solution (10 mL) was stirred at 70° C. for 1 hour. After decantation of aqueous layer, the residue was diluted with saturated ammonium chloride solution and extracted with ethyl acetate. The organic extracts were dried over anhydrous magnesium sulfate, filtered, and then concentrated in vacuo. Flash chromatography (silica, hexane:ethyl acetate=7:3) of the residue gave 5-bromo-2-(4-cyanotetrahydropyran-4-yl)pyridine (104 mg). [1096] MS (EI + ) m/z: 266 (M + ). [1097] HRMS (EI + ) for C 11 H 11 BrN 2 O (M + ): calcd, 266.0055; found, 266.0038. REFERENCE EXAMPLE 45 5(R)-3-[4-[2-[(1α,5α,6β)-3-t-Butoxycarbonyl-6-cyano-3-azabicyclo[3.1.0]hexan-6-yl]-3,5-difluorophenyl]-5-hydroxymethyloxazolidin-2-one [1098] Reference Example 45 (105 mg) was prepared from 5(R)-3-(3,5-difluoro-4-iodophenyl)-5-hydroxymethyloxazolidin-2-one (813 mg) and 5-bromo-2-[(1α,5α,6β)-6-cyano-3-oxabicyclo[3.1.0]hexan-6-yl]pyridine (1.00 g) in the same manner as described for Reference Example 31. [1099] MS (FAB + ) m/z: 513 (MH + ). [1100] HRMS (FAB + ) for C 26 H 27 F 2 N 4 O 5 (MH + ): calcd, 513.1950; found, 513.1978. REFERENCE EXAMPLE 46 5(R)-3-(3,5-Difluoro-4-iodophenyl)-5-hydroxymethyloxazolidin-2-one [1101] Reference Example 46 (1.91 g) was prepared from 5(R)-3-(3,5-difluorophenyl)-5-hydroxymethyloxazolidin-2-one (2.00 g) in the same manner as described for Reference Example 13. [1102] MS (EI + ) m/z: 354 (M + ). [1103] HRMS (EI + ) for C 10 H 8 F 2 INO 3 (M + ): calcd, 354.9517; found, 354.9522. REFERENCE EXAMPLE 47 5(R)-Azidomethyl-3-(3,5-difluoro-4-iodophenyl)oxazolidin-2-one [1104] Reference Example 47 (2.44 g) was prepared from 5(R)-3-(3,5-difluoro-4-iodophenyl)-5-hydroxymethyl-oxazolidin-2-one (2.30 g) in the same manner as described for REFERENCE EXAMPLE 13. [1105] MS (FAB + ) m/z: 381 (MH + ). [1106] HRMS (FAB + ) for C 10 H 8 F 2 IN 4 O 2 (MH + ): calcd, 380.9660; found, 380.9685. REFERENCE EXAMPLE 48 1-[5(R)-3-(3,5-Difluoro-4-iodophenyl)-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [1107] Reference Example 48 (876 mg) was prepared from 5(R)-azidomethyl-3-(3,5-difluoro-4-iodophenyl)oxazolidin-2-one (875 mg) in the same manner as described for REFERENCE EXAMPLE 13. [1108] MS (EI + ) m/z: 406 (M + ). [1109] HRMS (EI + ) for C 12 H 9 F 2 IN 4 O 2 (M + ): calcd, 405.9738; found, 405.9750. REFERENCE EXAMPLE 49 4-Fluoro-1-[5(R)-3-(3-fluoro-4-iodophenyl)-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole and 5-Fluoro-1-[5(R)-3-(3-fluoro-4-iodophenyl)-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [1110] A mixture of 5(R)-azidomethyl-3-(3-fluoro-4-iodophenyl)oxazolidin-2-one (700 mg) and 1-fluoro-1-ethenyl phenyl sulfoxide (987 mg) was heated at 110° C. for 15 hours. Flash chromatography (silica, toluene:ethyl acetate=2:1) of the residue gave 4-fluoro-1-[5(R)-3-(3-fluoro-4-iodophenyl)-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (125 mg) and 5-fluoro-1-[5(R)-3-(3-fluoro-4-iodophenyl)-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (258 mg). [1111] 4-Fluoro-1-[5(R)-3-(3-fluoro-4-iodophenyl)-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole: [1112] MS (EI + ) m/z: 406 (M + ). [1113] HRMS (EI + ) for C 12 H 9 F 2 IN 4 O 2 (M + ): calcd, 405.9738; found, 405.9744. [1114] 5-Fluoro-1-[5(R)-3-(3-fluoro-4-iodophenyl)-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole: [1115] MS (EI + ) m/z: 406 (M + ). [1116] HRMS (EI + ) for C 12 H 9 F 2 IN 4 O 2 (M + ): calcd, 405.9738; found, 405.9753. REFERENCE EXAMPLE 50 4-Fluoro-1-[5(R)-3-[3-fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolyl)phenyl]-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole [1117] Reference Example 50 (380 mg) was prepared from 4-fluoro-1-[5(R)-3-(3-fluoro-4-iodophenyl)-2-oxooxazolidin-5-ylmethyl]-1,2,3-triazole (430 mg) in the same manner as described for Reference Example 1. [1118] MS (FAB + ) m/z: 407 (MH + ). [1119] HRMS (FAB + ) for C 18 H 22 BF 2 N 4 O 4 (MH + ): calcd, 407.1702; found, 407.1693. REFERENCE EXAMPLE 51 5-Bromo-2-[(1α,5α,6β)-6-carboxyl-3-thiabicyclo[3.1.0]hexan-6-yl]pyridine [1120] A mixture of 5-bromo-2-[(1α,5α,6β)-6-cyano-3-thiabicyclo[3.1.0]hexan-6-yl]pyridine (1.77 g) and concentrated hydrochloric acid (17 mL) was heated at 80° C. for 70 minutes and concentrated in vacuo. Treatment of the residue with water gave Reference Example 51 (1.81 g). [1121] MS (FAB + ) m/z: 299 (MH + ). [1122] HRMS (FAB + ) for C 11 H 10 BrNO 2 S (MH + ): calcd, 298.9616; found, 298.9612. REFERENCE EXAMPLE 52 5-Bromo-2-[(1α,5α,6β)-6-t-butoxycarbonylamino-3-thiabicyclo[3.1.0]hexan-6-yl]pyridine [1123] To a suspension of 5-bromo-2-[(1α,5α,6β)-6-carboxyl-3-thiabicyclo[3.1.0]hexan-6-yl]pyridine (760 mg) in toluene (10 mL) was added diphenylphosphoryl azide (0.60 mL) and triethylamine (0.46 mL) at room temperature, the mixture was stirred at the same temperature for 75 minutes. The mixture was washed with water and brine. The organic extracts were dried over anhydrous magnesium sulfate, filtered, and then concentrated in vacuo. A solution of the residue in t-butanol (5 mL) was stirred at 120° C. for 9.5 hours and concentrated in vacuo. Flash chromatography (silica, hexane:ethyl acetate=9:1) of the residue gave Reference Example 52 (502 mg). [1124] MS (FAB + ) m/z: 371 (MH + ). [1125] HRMS (FAB + ) for C 15 H 20 BrN 2 O 2 S (MH + ): calcd, 371.0429; found, 371.0407. REFERENCE EXAMPLE 53 5-Bromo-2-pyridylacetonitrile [1126] Step 1. t-Butyl (5-Bromo-2(1H)-pyridinylidene)cyanoacetate [1127] To a suspension of NaH (66.4 g, 60% oil dispersion) in dry DMSO (1.5 L) was added t-butyl cyanoacetate (243 mL) at 18-25° C. for 1 hour, the mixture was stirred at room temperature for 2 hours. 2,5-Dibromopyridine (150 g) was added to the resulting mixture, the mixture was stirred at 120° C. for 6.5 hours. After cooling, the mixture was poured into saturated ammonium chloride solution, the resulting precipitates were collected by filtration, washed with water and cooled EtOH to give t-butyl (5-bromo-2(1H)-pyridinylidene)cyanoacetate (466 g). [1128] 1 H NMR (CDCl 3 ) δ 1.53 (s, 9H), 7.20 (dd, J=9.8, 1.8 Hz, 1H), 7.53 (dd, J=9.8, 2.4 Hz, 1H), 7.64 (dd, J=6.1, 1.8 Hz, 1H), 14.15 (brs, 1H). [1129] Step 2. [1130] Reference Example 53 A suspension of the compound Step 1 of Reference Example 53 (120 g) and KSF clay (80 g) in acetonitrile (800 mL) was heated under reflux for 6 hours. After insoluble materials were filtered off, the filtrate was concentrated in vacuo. Flash chromatography (silica, hexane:ethyl acetate=4:1) of the residue gave Reference Example 53 (57.2 g). [1131] MS (EI + ) m/z: 197 (M + ). [1132] Antibacterial Activity [1133] The pharmaceutically-acceptable compounds of the present invention are useful antibacterial agents having a good spectrum of activity in vitro against standard bacterial strains, which are used to screen for activity against pathogenic bacteria. Notably, the pharmaceutically-acceptable compounds of the present invention show activity against vancomycin-resistant enterococci, streptococci including penicillin-resistant S. pneumoniae, methicillin-resistant S. aureus, M. catarrhalis, and C. pneumoniae. The antibacterial spectrum and potency of a particular compound may be determined in a standard test system. [1134] The following in vitro results were obtained based on an agar dilution method except for C. pneunioniae. The activity is presented as the minimum inhibitory concentration (MIC). [1135] S. aureus and M. catarrhalis were tested on Mueller-Hinton agar, using an approximate inoculum of 1×10 4 cfu/spot an incubation temperature of 35° C. for 24 hours. The MIC was defined as the lowest concentration at which no visible bacterial growth was observed. [1136] Streptococci and enterococci were tested on Mueller-Hinton agar supplemented with 5% defibrinated horse blood, using an approximate inoculum of 1×10 4 cfu/spot an incubation temperature of 35° C. in an atmosphere of 5% CO 2 for 24 hours. The MIC was defined as the lowest concentration at which no visible bacterial growth was observed. [1137] C. pneumoniae was tested using minimum essential medium supplemented with 10% heat-inactivated fetal bovine serum, 2 mM L-glutamine, 1 mg/ml cycloheximide and non essential amino acid. HeLa 229 cells were inoculated with 10 4 inclusion-forming units of C. pneumoniae strain per mL. Infected cells were incubated with test compounds in complete medium at 35° C. in an atmosphere of 5% CO 2 for 72 hours. Cells monolayers were fixed in methanol, stained for chlamydial inclusions with an fluorescein-conjugated anti-Chlamydia monoclonal antibody, and were observed with fluorescence microscope. The MIC was defined as the lowest concentration at which no inclusion was observed. MIC (μg/ml) Strains example 13 example 15 example 23 Linezolid Staphylococcus aureus Smith 0.125 0.25 0.06 1 CR 0.5 1 0.5 16 MR 0.125 0.25 0.06 1 Streptococcus pneumoniae IID553 0.125 0.25 0.06 2 PRQR 0.06 0.25 0.06 1 Streptococcus pyogenes IID692 0.06 0.25 0.06 1 Enterococcus faecium VRQR 0.125 0.5 0.06 2 Morcaxella catarrhalis ATCC25238 1 4 0.5 4 CR = chloramphenicol resistant MR = methicillin resistant PRQR = penicillin resistant, quinolone resistant VRQR = vancomycin resistant, quinolone resistant NT = not tested [1138] The invention described herein is exemplified by the following non-limiting examples. The compound data is designated in accordance to General Guidelines for Manuscript Preparation, J. Org. Chem. Vol. 66, pg. 19A, Issue 1, 2001.
This invention relates to new oxazolidinones having a cyclopropyl moiety, which are effective against aerobic and anerobic pathogens such as multi-resistant staphylococci, streptococci and enterococci, Bacteroides spp., Clostridia spp. species, as well as acid-fast organisms such as Mycobacterium tuberculosis and other mycobacterial species. The compounds are represented by structural formula I: its enantiomer, diastereomer, or pharmaceutically acceptable salt or ester thereof.
2
BACKGROUND OF THE INVENTION [0001] 1. Field of the Invention [0002] The present invention relates to an apparatus for collecting, bagging and transporting snow and other movable objects or articles outdoors and indoors. [0003] 2. General Background and State of the Art [0004] This invention was primarily designed to facilitate the removal of snow from driveways and walkways during the winter time. It became subsequently obvious that it could also be used to facilitate the removal of dead leaves from yards during the fall and also serve for the transportation of various movable objects outdoors and indoors. [0005] With respect to snow removal from driveways and walkways outdoors, the snow removal tools currently used such as shovels, various types of salt or snow/ice melters, snow blowers, etc. are either labor intensive, time consuming, energy consuming, financially expensive, risky and not necessarily environment friendly. The proposed invention attempts to address all these concerns with a simple less labor intensive, less time consuming, less expensive and more environment friendly tool. With the proposed invention, snow accumulation of up to 10 inches or more on a fifty square feet surface of driveways or sidewalks can be removed within two to three minutes, about one fifth of the time needed to do so when using conventional methods and tools. [0006] Attempts have been made in the past to tackle these concerns with electric heated mats (U.S. Pat. Nos. 6,051,811, 5,380,988; 5,291,000; . . . ), snow removal and transportation devices (U.S. Pat. No. 4,185,403), snow and ice melting blanket devices (U.S. Pat. No. 6,051,812); all of which are more complex, pose more health and environment risks, and are more expensive than the proposed invention. [0007] With respect to collection and disposal of leaves and debris from yards, excessive energy is conventionally used by using blowers over large distances or by filling and transporting several leave bags out of the yard, in all cases by spending enormous amounts of energy. My invention provides a simple alternative solution at the lowest possible energy cost. [0008] With respect to other domestic or outdoor usages of this bag, such as taking out a big load of clothes to laundry, collecting and moving harvested fruits or grains to trucks and/or storage, these tasks are usually accomplished by using for a big load of objects several small containers with several trips to get done. My invention provides a simpler, cheaper and more efficient solution to get the job done quickly with fewer trips. SUMMARY OF INVENTION [0009] My invention is based on the very simple concept of laying down in the driveway or on the sidewalk a rectangular and flat piece of flexible waterproof material/fabric such as plastic tarpaulin or canvas, equipped with zippers, straps and ropes on its edges, use it first as a mat to collect the snow during snow accumulation, and then transform the mat into a bag after the snow accumulation by closing the zippers and tying up the straps and ropes. The bagged snow can then be easily moved out of the driveway or walkway by pulling or lifting the loaded mat-bag using handles located on its four sides. The same principles are used to collect and move other items such as dead leaves during the fall, clothes for laundry, grains and fruits to storage on farm, etc. My invention as further described and demonstrated in the attached drawings and text has two basic designs: a light duty Type A design made with a relatively light plastic material and a heavy duty Type B design made out of a heavier duty material such as thick military-style canvas. BRIEF DESCRIPTION OF THE DRAWINGS [0010] FIG. 1 is an elevational view of the face of the mat-bag in accordance with its light duty type A design at the mat stage. [0011] FIG. 2 is an elevational view of the back of the mat-bag in accordance with the type A design of this invention at the mat stage. [0012] FIG. 3 is an elevational view of the mat-bag, in accordance with its Type A design at the bag stage [0013] FIG. 4 shows a perspective view of the first operation step of the type A mat-bag, with the mat laid down on the floor, all four side flaps folded underneath and conic bricks placed on top of the mat-bag in all four corners, carrying the free ends of the ropes. [0014] FIG. 5 shows the second operation step of the type A mat-bag: the pulling-up of the ropes to wrap-up the snow and form the bag [0015] FIG. 6 is a graphic view of the internal and external components of the mat-bag in accordance with its heavy duty type B design at the mat stage [0016] FIG. 7 is a perspective view of the face of the mat-back in accordance with its type B design at the mat stage [0017] FIG. 8 is a perspective view of the back of the mat-back in accordance with its type B design at the mat stage [0018] FIG. 9 is an elevational view of the mat-bag in accordance with its type B design at the bag stage. [0019] FIG. 10 shows an operation step: the conversion from mat to bag, with the type B design DESCRIPTION OF THE PREFERRED EMBODIMENTS [0020] 1. The Light Duty Type A Design: Construction and Operation [0021] With reference to FIG. 1 and FIG. 2 . The central piece of the light duty type A mat-bag is a rectangular piece of thick plastic tarpaulin material 1 (at least 5 mils thickness) of various sizes (standard 5.2′×7.2′), commonly sold in home stores. Squared pieces of about one square foot (for the standard size) or more are removed from each corner 2 to allow for the installation of heavy duty straps 3 and zippers 4 which when tied and/or closed transform the flat plastic piece or mat into a boat-like bag ( FIG. 3 ) to contain the snow. The plastic mat has on its edges (or side flaps) 5 on each side one to two ringed holes 6 (of about one inch diameter each) through which ropes 7 can be inserted to bring the opposite edges or flaps 5 of the mat together to form the bag. [0022] The ropes 7 are about four to five feet long with a knot 10 at one end ( FIG. 2 ); the end without the knot is inserted into the ringed hole trough the back of the mat and the knot which is bigger than the hole acts as a stopper. The ropes used are ordinary strong ropes made of nylon with about one half inch diameter. As in the case of ordinary tarpaulin and canvas sold in stores, a metallic or plastic ring covers and protects the edges of the holes 6 through which the ropes are inserted. When the ropes 7 on opposite sides are tied up together two by two, they transform the mat into a bag for carrying objects ( FIG. 3 ). [0023] Other stronger straps 8 ( FIG. 2 ), one or two on each side of the bag provide the handles 8 to be gripped to take the bag away either by carrying it (two people or more, each holding one or two handles) or by dragging it away on the floor from one end by pulling on the handles 8 on one side (one person). Areas that carry the handles and ringed holes are reinforced by doubling the plastic material 9 , so as to provide greater resistance against tearing forces when carrying or pulling the bag. [0024] The straps 3 , two to four in each cut corner 2 , are made of the same plastic tarpaulin fabric, they are sown at the top and/or near the middle of each cut corner about two inches away from the corner edges. In addition one heavy duty zipper 4 may be installed per cut corner, with each one of the two parts of the zipper covering each one of the two edges of the cut corner. [0025] Regarding operation, the four to five feet long ropes with knots 10 on one end are inserted into the ringed holes through the back of the mat-bag. The knots are big enough to not go through the holes and consequently act as the rope stoppers. In the next step, the four side flaps 5 are turned down, folded down against the back of the mat-bag before laying the latter in the driveway as shown in FIG. 4 . [0026] The ropes can be left below the mat-bag making sure that they are easily accessible below the edges after the snow accumulation. One easier option is to put conic bricks 11 on the four corners of the mat-bag as shown in FIG. 4 to stabilize it on the floor especially in windy conditions and place the free ends of the ropes on a metallic (iron) ringed rod encrusted inside and on top of the bricks, so as to easily locate the ropes after the snow fall or storm and pull them to wrap up and bag the snow. Alternatively, the ropes can also be tied up together and left on the top iron rod ring of a single conic brick in the middle of the mat so as to be easily reached after the snow fall. The conic brick, measuring about 8 to 10 inches wide and high, may be made of concrete (cement) and molded with the encrusted iron rod, both forming one piece. The iron rod is 3 to 4 feet high above the conic brick, has a circular section of about one half inch in diameter and the same applies for its top ring. [0027] The ropes can also be tied to sticks or to plants or trees near the driveway or walkway so as to be easily visible and accessible after a heavy snow fall. [0028] After the snow accumulation on the mat-bag, the operator pulls up the free ends of the ropes as shown in FIG. 5 . When the ropes 7 are pulled upward, the side flaps 5 automatically unfold upward and wrap the snow content 12 on its sides. Once all ropes are pulled up and all four side flaps are unfolded, the operator ties the opposite ropes two by two so as to form the bag ( FIG. 3 ) to contain and move the snow away. [0029] Regarding operation for other usages of the mat-bag such as removing dead leaves from yards during the fall, the mat-bag is laid down at its mat stage on the floor with all four flaps folded down underneath as in the case of snow collection. The leaves are then pushed onto the mat by using either brooms, racks or blowers. Once a large quantity of leaves is piled on top of the mat the operator pulls up the ropes to unfold the side flaps, wrap and bag the leaves by tying up ropes and straps and by closing zippers. The same process will be used for collecting and bagging other items such as clothes, grains or fruits on the farm, etc. [0030] 2. The Heavy Duty Type B Design: Construction and Operation [0031] With reference to FIG. 6 through FIG. 10 the Type B mat-bag is designed to be a heavy duty mat-bag. It is made out of army-style canvas material, typically 82″ long and 55″ wide. The principle of a flat piece of material for items collection and of tying up edges to transform the flat piece (mat stage) into a bag for transporting the collected items remains the same. In this case, there are no ropes, adjustable or fixed belts 13 , made out of the same canvas fabric and placed across the length and the width of the canvas are used to form and tie the bag. The canvas is doubled all across its surface 14 . Reinforcements 15 along the belts and reinforcements 16 beneath the handles are sown to provide greater resistance to all tearing forces. [0032] With reference to FIG. 6 showing the interior of the type B mat-bag, the canvas may be sown in such a way as to provide furrows 17 within which the belts 13 could move freely and be adjusted as needed. Alternatively and preferably, the mid sections of the belts can instead be fixed by sowing them onto the canvas layers leaving only the external ends (3-4 feet) free. Typically the mat-bag is constructed with equidistant belts across the length and the width of the mat-bag, with the two exterior belts along the length as close as possible (two to ten inches) to the edges of the mat so as to provide good control of the snow content in the four corners of the mat-bag. Doubled pieces of the canvas, about two inches wide and one foot long are sown on the back of the mat-bag, about one foot away from the edges to provide the handles to carry the bag. Typically six handles are provided, one along each width and two along each length of the rectangular mat-bag. [0033] Regarding operation, the mat-bag is laid down on the driveway or walkway before the snow fall, with about one foot of all four sides folded underneath to act as flaps and the free ends of the belts are left hanging or tied on top of conic bricks placed above the mat-bag in all four corners and/or in the middle of the mat-bag as judged appropriate by the operator. After the snow accumulation, the operator pulls up the free ends of the top corner belts 13 and tie them up diagonally (tie top belts located at diagonally opposite corners) as shown in FIG. 9 before tying up two by two the remaining laterally located opposite belts as shown in FIG. 9 and FIG. 10 to contain the snow. The result is a bag of snow that can be moved away by lifting the bag or by dragging it on the floor using some or all of the six handles. References Cited [0034] [0000] U.S. Patents Documents 6051811 April, 2000 Hardison 5380988 January, 1995 Dyer 5291000 March, 1994 Hornberger 4185403 January, 1980 Hardgrove 6051812 April, 2000 Walker
The snow mat-bag is a rectangular piece of flat plastic tarpaulin or canvas of different sizes as needed, equipped with straps, ropes, handles and zippers on its edges to collect, bag and transport snow away from driveways and sidewalks during the winter by closing the zippers and tying the straps and ropes. It can also be used to collect, bag and move away other objects such as dead leaves from yards during the fall, clothes for laundry, grains and fruits for storage on farms.
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CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to DE Application No. 102013205211.1, having a filing date of Mar. 25, 2013, the entire contents of which are hereby incorporated by reference. FIELD OF TECHNOLOGY The following relates to a radiotherapy treatment device comprising an image acquisition device, in particular a magnetic resonance device, an irradiation device comprising in particular a linear accelerator, and a patient positioning device having a patient positioning platform. The following relates in addition to a radiotherapy method for treating an irradiation target in a patient by means of such a radiotherapy treatment device. BACKGROUND Radiation therapy is already widely known in the prior art. It finds application principally in the treatment of cancerous diseases, whereby accelerated particles are emitted in a targeted manner in such a way that they deposit the majority of their energy in an irradiation target, in particular a tumor. In most cases linear accelerators, often referred to also in abbreviated form as LINACs, are employed for this purpose. What is essential in this context is optimally precise planning of the irradiation that is to be carried out, since it is aimed to strike the actual irradiation target, in particular a tumor, with the utmost precision and to spare healthy tissue as far as possible. In this regard imaging modalities such as computed tomography or magnetic resonance can be used, for example, for irradiation planning purposes. A three-dimensional image dataset of the body region that is to be irradiated, i.e. of the target region containing the irradiation target, is acquired and a unique reference established to the outer shell (surface) of the patient by means of markers or stereotactic frames. In this regard there exist target regions within the patient, in particular organs, which are subject to displacements inside the body, in the range of several centimeters for example. Examples of this are the lung, which is moved by regular respiration, and the prostate, which can likewise be displaced in the centimeter range due to involuntary intestinal motions. This is why in practice irradiations, of the prostate for example, are performed with a considerable safety margin, which results in substantially the entire organ being irradiated, which can lead to undesirable side effects. In order to solve this problem it has been proposed to use combination devices in which an image acquisition device, for example a computed tomography device, a magnetic resonance device or an X-ray fluoroscopy system, is combined with an irradiation device, in particular comprising a LINAC. The idea informing the systems proposed here is as complete an integration as possible so that the image acquisition device continuously acquires image data of the target region such that a current position of the irradiation target can be determined and used to control the beam of the irradiation device in such a way that the irradiation target is bombarded to maximum effect, in other words with an optimal dose. In particular irradiation devices in which an X-ray fluoroscopy system (X-ray device) is already integrated are known in this context. For example, a radiation source whose X-ray beams are received by an oppositely arranged detector can be provided adjacent to a beam exit of the LINAC. On the other hand, soft tissue resolution in particular and also three-dimensional imaging capability are severely limited in the case of X-ray devices, with the result that combination systems composed of magnetic resonance devices and irradiation devices including a linear accelerator have also been proposed. Radiotherapy treatment devices in which a magnetic resonance device and an irradiation device have been integrated with one another are known for example from WO 2003/008986, US 2005/0197564, U.S. Pat. No. 6,366,798, U.S. Pat. No. 6,198,957, DE 10 2008 007 245, DE 10 2010 001 746, DE 10 2007 054 324 and DE 10 2006 059 707. The solutions described in each of the cited publications necessitate large-scale changes to the magnetic resonance configuration and are accompanied by limitations in terms of image quality and enormous costs for the radiotherapy treatment device. Consequently the performance of the devices, the range of applications and patient comfort are frequently severely restricted. What is advantageous about these systems, however, is that often it is no longer necessary to move the precisely positioned patient. SUMMARY An aspect relates to an easier-to-realize possibility of having available further imaging modalities delivering high-quality data during a radiation therapy treatment session in spite of an ideally motionless patient. It is inventively provided in the case of a radiotherapy treatment device of the type cited in the introduction that a movement device is provided for in particular jointly moving the image acquisition device and the irradiation device between an irradiation position, in which a radiotherapeutic treatment of a patient located on the patient positioning platform is possible by means of the irradiation device, and an image acquisition position, in which acquiring an image of the patient located on the patient positioning platform is possible by means of the image acquisition device. It is therefore proposed to continue to implement the irradiation device, which in particular can include a linear accelerator (LINAC), and an image acquisition device, in particular a magnetic resonance device offering good soft tissue contrast, as separate functional units, yet to guide the irradiation device and the image acquisition device in a kind of “shuttle mode” around the preferably completely motionless patient located on the patient positioning platform. Thus, the subsystems of the image acquisition device and the irradiation device, still realized as separate functional units, are jointly adjusted in terms of their position such that at least two predetermined positions exist. The first of these predetermined positions is the irradiation position, in which a radiotherapeutic treatment of the patient by means of the irradiation device is possible in the conventional manner. The image acquisition device is in this case arranged at a distance, with the result that acquiring an image of the irradiation target at this moment in time is no longer possible. The second of these positions is the image acquisition position. The image acquisition device is then located in a position in which it is possible to acquire an image of the irradiation target or, as the case may be, of the target region comprising the irradiation target, yet the irradiation device is arranged at a distance, with the result that an irradiation of the irradiation target cannot take place. In the image acquisition position it is therefore possible to acquire image data which can be evaluated in respect of the irradiation target's position, which may need to be updated, in particular at least prior to the commencement of the irradiation. Ideally without a movement of the patient, hence of the patient positioning platform, taking place, the image acquisition device and the irradiation device are then repositioned so that thereafter the irradiation can be started using the information obtained from the image data. Approaches are also conceivable in which the image acquisition device and the irradiation device are moved toward the irradiation region, i.e. irradiation target, of the patient in alternation. The diagnostic image information that can be obtained from the image data is used in particular in order to adapt the irradiation planning to the current position of the body organs that are to be irradiated (the irradiation target) or, as the case may be, to check the correspondence. In this case it is possible, in particular when a magnetic resonance device is used as the image acquisition device, to minimize the interaction between the image acquisition device and the irradiation device by separating the subsystems by a suitable distance and where necessary by means of shielding measures. The treatment device therefore enables a complicated and expensive integration of irradiation device and imaging device to be avoided in order instead to allow a “shuttle mode of operation” of existing subsystems in relation to a permanently stationary patient positioning device. In this way the implementation overhead is reduced to the mounting or guidance of the subsystems, though solutions for this purpose, for example from the field of intraoperative magnetic resonance or computed tomography, are already well-known. A particular advantage of the invention in this regard is that there is nonetheless no requirement to move the patient during the radiation therapy. As is generally known, a patient is not a rigid system and can react to movements with changes, so that movements of the patient, in particular rotary movements, can be largely or preferably completely avoided by means of the present treatment device. The radiotherapy device and the image acquisition device are moved instead. The fact that a movement of the patient is not really necessary is also of psychological advantage to the patient, who can have greater confidence that the irradiation target will be reached correctly. Actual possibilities for realizing a movement of subsystems which continue to be functionally largely independent are to be expounded in more detail hereinbelow and are described by means of the dependent claims. It is beneficial if the movement device comprises an in particular common means of guidance for the irradiation device and the image acquisition device. A rail guidance system in which the two subsystems are guided lends itself as particularly suitable in this regard. The guidance system is arranged on the ceiling and/or on the floor of a room containing the radiotherapy treatment device. In particular devices suspension-mounted by means of the guidance system and guided along a ceiling have the advantage that the floor area can be kept largely free for other activities, for example for access to the patient and for the placement of further devices. A beneficial development of the treatment device in this connection furthermore provides that the linear guidance system extends along a longitudinal axis of the patient positioning platform of the patient positioning device. Such a solution presents itself as particularly attractive since in irradiation devices the irradiation head can in most cases be moved around the patient, in particular on a circular trajectory, and consequently a corresponding guidance device is present for the irradiation head, which is frequently arranged on a gantry. This can then simply be driven over or around the patient positioning platform or moved further away from the latter, while many image acquisition devices also comprise annular components at least partially encircling the patient positioning platform during the imaging, for example a gantry in the case of a computed tomography device or the main magnet array in the case of a magnetic resonance device. Linear guidance systems along a particular direction can furthermore be realized in a particularly simple manner. Basically it should be noted that guidance systems of said type for medical equipment, including devices having a relatively great weight, are in principle already well-known in the prior art, such that the corresponding knowledge can also be applied to the present treatment device. For example, image acquisition devices have been proposed which can be maneuvered by way of such a guidance system during an operation toward a patient and away from the patient again, and the like. The movement range of the image acquisition device and/or the irradiation device between the irradiation position and the image acquisition position can amount to between 10 cm and 200 cm. It has been demonstrated that traversing distances in the range from 10 cm up to 2 m should normally suffice for irradiation tasks in the region of the head, chest, lung, liver and prostate. Even when a magnetic resonance device is used, an adequate distance in order to minimize the interaction between the subsystems can already be achieved with such ranges of movement. In order to further improve the shielding and to further reduce the interaction between the irradiation device and the image acquisition device, that is to say the subsystems, it can also be provided that at least one, in particular co-movable, shielding device is disposed between the irradiation device and the image acquisition device. It is conceivable for example to arrange a metallic shield at least partially around the image acquisition device, which can be embodied in particular as a magnetic resonance device, such that ultimately a kind of Faraday cage is formed. Metallized surfaces in the direction of the irradiation device can also beneficially be provided on a magnetic resonance device. It is also particularly beneficial if the radiotherapy treatment device comprises a collision avoidance device having at least one sensor for monitoring the relative position of a patient located on the patient positioning platform and components of the image acquisition device and the irradiation device. The safety of the patient can be further increased in this way, since sensors, for example contact sensors and/or motion sensors and/or cameras, can constantly monitor the position of the patient and the moving devices and interrupt the movement in the event of imminent contact, in particular an imminent collision, between components and the patient. Such collision avoidance devices, which are already known in principle in the prior art, for example from X-ray devices having a movable C-arm and the like, can therefore also advantageously be used within the scope of the present treatment device in order to realize the best possible protection of the patient. It is also preferred in this connection if the patient positioning device has at least one protection means protecting the patient against moving components of the image acquisition device. The embodiment of the patient positioning device itself can therefore already be chosen with a view to ensuring that as far as possible the risk of a collision occurring with the patient can be eliminated from the outset. It can be provided for example that the protection means has at least one protective body at the edge of the patient positioning platform of the patient positioning device, in particular a protective cushion and/or a protective section integrally molded to the shape of the patient positioning platform. It is therefore conceivable for example to provide a protective body in a tubular and/or cushion shape at the edge of the patient positioning platform so that a stable enclosure of the patient of said kind can protect the patient against the movement of the irradiation device and the image acquisition device. It is also conceivable to realize such a protective body through provision of a corresponding profiling of the patient positioning platform in the edge region. Thus, for example, the patient positioning platform can be embodied in the manner of a tray in the edge region in order thereby to form a protective cradle around the patient. It may also be conceivable to extend the protective body to form a complete protective capsule around the patient, provided that said capsule is at least to a large degree transparent to the image acquisition device and the irradiation device and also does not negatively affect the beam quality of the irradiation device too severely. It is also possible in another alternatively or additionally usable embodiment variant for the protection means to be realized as at least partially integral with a patient immobilizing device. In this case it can for example be provided that the patient immobilizing device has a positioning means which can be stiffened by vacuumization. Thus, for example, grain cushions are known on which a patient is positioned. If the air is then extracted from the grain cushion, i.e. it is vacuumized, it rigidly maintains the shape molded to the patient, with the result that the patient is stably positioned, yet at the same time is surrounded toward the outside by the grain cushion, which therefore acts also as a protection means. Special attention should also be directed to the patient positioning device, which should provide the necessary freedom of movement for the irradiation device and/or the image acquisition device. As has already been indicated, in magnetic resonance devices the magnet arrangement typically encloses the patient in a kind of cylinder, which should be possible in the embodiment of the patient positioning device. Irradiation devices are also known in which the irradiation head is designed to be rotatable through 360° around the patient. In such cases it is extremely advantageous if a support structure of the patient positioning device is arranged such that parts of the image acquisition device and/or the irradiation device can be driven under the patient positioning platform. In particular with image acquisition devices and irradiation devices which have components encircling the patient in the manner of a ring, it is then possible to arrange said components around the patient by driving them under the patient positioning platform. In this case it is conceivable in a first embodiment for the support structure to be provided on the side of the irradiation device that is not partly driven under the patient positioning platform. The support structure for the patient positioning platform can therefore be mounted on the side of the irradiation device, since in the case of the irradiation device it can to some extent be tolerated that the irradiation head is not able to be rotated through 360° around the patient. Then the irradiation device can be driven above the support structure and finally above the patient positioning platform, since it is not necessary for it to be driven under on this side. It nevertheless continues to remain possible on the part of the image acquisition device, embodied in particular as a magnetic resonance device, which makes its approach from the other side, to be driven under the platform. In another embodiment it can be provided that a retaining device of the irradiation device at least partially surrounds the support structure or is at least partially surrounded by said support structure. Thus, if the irradiation device has for example a pillar carrying the actual irradiation arrangement with the linear accelerator and the irradiation head, the support structure can be guided around such a retaining device or else the support structure can also be guided through a corresponding opening in said retaining device. This has the advantage that then the irradiation device too can be realized in such a way that it is driven under the patient positioning platform and in particular permits the irradiation head to rotate through 360° around the patient. In a third, alternative embodiment of the present invention it is provided that the support structure has two substructures, each of which is connected to the irradiation device and the image acquisition device and can be moved jointly with said devices. The patient positioning device can therefore have different support structures having substructures which are moved together with the respective device, wherein when a magnetic resonance device is used, for example, the support structure on the magnetic resonance side can be formed in whole or in part by the main magnet arrangement or its housing. However, such an embodiment variant itself requires moving portions of the substructures, in particular drives synchronized with the movement of the irradiation device and the image acquisition device, in order to hold the patient positioning platform in its actual position. For this reason this variant is less preferred. A fourth embodiment variant of the invention, likewise an alternative to the other embodiment variants, provides in this connection that the patient positioning device has the central support structure and the patient positioning platform, wherein the patient positioning platform is movable in the direction of the irradiation device in order to assume the irradiation position and in the direction of the image acquisition device in order to assume the image acquisition position. This embodiment therefore includes for example as support structure a central pillar which has extended traversing paths of the patient positioning platform in both directions along the longitudinal axis of the patient positioning platform so that the patient positioning platform can be driven as it were toward the irradiation device and the image acquisition device. However, since in this case a movement of the patient positioning platform, and hence of the patient, is necessary, though only linearly, this exemplary embodiment is may be less preferred. In a further embodiment of the radiotherapy treatment device it can generally be provided that an X-ray device is integrated into the irradiation device. This therefore means that as an irradiation device that is functionally separate from the image acquisition device it is also possible to use such a device into which an X-ray device for imaging is already integrated, so that an imaging modality of said kind can also continue to be used in order to supplement image data material of the image acquisition device, in particular also to enable further movements of the patient, for example periodic respiratory motions, to be tracked and to provide other monitoring possibilities. Particularly when a magnetic resonance device is used as an image acquisition device, which is far more difficult and costly to implement and in which integrating a linear accelerator is relatively complicated, but which offers good soft tissue contrast, an X-ray device which can be integrated easily into the irradiation device constitutes a useful extension of the imaging possibilities. Another beneficial development provides that an ultrasound device for imaging is integrated into the patient positioning device. It is therefore also conceivable to combine an ultrasound device, in particular one that is magnetic-resonance- and radiation-compatible, in a stationary manner with the patient, which device can also be used in order to establish the validity of the magnetic resonance data or in this case also to track movements of the patient. In this case a data fusion is conceivable, for example; using a motion model also affords the possibility of using data of the ultrasound device during the irradiation. At least one local coil of the image acquisition device embodied as a magnetic resonance device can beneficially be movable together with the image acquisition device. In this embodiment the magnetic resonance local coils, embodied as receive and/or transmit coils, are therefore moved together with the magnetic resonance device. Toward that end the local coils can be fixedly mounted for example on the main magnet arrangement, in particular its housing, and consequently can be moved out of the target region when the magnetic resonance device is moved. In the context of the magnetic resonance device as image acquisition device it is also conceivable that in the irradiation position the irradiation target can be positioned inside a patient receiving means of the image acquisition device, but outside of the homogeneity region of the image acquisition device. It is therefore not necessary to remove the irradiation target completely from the patient receiving means, but it is also conceivable, for example using an obliquely inclined irradiation head, to leave this irradiation target at least a short way inside the patient receiving means. The irradiation target is then no longer located in the isocenter, i.e. in the homogeneity region, so that although no simultaneous imaging is made possible any longer, the overall movement distances can be kept small. Care should of course be taken to ensure in this case that the irradiation device and the image acquisition device, which is embodied as a magnetic resonance device, are not too strongly affected. In addition to the radiotherapy treatment device, the present also relates to a radiotherapy method for treating an irradiation target in a patient by means of a radiotherapy treatment device. In the method said device therefore comprises an image acquisition device, in particular a magnetic resonance device, an irradiation device, in particular comprising a linear accelerator, and a patient positioning device having a patient positioning platform, the method being characterized in that by means of a movement device provided for jointly moving the image acquisition device and the irradiation device an irradiation position is assumed in which a radiotherapeutic treatment of a patient located on the patient positioning platform by means of the irradiation device takes place, and an image acquisition position is assumed in which an image of the patient located on the patient positioning platform is acquired by means of the image acquisition device. All embodiments in respect of the inventive radiotherapy treatment device can be applied analogously to the inventive radiotherapy method, by means of which device and method the already cited advantages can therefore be achieved. It can be provided in this case that image data acquired with the image acquisition device is analyzed by means of an evaluation device in order to determine and/or monitor a position of the irradiation target. When the radiotherapy treatment device is used, it can therefore be provided that in the first instance an image is acquired by means of the image acquisition device, in particular the magnetic resonance device, image data accordingly being acquired in an image acquisition mode. This happens in the image acquisition position. The image data can be analyzed by means of a control device in order to establish the current position of the irradiation target with the greatest possible accuracy. Next, the image acquisition device is moved away from the patient and the irradiation target, but the irradiation device is moved toward the patient so that the irradiation position is assumed and the irradiation can take place taking the analysis of the image data into account. If necessary, however, it is also possible to switch to the image acquisition position again during or after the irradiation, in which case the frequency of these switchovers can be made dependent on the speed at which the target organ comprising the irradiation target moves, as well as on the technical possibilities. If just the correct position of the patient, and hence of the irradiation target, is to be checked at the commencement of the irradiation, a single image acquisition in the image acquisition position is sufficient. If, on the other hand, checks are also to take place intermittently during the irradiation, it can be provided that the irradiation is interrupted at least once during the entire period of the irradiation and the radiotherapy treatment device is moved into the image acquisition position in order to acquire the image data serving for monitoring the position of the target. In a particularly beneficial embodiment it can be provided that during a periodic movement in a target region comprising the irradiation target, in particular a respiratory motion, a series of image data reflecting at least one cycle of the periodic movement is recorded in the image acquisition position, motion information of the irradiation target is determined from the series of image data and taking into account the signals of at least one monitoring device monitoring the periodic movement, in particular a respiratory belt and/or an X-ray device integrated in the irradiation device and/or an ultrasound device integrated in the patient positioning device, for the purpose of controlling the irradiation device in order to ensure correct irradiation of the irradiation target. With periodic movements, for example breathing, it is therefore also possible firstly to acquire a series of image data which records one or more cycles of the periodic movement in an imaging manner. Motion information derived therefrom can be applied during the irradiation without further image acquisitions. In this case information on the breathing position or other phase of the periodic movement can be used by other devices, for example by a respiratory belt, an ultrasound device or an X-ray device, as has already been described. It should be emphasized once again at this point that the possibility of using image data acquired by means of the image acquisition device is based on the fact that on account of the predefined overall geometry of the system and the automatic movement, realized for example by way of a control device, the image acquisition device and the irradiation device are registered with each other at all times. The control device therefore actuates the movement device in order to effect movements from the image acquisition position to the irradiation position and vice versa. Both positions are well-known in the system and permit the assignment of positional information in both subsystems. BRIEF DESCRIPTION Further advantages and details of the present invention will emerge from the exemplary embodiments described hereinbelow as well as with reference to the drawing, wherein: FIG. 1 is a schematic illustrating the basic principle of the radiotherapy treatment device according to an embodiment of the invention, FIG. 2 shows a first actual embodiment variant of a radiotherapy treatment device according to an embodiment of the invention, FIG. 3 shows a second actual embodiment variant of a radiotherapy treatment device according to an embodiment of the invention, and FIG. 4 is a schematic diagram illustrating a third actual embodiment variant of a radiotherapy treatment device according to an embodiment of the invention. DETAILED DESCRIPTION FIG. 1 illustrates the basic principle of a radiotherapy treatment device 1 . This comprises a patient positioning device 2 having a patient positioning platform 3 . The patient positioning platform 3 and therefore the patient ideally immobilized thereon are kept motionless during an entire radiation therapy treatment. The radiotherapy treatment device 1 further comprises two essentially independent subsystems, namely a treatment device 4 and an image acquisition device 5 . These can be displaced linearly via a movement device 6 , as indicated by the arrow 7 , relative to the patient positioning platform 3 , in this case in the longitudinal direction thereof, so that in an image acquisition position the image acquisition device 5 is moved toward the patient such that an image acquisition can take place, and in a treatment position the treatment device 4 can be directed to a treatment target in the patient. In the present case the movement of the image acquisition device 5 is coupled to that of the treatment device 4 . The operation of the radiotherapy treatment device 1 is controlled by a control device 8 , also indicated in FIG. 1 , which may also comprise an evaluation device 9 for image data of the image acquisition device 5 . It is therefore conceivable to move the devices 4 , 5 via the movement device 6 at the commencement of a radiation therapy treatment initially in such a way that the image acquisition position is assumed. Image data of the patient on the patient positioning platform 3 is recorded and analyzed in the evaluation device 9 in order to determine whether the position of the irradiation target corresponds to the irradiation planning that was carried out beforehand. If this is not the case, appropriate adjustments can be made on the part of the irradiation device 4 , this being performed under the control of the control device 8 . During periodic movements of the patient, in particular a respiratory motion, it is also possible in the first instance to use the image acquisition device 5 to acquire a series of image data from which parameters describing said movement can be derived over a cycle of the movement, for example a motion model. If a further image acquisition device integrated into the irradiation device 4 or the patient positioning device 5 is then used during the irradiation, the parameters describing the movement can be used to adjust the irradiation. Of course, a respiratory belt or the like can also be used. It should be emphasized at this point that the relative position of the irradiation device 4 and the image acquisition device 5 is always known, so that a registration is necessarily present and conclusions about the irradiation that is to be performed can be drawn from the image data. Embodiments are conceivable in which the overall period of irradiation is also interrupted in order to check the position of the irradiation target with the image acquisition device 5 in the image acquisition position and if necessary to adjust irradiation parameters of the irradiation device 4 . In this and the following exemplary embodiments of the present invention the image acquisition device 5 is a magnetic resonance device which provides excellent soft tissue contrast and with its three-dimensional data outstandingly supplements an X-ray device integrated for example into the irradiation device 4 . A first actual embodiment variant of the present invention is shown in FIG. 2 . Firstly to be seen are the ceiling 10 and the floor 11 of a room in which the radiotherapy treatment device 1 a is arranged. For the sake of simplicity like parts in this and the following figures are labeled with the same reference numerals. Arranged on the ceiling 10 is a guidance system 12 which is associated with the movement device 6 and in which the irradiation device 4 and the image acquisition device 5 , in this case, as mentioned, a magnetic resonance device, are guided by means of their retaining devices 13 , 14 . This happens here in the sense of an overhead suspension mounting. The movement device 6 additionally comprises drive means (not shown in detail) which can act via the rail or a mechanical coupling both on the irradiation device 4 and on the image acquisition device 5 , or else can be provided synchronized on the irradiation device 4 and the image acquisition device 5 . The retaining device 13 of the irradiation device 4 carries a gantry 15 , only part of which is indicated, via which a radiation head 16 having a linear accelerator 17 can be moved on a circular path around a patient, in this case through a full 360°, since a support structure 18 of the patient positioning device 2 is arranged at a distance and the gantry 15 can therefore fully encircle the patient positioning platform 3 . Additionally integrated into the irradiation device 4 , in this case actually the gantry, is an X-ray device, of which only the detector 19 is indicated here for the sake of simplicity. As can be seen, the radiotherapy treatment device 1 a in FIG. 2 is actually located currently in a treatment position, since the gantry 15 encloses the patient positioning platform 3 . The image acquisition device 5 , which is arranged relatively remotely in the view shown in FIG. 2 , comprises the main magnet arrangement 20 with the patient receiving means 21 , with no movement restrictions whatsoever existing in this case since the support structure 18 is arranged on the side of the irradiation device 4 . In order to maneuver the image acquisition device 5 into the image acquisition position, the irradiation device 4 and the image acquisition device 5 are moved along the guidance system 12 , in this case incidentally a rail guidance system, as indicated by the arrows 22 . The interaction between the irradiation device 4 and the image acquisition device 5 is minimized on the one hand by the two devices 4 , 5 being arranged spaced apart from each other; on the other hand, however, shielding devices (not shown here for the sake of simplicity), in particular metal surfaces, can also be provided. Local coils 23 , as indicated in FIG. 2 , are attached to the main magnet arrangement 20 and are therefore moved together with the image acquisition device 5 . Various measures are provided in order not to expose a patient placed on the patient positioning platform 3 to risk due to the movement. On the one hand, a collision avoidance system 24 is provided which is also integrated in the control device 8 , cf. FIG. 1 , and which evaluates data from at least one sensor 25 , in this case by way of example a camera 26 (cf. FIG. 2 again), with regard to imminent collisions and immediately stops a movement upon detecting a potential or actually occurring collision. In this situation the collision does not necessarily have to be a collision with the patient alone, but other types of collisions can also be avoided. On the other hand, protection means 27 are provided on the patient positioning device 2 itself, in this case in the form of a cushion-like protective body 28 running around the edge of the patient positioning platform 3 . By this means the patient is also protected to a greater extent against possible collisions. It should be pointed out that in another exemplary embodiment the patient positioning platform 3 also can be embodied in the manner of a tray in order to ensure better protection of the patient. In order to improve the data acquisition possibilities further, an ultrasound device 29 (merely indicated here) is also integrated into the patient positioning device 2 for imaging purposes, which device 29 can provide image data for validating magnetic resonance image data of the image acquisition device 5 and/or else data relating to a periodic motion in the patient. Toward that end the ultrasound device 29 is embodied in a known manner to be both magnetic-resonance- and irradiation-compatible. FIG. 3 shows a second, alternative embodiment variant of a radiotherapy treatment device 1 b . In contrast to that shown in FIG. 2 , the rail guidance system 12 is in this case embodied on the floor side, so the treatment device 4 and the image acquisition device 5 are accordingly positioned on the floor side. Since it would now be possible on the one hand to implement the retaining device 13 in a longer design and to arrange it on the side of the support structure 18 of the patient positioning means 2 facing away from the patient positioning platform 3 , in which case the gantry 15 would then possibly no longer permit a 360° revolution of the radiation head 16 , it is nonetheless provided in this exemplary embodiment that a support arm 30 of the, in this case elongated, support structure 18 projects through a corresponding opening 31 of the retaining device 13 such that full mobility of the radiation device 4 and a gantry 15 encompassing the full angular range also continue to be possible without problem. Obviously, embodiments are also conceivable in which the support arm 30 is guided around the retaining device 13 at least on one side and the like. A further modification compared to FIG. 2 is that in this case the protection means 27 are integrated into a patient immobilizing device 32 . The patient immobilizing device 32 is a vacuumizable grain cushion into which the patient is bedded on the patient positioning platform 3 . After the vacuumization the latter becomes rigid and the patient remains embedded motionless and also protected from collisions toward the outside in the patient immobilizing device 32 . It should furthermore be remarked that for illustration purposes the radiotherapy treatment device 1 b of FIG. 3 is shown in the image acquisition position. It should furthermore be noted at this juncture that in order to register the movement range between the positions, i.e. the treatment position and the image acquisition position, further, it is by all means possible, even with radiation head 16 tilted at an angle, to perform an irradiation of an irradiation target which is still partially located in the patient receiving means 21 , though in that case no imaging by means of the image acquisition device 5 is then possible since the irradiation target is located outside of the homogeneity region (isocenter). Finally, the schematic diagram of FIG. 4 shows, still indicated, a third embodiment variant of an inventive radiotherapy treatment device 1 c . Here, the support structure 18 of the patient positioning device 2 is arranged centrally in this case, the patient positioning platform 3 being able to be displaced in its longitudinal direction, as indicated by the positions 33 , 34 , such that the irradiation position or the image acquisition position can also be assumed even in the presence of movement of the image acquisition device 5 and the irradiation device 4 . In this embodiment variant, therefore, the patient positioning platform 3 finally moves “toward” the devices 4 , 5 . However, since in this case the patient positioning platform 3 with the patient thereon is also moved, this is, as explained, less preferred. Although the invention has been illustrated and described in greater detail on the basis of the preferred exemplary embodiment, it is not limited by the disclosed examples and other variations can be derived herefrom by the person skilled in the art without leaving the scope of protection of the invention.
A radiotherapy treatment device comprising an image acquisition device, in particular a magnetic resonance device, an irradiation device comprising in particular a linear accelerator, and a patient positioning device having a patient positioning platform, wherein a movement device is provided for jointly moving the image acquisition device and the irradiation device between an irradiation position, in which a radiotherapeutic treatment of a patient located on the patient positioning platform is possible by means of the irradiation device, and an image acquisition position, in which an image acquisition of the patient located on the patient positioning platform is possible by means of the image acquisition device is provided. A radiotherapy method for treating an irradiation target in a patient by means of such a radiotherapy treatment device is also disclosed.
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[0001] This application relates to a three-dimensional (3D) preform with channels through the thickness of the preform that may be used in applications such as forming light weight preforms with an increased thickness. DESCRIPTION OF RELATED ART [0002] A leno weave is a weave in which two warp yarns are twisted around the weft yarns to provide a strong yet sheer/open fabric. The traditional leno, a single layer weave structure, is made by wrapping the warp yarns around each other between weft yarns. A variety of mechanical means are used, such as horizontally translating one warp to the other side of its neighbor with a mechanical actuator; using a propeller device that spins one direction for a long time, then spins the other direction, etc. A traditional leno weave acts to keep the two yarns locked very close to each other to either make an open fabric (like gauze), or to lock nearby yarn ends in place. [0003] The leno weave (also called Gauze Weave or Cross Weave) is a weave in which two warp yarns are twisted around the weft yarns to provide a strong yet sheer/open fabric. The standard warp yarn is paired with a skeleton or ‘doup’ yarn; these twisted warp yarns grip tightly to the weft yarn which improves the durability of the fabric. A leno weave produces an open fabric with almost no yarn slippage or misplacement of yarns. [0004] A leno weave fabric allows light and air to pass through freely so are used in any area where a sheer, open weave fabric is required that will not bruise or shove (where the yarns shift away from their woven uniformity disturbing the uniformity of the weave). If a simple in-and-out flat weave were woven very loosely to achieve the same effect, the yarns would have a tendency to this bruising/shoving/misplacement. [0005] Mock lenos, also known as imitation lenos, are a variety of weaves of ordinary construction which produce effects that are similar in appearance to the gauze or leno styles obtained without the aid of a doup mounting, These weaves are generally produced in combination with plain, twill, satin or other simple single layer weaves or even with brocade configuring, to produce striped fabrics, which bear a very close resemblance to true leno fabrics. This weave is also referred to as imitation gauze weave. [0006] The weave is a single layer weave arranging yarns in groups of equal or unequal sizes. Yarns working in a plain weave alternate with yarns floating on the face or back of the fabric. The yarn ends from each individual yarn group can be drawn into the same dent; this bunches the floating yarn ends together and causes a slight gap or opening between yarn groups in the fabric giving an appearance similar to a gauze or leno weave, hence the name “mock leno”. [0007] Mock leno woven fabrics may be generally defined as fabrics wherein groups of three or more warp or weft yarns are interlaced in such a way that the yarns of each group can come together easily in one group, while they are separated from the adjacent groups by reason of the last yarn of one group and the first yarn of the next group being interlaced in directly opposite order. Such an intersection prevents the two adjacent yarns from coming together and causes an opening at this point. These single layer woven fabrics may, be made from fibers or yarns of any well-known weavable materials such as glass or cotton, and are well known articles of commerce. [0008] FIG. 1A illustrates an example of a related art single-layer mock leno fabric structure 1000 wherein both the warp and the weft yarns are grouped in groups of three yarns each. As shown in FIG. 1A , the fabric comprises two kinds of mock leno patterns, i.e., 3×3 mock leno pattern I, and 3×3 mock leno pattern II. The 3×3 mock leno pattern I is formed by a group of three weft yarns a 1 -a 3 and a group of three warp yarns b 1 -b 3 , and the 3×3 mock lend pattern II is formed by a group of three weft yarns a 1 -a 3 and a group of three warp yarns b 4 -b 6 . The group of weft yarns a 1 -a 3 includes a first edge yarn a 1 , a central yarn a 2 , and a second edge yarn a 3 . The group of warp yarns b 1 -b 3 includes a first edge yarn b 1 , a central yarn b 2 , and a second edge yarn b 3 . Similarly, the group of warp yarns b 4 -b 6 includes a first edge yarn b 4 , a central yarn b 5 , and a second edge yarn b 6 . [0009] As shown in FIG. 1A , during the weaving of the 3×3 mock leno pattern I, both of the first edge warp yarn b 1 and the second edge warp yarn b 3 are woven under the first edge weft yarn a 1 , then over the central weft yarn a 2 , and finally under the second weft edge yarn a 3 . The central warp yarn b 2 is woven over all of the three weft yarns a 1 -a 3 . During the weaving of the 3X3 mock leno pattern II, both of the first edge warp yarn b 4 and the second edge warp yarn b 6 are woven over the first edge weft yarn a 1 , then under the central weft yarn a 2 , and finally over the second weft edge yarn a 3 . The central warp yarn b 5 is woven under all of the three weft yarns a 1 -a 3 . [0010] FIG. 1B illustrates the interlacing of the yarns of another example of a single-layer mock leno weave fabric structure wherein both the warp and the weft yarns are also grouped in groups of three yarns each. As shown in FIG. 1B , there are sections where all of the weft yarns cross between two warp yarns as indicated by the circle. Within the groupings of three warp yarns, weft yarns do cross between a pair of warp yarns, but not all weft yarns cross at the same time. [0011] FIG. 1C illustrates another example of a single-layer mock leno weave fabric structure. This mock leno is another version of a plain weave in which occasional warp yarns, at regular intervals but usually several yarns apart, deviate from the alternate under-over interlacing and instead interlace every two or more yarns. This happens with similar frequency in the weft direction, and the overall effect is a fabric with increased thickness and a rougher surface. [0012] FIG. 2 illustrates another example of a single-layer mock leno weave fabric structure 2000 wherein both the warp and the weft yarns are grouped in groups of four yarns each. As shown in FIG. 2 , the fabric comprises two kinds of mock leno patterns, i.e., 4×4 mock lend pattern I, and 4×4 mock leno pattern II. The 4×4 mock leno pattern I is formed by a group of four weft yarns c 1 -c 4 and a group of four warp yarns d 1 -d 4 , and the 4×4 mock leno pattern II is disrupted by a group of four weft yarns c 1 -c 4 and a group of four warp yarns d 5 -d 8 . Similarly, a group of four weft yarns c 5 -c 6 and a group of four warp yarns d 1 -d 4 form the 4×4 mock leno pattern II, and a group of four weft yarns c 5 -c 8 and a group of four warp yarns d 5 -d 8 form the 4×4 mock leno pattern I. [0013] The group of weft yarns c 1 -c 4 includes a first edge yarn c 1 , two central yarns c 2 and c 3 , and a second edge yarn c 4 . Similarly, the group of weft yarns c 5 -c 8 includes a first edge yarn c 5 , two central yarns c 6 and c 7 , and a second edge yarn c 8 . The group of warp yarns d 1 -d 4 includes a first edge yarn d 1 , two central yarns d 2 and d 3 , and a second edge yarn d 4 , Similarly, the group of warp yarns d 5 -d 8 includes a first edge yarn d 5 , two central yarns d 6 and d 7 , and a second edge yarn d 8 . [0014] FIGS. 3A-3H illustrate sections along the warp yarns d 1 -d 8 , respectively, in the single-layer mock leno weave fabric structure 2000 shown in FIG. 2 . As shown in FIGS. 3A-3D , during the weaving of the 4×4 mock leno pattern I, both of the first edge warp yarn d 1 and the second edge warp yarn d 4 are woven under the first edge weft yarn c 1 , then over all the central weft yarns c 2 and c 3 , and finally under the second weft edge yarn c 4 , The two central warp yarns d 2 and d 3 are woven over all of the four weft yarns c 1 -c 4 . During the weaving of the 4×4 mock leno pattern II on the right side of the 4×4 mock leno pattern I, both of the first edge warp yarn d 1 and the second edge warp yarn d 4 are woven over the first edge weft yarn c 5 , then under the central weft yarns c 6 and c 7 , and finally over the second weft edge yarn c 8 . The two central warp yarns d 2 and d 3 are woven under all of the four weft yarns c 5 -c 8 . [0015] As shown in FIGS. 3E-3H , during the weaving of the 4×4 mock leno pattern II, both of the first edge warp yarn d 5 and the second edge warp yarn d 8 are woven over the first edge weft yarn c 1 , then under all the central weft yarns c 2 and c 3 , and finally over the second weft edge yarn c 4 , The two central warp yarns d 6 and d 7 are woven under all of the four weft yarns c 1 -c 4 . During the weaving of the 4×4 mock leno pattern I on the right side of the 4×4 mock leno pattern II, both of the first edge warp yarn d 5 and the second edge warp yarn d 8 are woven under the first edge weft yarn c 5 , then over the central weft yarns c 6 and c 7 , and finally under the second weft edge yarn c 8 , The two central warp yarns d 6 and d 7 are woven over all of the four weft yarns c 5 -c 8 . SUMMARY OF THE DISCLOSURE [0016] A three dimensional (3D) woven preform with large channels in the warp and weft directions can be used itself or as part of a composite structure requiring light weight at an increased thickness versus other 3D or laminated preform structures. For 3D woven preforms that will be densified by Chemical Vapor Infiltration (CVI), larger channels within a preform can also provide multiple, large pathways for the chemical vapor to pass through the preform. In addition, the 3D weave that creates the channels can also create a preform with high thickness and a low fiber volume that might or might not be densified. Such an architecture might be useful in the preform state as a lightweight thermal or electrical insulator between two surfaces. The present invention discloses a 3D woven preform with channels. In the 3D woven version, warp yarns cluster together and weft yarns cluster together in groups. This creates channels in the through-thickness direction. These channels are created by locking the warp and weft yarns into place through a unique series of 3D weave patterns using a concept similar to the single layer mock leno weave. This differs from the traditional single layer leno pattern that is achieved through the use of a mechanical device that twists a warp yarn around another warp yarn as they cross a weft yarn to look them all into place. The traditional style leno mechanical devices are typically used in single layer preform weaves for composites for selvedges of the single layer woven preforms, where a tight weave is required to prevent-yarns from sliding out of place. [0017] In one aspect of the disclosure, a three-dimensional (3D) woven preform can include a plurality of groups of warp yarns and a plurality of groups of weft yarns, the warp yarns woven with the weft yarns to form a mock leno structure having a plurality of layers of the 3D woven preform. A first group of warp yarns in a particular layer can include a first set of at least one warp central yarn that binds weft yarns in the particular layer to weft yarns in a subsequent layer and at least two first warp edge yarns, one on each side of the first set of the at least one warp central yarn. A second group of warp yarns in the particular layer can include a second set of at least one warp central yarn that binds weft yarns in the particular layer to weft yarns in a preceding layer and at least two second warp edge yarns, one on each side of the second set of the at least one warp central yarn, such that through thickness channels are formed in the multilayer preform. [0018] This 3D woven preform of can include in a first group of weft yarns in the particular layer can include a first set of at least one weft central yarn that binds warp yarns in the particular layer to warp yarns in the subsequent layer and at least two first weft edge yarns, one on each side of the first set of the at least one weft central yarn. Also included can be a second group of weft yarns in the particular layer that can include a second set of at least one weft central yarn that binds warp yarns in the particular layer to warp yarns in the preceding layer and at least two second weft edge yarns, one on each side of the second set of the at least one weft central yarn. The first and second warp edge yarns can be woven over the first set of at least one weft central yarn and under the second set of at least one weft central yarn in the particular layer. The first and second weft edge yarns can be woven over the first set of at least one warp central yarn and under the second set of at least one warp central yarn in the particular layer. [0019] Another aspect of the disclosure is a three-dimensional (3D) woven preform including a plurality of groups of warp yarns and a plurality of groups of weft yarns, the warp yarns woven with the weft yarns to form a mock leno structure having a plurality of layers of the 3D woven preform. A first group of weft yarns in a particular layer can include a first set of at least one weft central yarn that binds warp yarns in the particular layer to warp yarns in a subsequent layer and at least two first weft edge yarns, one on each side of the first set of the at least one weft central yarn. A second group of weft yarns in the particular layer can include a second set of at least one weft central yarn that binds warp yarns in the particular layer to warp yarns in a preceding layer and at least two second weft edge yarns, one on each side of the second set of the at least one weft central yarn, such that through thickness channels are formed in the multilayer preform. [0020] In this second aspect of the 3D woven preform, a first group of warp yarns in the particular layer can include a first set of at least one warp central yarn that binds weft yarns in the particular layer to weft yarns in the subsequent layer and at least two first warp edge yarns, one on each side of the first set of the at least one warp central yarn. A second group of warp yarns in the particular layer can include a second set of at least one warp central yarn that binds weft yarns in the particular layer to weft yarns in the preceding layer and at least two second warp edge yarns, one on each side of the second set of the at least one warp central yarn. The first and second weft edge yarns can be woven over the first set of at least one warp central yarn and under the second set of at least one warp central yarn in the particular layer. The first and second warp edge yarns can be woven over the first set of at least one weft central yarn and under the second set of at least one weft central yarn in the particular layer. [0021] It is noted that in this disclosure and particularly in the claims and/or paragraphs, terms such as “comprises”, “comprised”, “comprising” and the like can have the meaning attributed to it in U.S. Patent law; e.g., they can mean “includes”, “included”, “including”, and the like. [0022] The terms “threads”, “fibers”, “tows” and “yarns” are used interchangeably in the following description. “Threads”, “fibers”, “tows” and “yarns” as used herein can refer to monofilaments, multifilament yarns, twisted yarns, multifilament tows, textured yarns, braided tows, coated yarns, bicomponent yarns, as well as yarns made from stretch broken fibers of any materials known to those skilled in the art. [0023] The above and other objects, features, and advantages of various embodiments as set forth in the present disclosure will be more apparent from the following detailed description of embodiments taken in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS [0024] FIG. 1A illustrates an example of a related art single-layer mock leno weave fabric structure wherein both the warp and the weft yarns are grouped in threes. [0025] FIG. 1B illustrates another example of a related art single-layer mock leno weave fabric structure wherein both the warp and the weft yarns are grouped in threes. [0026] FIG. 1C illustrates another example of a related art single-layer mock lend weave fabric structure. [0027] FIG. 2 illustrates another example of a related art single-layer mock leno weave fabric structure wherein both the warp and the weft yarns are grouped in fours. [0028] FIGS. 3A-3H illustrate sections along the warp yarns in the single-layer mock leno weave fabric structure shown in FIG. 2 . [0029] FIG. 4A illustrates a top view of an example of a 3D woven preform with channels of the present disclosure. [0030] FIG. 4B illustrates an oblique view of the 3D woven preform with channels. [0031] FIGS. 5A-5H illustrate sections along the warp yarns in the 3D woven preform of the present disclosure. [0032] FIG. 6 illustrates the plans used to generate the top of a 3D woven preform with channels [0000] of the present disclosure. [0033] FIG. 7 illustrates other examples of 3D woven preforms of the present disclosure. DETAILED DESCRIPTION [0034] FIG. 4A illustrates a top view of an example of 3D woven preform with channels of the present disclosure. FIG. 4B illustrates an oblique view of the 3D woven preform with channels. As shown in FIGS. 4A-4B , the 3D woven preform with channels of the present disclosure includes a multi-layer mock leno weave fabric structure wherein both the warp and the weft-yarns are grouped in fours. [0035] The 3D woven preform may comprise two kinds of 3D mock leno weave patterns, i.e., 3D mock leno weave pattern I, and 3D mock leno weave pattern II. FIGS. 5A-5D show an example of 3D mock leno weave pattern I, and FIGS. 5E-5H show an example of 3D mock leno weave pattern II. Both of the 3D mock leno weave patterns I and II are formed by a group of four warp yarns and a group of four weft yarns in a plurality of layers. Each group of four warp yarns includes a first edge warp yarn, two central warp yarns, and a second edge warp-yarn, the edge yarns on opposite sides of the central yarns. Similarly, each group of four weft yarns includes a first edge weft yarn, two central weft yarns, and a second edge weft yarn, the edge yarns on opposites of the central yarns. [0036] A 4×4 (4 warp yarns in each group and 4 weft yarns in each group) mock leno weave pattern is illustrated and described, However, it should be appreciated that there do not necessarily have to be an equal number of yarns in the warp and weft yarn groups. Moreover, it is not necessary to have 4 yarns in a group as long as there is at least one central yarn and at least one edge yarn on either side of the central yarn in each warp and weft group. [0037] In the 4×4 3D mock leno weave patterns I shown in FIGS. 5A-5D , there are two central warp yarns in the warp yarn group in a particular layer, e.g. layer n, that alternate between being woven over all of the four yarns in the weft yarn group in the same layer n, and then woven under all of the four yarns in the weft yarn group in the next layer n+1, which is under this particular layer n in the through-thickness direction. [0038] In the 3D mock leno weave patterns II shown in FIGS. 5E-5H , there are two central warp yarns in the warp yarn group in a particular layer, e.g. layer n, that alternate between being woven under all of the four yarns in the warp yarn group in the same layer n, and then woven over all of the four yarns in the warp yarn group in the upper layer n−1, which is over this particular layer n in the through-thickness layers of the fabric. [0039] In more detail, FIGS. 5A-5H illustrate sections along two groups of warp yarns in the 3D woven preform which structure has, for example, 12 layers. As shown in FIGS. 5A-5H , the two groups of warp yarns include warp yarns 11 - 14 of a first warp group and warp yarns 15 - 18 of a second warp group in the first layer of the 3D preform. Also illustrated are warp yarns 21 - 24 and 25 - 28 of first and second warp groups of the second layer. This pattern continues to warp yarns 111 - 114 ; 115 - 118 of first and second warp groups of the eleventh layer, and warp yarns 121 - 124 and 125 - 128 of first and second warp groups of the twelfth layer. [0040] FIGS. 5A-5H also show two groups of 4 weft yarns each that includes weft yarns 54 , 69 , 78 , and 93 in a first weft yarn group and weft yarns 49 , 63 , 73 , and 87 in a second weft yarn group on the first layer of the 3D woven preform, and two groups of 4 weft yarns that includes weft yarns 56 , 67 , 80 , and 91 in a first weft yarn group and weft yarns 52 , 71 , 76 , and 95 in a second weft yarn group on the second layer. The weft groupings continue in a similar manner to two groups of weft yarns 58 , 65 , 82 , and 89 in a first weft yarn group 59 , 64 , 83 , and 88 in a second weft yarn group in the tenth layer, weft yarns 60 , 62 , 84 , and 86 in a first weft yarn group and weft yarns 51 , 61 , 75 , and 85 in a second weft yarn group in the eleventh layer. [0041] In the following discussion the term “subsequent layer” is used for convenience of discussion only. However, “subsequent layer” as used herein means “another layer” not necessarily a layer lower or deeper in the 3D preform than a particular layer. Indeed, a “subsequent layer” could be above or higher in the 3D preform than the particular layer, The term “preceding layer” is only used to describe a layer in a direction opposite to that of the “subsequent layer.” [0042] As shown in FIGS. 5A and 5D there are 4 yarns in a first group of warp yarns: warp yarns 11 , 14 , one on either side of central yarns 12 , 13 . During the weaving of the 3D mock leno weave pattern I, the first edge warp yarn 11 and the second edge warp yarn 14 are woven under the first edge weft yarn 54 of the first weft yarn group of the first layer, then over all the central weft yarns 69 and 78 , and finally under the second weft edge yarn 93 in the weft yarn group. Edge warp yarns 11 , 14 are then woven over the first edge weft yarn 49 of the first layer, then under all the central weft yarns 63 and 73 , and finally over the second weft edge yarn 87 . Edge warp yarns 11 , 14 alternate the over/under in this manner for subsequent columns of weft yarns. [0043] As shown in FIGS. 5B and 5C , the two central warp yarns 12 and 13 of the warp yarn group 11 - 14 in the first layer are woven over all of the four weft yarns 54 , 69 , 78 , and 93 of the first layer and under the four weft yarns 52 , 71 , 76 , and 95 of the second layer. Therefore, the first layer and the second layer are tied to each other. [0044] In a similar manner, the first edge warp yarn 21 and second edge warp yarn 24 of the warp yarn group 21 - 24 in the second layer are woven under the first edge weft yarn 56 of the first weft yarn group of the second layer, then over the central weft yarns 67 and 80 , and under the second weft edge yarn 91 . And the first edge warp yarn 21 and the second edge warp yarn 24 are woven over the first edge weft yarn 52 of the second weft yarn group of the second layer, then under the central weft yarns 71 and 76 , and finally over the second weft edge yarn 95 . [0045] The two central warp yarns 22 and 23 of the warp yarn group 2124 in the second layer are woven over all of the four weft yarns 56 , 67 , 80 , and 91 of the second layer and under all four weft yarns 53 , 70 , 77 , and 94 in the third layer. Therefore, the second layer and the third layer are tied to each other. [0046] As shown in FIGS. 5E and 5H there are 4 yarns in a second group of warp yarns: edge warp yarns 15 , 18 , one on either side of central yarns 16 , 17 . During the weaving of the 3D mock leno weave pattern II, the first edge warp yarn 15 and the second edge warp yarn 18 are woven over the first edge weft yarn 54 of the first weft yarn group of the first layer, then under all the central weft yarns 69 and 78 , and finally over the second weft edge yarn 93 in the weft yarn group. And edge warp yarns 15 , 18 are then woven under the first edge weft yarn 49 of the first layer, then over all the central weft yarns 63 and 73 , and finally under the second weft edge yarn 87 , Edge warp yarns 15 , 18 alternate the over/under in this manner for subsequent columns of weft yarns. [0047] As shown in FIGS. 5F and 5G , the two central warp yarns 16 and 17 of the warp yarn group 15 - 18 in the first layer are woven under all of the four weft yarns 54 , 69 , 78 , and 93 of the first layer and over the four weft yarns 50 , 72 , 74 , and 76 of the layer above the first layer. Therefore, the first layer and the layer above the first layer are tied to each other. [0048] In a similar manner, the first edge warp yarn 25 and second edge warp yarn 28 of the warp yarn group 25 - 28 in the second layer are woven over the first edge weft yarn 56 of the first weft yarn group of the second layer, then under the central weft yarns 67 and 80 , and over the second weft edge yarn 91 . And the first edge warp yarn 25 and the second edge warp yarn 28 are woven under the first edge weft yarn 52 of the second weft yarn group of the second layer, then over the central weft yarns 71 and 76 , and finally under the second weft edge yarn 95 . [0049] The two central warp yarns 26 and 27 of the warp yarn group 25 - 28 in the second layer are woven under all of the four weft yarns 56 , 67 , 80 , and 91 of the second layer and over all four weft yarns 49 , 63 , 73 , and 87 in the first layer. Therefore, the second layer and the first layer are tied to each other. [0050] Therefore, as shown in FIGS. 5A 5 H, warp yarn 11 and warp yarn 21 may come in contact with each other, but weft yarn 93 and weft yarn 49 are inhibited from contacting each other, In fact, all the weft yarns in the columns containing yarns 45 and 54 are inhibited from contacting each other. As a result channels are formed through the thickness of the fabric layers. [0051] In a similar manner, of the 4 weft yarns in groups of a particular layer, n, the two central weft yarns are woven with the warp yarns in the particular layer alternating between being woven under all of the four yarns in the warp yarn group in the same layer, n, and then woven over all of the four yarns in the warp yarn group in the upper layer n−1, which is over this particular layer n in the through-thickness direction. [0052] For example, as shown in FIGS. 5A-5H , in a first group of four weft yarns 54 , 69 , 78 , and 93 , edge weft yarns 54 , 93 are woven over first warp edge yarn 11 , under all central warp yarns 12 , 13 and then over second warp edge yarn 14 in the first warp group of the first layer, and then edge weft yarns 54 , 93 are woven under first warp edge yarn 15 , over all central warp yarns 16 , 17 and then under second warp edge yarn 18 in the second warp group of the first layer. [0053] As shown in FIGS. 5A-5H , in the first group of four weft yarns 54 , 69 , 78 , and 93 , central weft yarns 69 , 78 are woven under all the warp yarns 11 - 14 in the first warp yarn group, and then over all the warp yarns 15 - 18 in the second warp yarn group. [0054] In the second weft yarn group 49 , 63 , 73 , and 87 , weft edge yarns 49 , 87 are woven under warp edge yarn 11 , over all central warp yarns 12 , 13 and then under second warp edge yarn 14 , and then edge weft yarns 49 , 87 are woven over first warp edge yarn 15 , under central warp yarns 26 , 27 of the second warp yarn group in the second layer and then under second warp edge yarn 18 of the second warp group of the first layer. Subsequent, weft edge yarns in each group alternate in a similar manner. [0055] Central weft yarns 63 , 73 of the second weft yarn group 49 , 63 , 73 , and 87 are woven under the first edge warp yarn 15 of the second warp yarn group in the first layer, and then under the warp yarn 26 , 27 of the second warp group in the second layer, and then under the second edge warp yarn 18 of the second warp yarn group in the first layer. Therefore, the first layer and the second layer are tied to each other. [0056] Similarly, as shown in FIGS. 5A-5H , in a first group of four weft yarns 56 , 67 , 80 , and 91 of the second layer, edge weft yarns 56 , 91 are woven over first warp edge yarn 21 , under all central warp yarns 22 , 23 and then over second warp edge yarn 24 in the first warp group of the second layer, and then edge weft yarns 56 , 91 are woven under first warp edge yarn 25 , over all central warp yarns 26 , 27 and then under second warp edge yarn 28 in the second warp group of the second layer. [0057] As shown in FIGS. 5A-5H , in the first group of four weft yarns 56 , 67 , 80 , and 91 , central weft yarns 67 , 80 are woven under all the warp yarns 21 - 24 in the first warp yarn group, and then over all the warp yarns 25 - 28 in the second warp yarn group. [0058] In the second weft yarn group 52 , 71 , 76 , and 95 , weft edge yarns 52 , 95 are woven under warp edge yarn 21 , over all central warp yarns 22 , 23 and then under second warp edge yarn 24 , and then edge weft yarns 52 , 95 are woven over first warp edge yarn 25 , under central warp yarns 36 , 37 of the second warp yarn group in the third layer and then under second warp edge yarn 28 of the second warp group of the second layer. Subsequent, weft edge yarns in each group alternate in a similar manner. [0059] Central weft yarns 71 , 76 of the second weft yarn group 52 , 71 , 76 , and 95 are woven under the first edge warp yarn 25 of the second warp yarn group in the second layer, and then under the warp yarn 36 , 37 of the second warp group in the third layer, and then under the second edge warp yarn 28 of the second warp yarn group in the second layer. Therefore, the second layer and the third layer are tied to each other. [0060] FIG. 6 illustrates the plans used to generate the top of a 3D woven preform with channels. The pattern, as shown in FIG. 6 , works by allowing some columns of yarns (warp and weft) to repel each other ( 4 and 5 ; 8 and 1 ) while others enable compact nesting ( 1 and 4 ; 5 and 8 ). Plans 2 , 3 , 6 , & 7 are used to tie one layer to the next. [0061] The stiffness of the fiber yarns, combined with a specific over and under weave path, lead to a natural repulsion of some yarns and attraction of other yarns. This leads to the grouping of yarns in each direction that is beneficial for some applications. Stiffer yarns result in larger spacings between yarns, thus resulting in larger channels. [0062] Certain selections of warp yarn groupings in the reed can mute or accentuate the formed paths or channels. Similarly, certain patterns of take-up spacing can also mute or accentuate the formed paths or channels. The most accentuated results come from arranging the yarns as in Plans 1 - 4 in a dent, Plans 5 - 8 in a dent, and smaller take-ups between weft yarn columns 1 - 4 and again 5 - 8 . [0063] Therefore, in the 3D woven preform of the instant invention, an open weave is accomplished by using only the up and down yarn movement pattern available on the weaving system and without using additional mechanical actuators. [0064] FIG. 7 illustrates other examples of 3D woven preforms. A variety of thicknesses (layers) and spacings may be used for a warp/weft column. [0065] The 3D mock leno weave pattern has the following characteristics and features: make 3D woven preforms with higher thickness at a lower fiber weight at the same thickness as a conventional 3D pattern or laminated structure. For example, a 3D preform with a traditional fiber volume (FV) has a certain thickness and a certain weight, and a preform with open channels disclosed in the instant invention, which has the same thickness, has a weight less than that of the 3D preform with the traditional fiber volume; create through thickness channels for fluid to flow either during processing of the preform into a composite; or as a “cooling channel” when the preform or composite is used as part of another assembly requiring heat dissipation; vary the channel spacing by varying the number of warp yarns grouped together; vary the dimensions of the channels in the Z (through thickness) direction; have less “bruising”, shoving or yarn displacement; have at least 3 warp and weft yarns in a group; stiffer warp and/or weft yarns will increase the repulsive force between yarn groups thus creating larger channels in the x or y planes (z being through thickness plane); vary take-up between yarn groupings to vary the channel size in the warp direction; groupings occur in both x-y plane directions, which results in “rectangular, other polygonal shaped channels”; warp and/or weft yarns bind from one layer to the next layer below, or bind multiple layers with one yarn. [0075] After the desired 3D woven preform structure has been formed, the structure may be impregnated in a matrix material to form a composite. The structure becomes encased in the matrix material and matrix material fills some or all of the interstitial areas between the constituent elements of the structure. The matrix material may be any of a wide variety of materials, such as epoxy, polyester, vinyl-ester, ceramic, carbon and/or other materials, which also exhibit desired physical, thermal, chemical, and/or other properties. The materials chosen for use as the matrix may or may not be the same as that of the structure and may or may not have comparable physical, chemical, thermal or other properties. Typically, however, they will not be of the same materials or have comparable physical, chemical, thermal or other properties, because a common objective sought in using composites is to achieve a combination of characteristics in the finished product that is not attainable through the use of one constituent material alone. So combined, the structure and the matrix material may then be cured and stabilized in the same operation by thermosetting or other known methods, and then subjected to other operations toward producing the desired component. After being so cured, the then solidified masses of the matrix material are adhered to the structure. As a result, stress on the finished component, particularly via its matrix material acting as an adhesive between fibers, may be effectively transferred to and borne by the constituent material of structure. Further, if Chemical Vapor Infiltration (CVI) is utilized to add the matrix material to form the composite, some or all of the channels formed in the substrate might remain open and free of the resin material. [0076] It should be appreciated that the yarns in the warp and weft directions may be of same or different materials and/or sizes. For example, the warp yarns and weft yarns can be made of carbon, nylon, rayon, fiberglass, cotton, ceramic, aramid, polyester, metal, polyethylene, and/or other materials that exhibit desired physical, thermal, chemical or other properties. [0077] It should be appreciated that other 3D mock leno weaves can be used to create the polygonal shaped channels, and that the number of layers of warp yarns is at least two or more. It should also be appreciated that in some embodiments, all the channels extend through the entire preform thickness. In other embodiments, a plurality of channels extend through the entire thickness. That is, in a desired pattern, not all of the channels necessarily extend through the entire thickness of the preform. [0078] It should also be appreciated that on one or both outer surfaces of the 3D woven preform, or one or both outer surfaces of the composite, other structures may be attached as a separate “skin” by methods such as stitch bonding, pinning, T-Forming (see U.S. Pat. No. 6,103,337), mechanically bolting, use of appropriate adhesives, or other methods known to those skilled in the art.
A three-dimensional (3D) woven preform with channels in the through thickness direction developed for applications such as forming light weight preforms with an increased thickness.
3
CROSS REFERENCES TO RELATED APPLICATIONS This application is an original application claiming priority to provisional application U.S. Ser. No. 61/379,929 filed Sep. 3, 2010, herein incorporated by reference to the extent it does not contradict the statements herein. FIELD OF THE INVENTION The present invention pertains to the field of alkyl carbonates of anti-aging ingredients, such as antioxidants and skin illuminating phenol ingredients. The present invention also pertains to processes for producing alkyl carbonates. BACKGROUND OF THE INVENTION A large number of anti-aging skin care ingredients are phenolic in nature. Many of these function as anti-oxidants or skin illuminating ingredients, and the free hydroxyl groups are key to the redox activity of these species. Unfortunately, many of these materials have physical properties that are not well-suited for use as cosmetic ingredients; they tend to have minimal solubility in most cosmetic solvents (both oils and water) and can be unstable in a cosmetic formulation (particularly towards oxidation). Derivatization of the phenolic groups can stabilize these materials. However, these derivatives must be readily removable under physiological conditions to liberate the phenolic groups to afford the desired anti-aging activity (Grasso et al, Bioorganic Chem. 2007, 35, 137-152). Derivatization of the phenolic groups can vastly improve the physical properties of these materials. One useful method for derivatization of hydroxyl or carboxyl-containing materials is to prepare esters of these materials. The usefulness of this approach often depends upon the ability of enzymes in the skin to hydrolyze these esters to liberate the parent active. This strategy is effective for the derivatization of many active ingredients containing aliphatic alcohols, but esters derived from phenols are often refractive or only slowly reactive towards enzymatic hydrolysis. Despite this, there has been interest in ester derivatives of phenolic active ingredients such as resveratrol (composition of matter patents: U.S. Pat. No. 6,572,882 and US Patent Appl 2009/0068132 A1; formulation patents: US Patent Appl 2009/0035236 A1, US Patent Appl 2009/0035237 A1, US Patent Appl 2009/0035240 A1, US Patent Appl 2009/0035242 A1, and US Patent Appl 2009/0035243 A1) and hydroxytyrosol (U.S. Pat. No. 7,098,246 and US Patent Appl 2003/0225160), even though the hydrolysis to release the parent phenolic active ingredient is questionable. Indeed, with hydroxytyrosol the aliphatic hydroxyl group is often the only functionality esterified (Grasso et al, Bioorganic Chem. 2007, 35, 137-152; Trujillo et al, J. Agric. Food Chem. 2006, 54, 3779-3785; Mateos et al, J. Agric. Food Chem. 2008, 56, 10960-10966; Gordon et al, J. Agric. Food Chem. 2001, 49, 2480-2485; Buisman et al, Biotechnology Lett. 1998, 20, 131-136; US Patent Appl 2005/015058 A1; Fr. Demande 2,919,800; ES 2,233,208; ES 2,246,603), leaving the phenolic groups underivatized, which will not improve the stability of the catechol functionality. Alkyl carbonate derivatives of these phenolic skin care active ingredients have not been described. Novel derivatives of phenolic actives that will hydrolyze under physiological (enzymatic) conditions would be of great utility and interest. SUMMARY OF THE INVENTION In one embodiment of the invention, an alkyl carbonate is provided having the general structure 1: wherein R is selected from substituted and unsubstituted, branched- and straight-chain, saturated, unsaturated, and polyunsaturated C 1 -C 22 alkyl. and R 1 , R 2 , R 3 , R 4 , and R 5 are independently selected from hydrogen, substituted and unsubstituted, branched- and straight-chain saturated, C 4 -C 22 alkyl, substituted and unsubstituted, branched- and straight-chain C 2 -C 22 alkenyl, substituted and unsubstituted, branched- and straight-chain C 2 -C 22 alkynyl, substituted and unsubstituted, branched- and straight-chain C 4 -C 22 dienyl, substituted and unsubstituted, branched- and straight-chain C 6 -C 22 trienyl, C 1 -C 6 -alkoxy, carboxyl, C 1 -C 15 aminocarbonyl, C 1 -C 15 amido, cyano, C 2 -C 15 -alkoxycarbonyl, C 2 -C 15 -alkoxycarbonyloxy, C 2 -C 15 -alkanoyloxy, hydroxy, aryl, heteroaryl, thiol, thioether, and halogen. In another embodiment of the invention, a process is provided for producing an alkyl carbonate having the general structure 1: wherein R is selected from substituted and unsubstituted, branched- and straight-chain, saturated, unsaturated, and polyunsaturated C 1 -C 22 alkyl. and R 1 , R 2 , R 3 , R 4 , and R 5 are independently selected from hydrogen, substituted and unsubstituted, branched- and straight-chain saturated, C 4 -C 22 alkyl, substituted and unsubstituted, branched- and straight-chain C 2 -C 22 alkenyl, substituted and unsubstituted, branched- and straight-chain C 2 -C 22 alkynyl, substituted and unsubstituted, branched- and straight-chain C 4 -C 22 dienyl, substituted and unsubstituted, branched- and straight-chain C 6 -C 22 trienyl, C 1 -C 6 -alkoxy, carboxyl, C 1 -C 15 aminocarbonyl, C 1 -C 15 amido, cyano, C 2 -C 15 -alkoxycarbonyl, C 2 -C 15 -alkoxycarbonyloxy, C 2 -C 15 -alkanoyloxy, hydroxy, aryl, heteroaryl, thiol, thioether, and halogen, comprising reacting at least one alcohol of Formula 4: with a chloroformate, bromoformate, or dicarbonate to produce said alkyl carbonate of Formula 1. DETAILED DESCRIPTION In this invention, novel alkyl carbonates of phenolic anti-aging skin care ingredients have been discovered of the general structure 1: wherein R is selected from substituted and unsubstituted, branched- and straight-chain, saturated, unsaturated, and polyunsaturated C 1 -C 22 alkyl; and R 1 , R 2 , R 3 , R 4 , and R 5 are independently selected from hydrogen; substituted and unsubstituted, branched- and straight-chain saturated, C 4 -C 22 alkyl; substituted and unsubstituted, branched- and straight-chain C 2 -C 22 alkenyl; substituted and unsubstituted, branched- and straight-chain C 2 -C 22 alkynyl; substituted and unsubstituted, branched- and straight-chain C 4 -C 22 dienyl; substituted and unsubstituted, branched- and straight-chain C 6 -C 22 trienyl; C 1 -C 6 -alkoxy; carboxyl; C 1 -C 15 aminocarbonyl; C 1 -C 15 amido; cyano; C 2 -C 15 -alkoxycarbonyl; C 2 -C 15 -alkoxycarbonyloxy; C 2 -C 15 -alkanoyloxy; hydroxyl; aryl; heteroaryl; thiol; thioether; and halogen. The terms “C 1 -C 6 -alkoxy”, “C 2 -C 15 -alkoxycarbonyl”, “C 2 -C 15 -alkoxycarbonyloxy”, and “C 2 -C 6 -alkanoyloxy” are used to denote radicals corresponding to the structures —OR 6 , —CO 2 R 7 , —OCO 2 R 7 , and —OCOR 7 , respectively, wherein R 6 is C 1 -C 6 straight or branched, substituted or unsubstituted alkyl and R 7 is C 1 -C 14 straight or branched, substituted or unsubstituted alkyl. The terms “C 1 -C 15 -aminocarbonyl” and “C 1 -C 15 amido” are used to denote radicals corresponding to the structures —NHCOR 8 , —CONHR 8 , respectively, wherein R 8 is C 1 -C 15 straight or branched, substituted or unsubstituted alkyl. Any two or more of the adjoining R 1 , R 2 , R 3 , R 4 , and R 5 can be connected to form one or more fused rings. The saturated, unsaturated, and polyunsaturated groups, which may be represented by R, may be straight- or branched-chain aliphatic hydrocarbon radicals containing up to about 22 carbon atoms and may be substituted, for example, with one to three groups selected from C 1 -C 6 -alkoxy, carboxyl, C 1 -C 15 aminocarbonyl, C 1 -C 15 amido, cyano, C 2 -C 15 -alkoxycarbonyl, C 2 -C 15 -alkoxycarbonyloxy, C 2 -C 15 -alkoxycarbonyloxyaryl, C 2 -C 15 -alkanoyloxy, hydroxy, aryl, substituted aryl, heteroaryl, substituted heteroaryl, thiol, thioether, and halogen. The terms “C 1 -C 6 -alkoxy”, “C 2 -C 15 -alkoxycarbonyl”, “C 2 -C 15 -alkoxycarbonyloxy”, and “C 2 -C 6 -alkanoyloxy” are used to denote radicals corresponding to the structures —OR 6 , —CO 2 R 7 , —OCO 2 R 7 , and —OCOR 7 respectively, wherein R 6 is C 1 -C 6 straight or branched, substituted or unsubstituted alkyl and R 7 is C 1 -C 14 straight or branched, substituted or unsubstituted alkyl. The terms “C 1 -C 15 -aminocarbonyl” and “C 1 -C 15 amido” are used to denote radicals corresponding to the structures —NHCOR 8 , —CONHR 8 , respectively, wherein R 8 is C 1 -C 15 straight or branched, substituted or unsubstituted alkyl. The term “C 2 -C 15 -alkoxycarbonyloxyaryl” is used to denote radicals corresponding to the structures —Ar—OCOOR 9 , wherein R 9 is a C 1 -C 14 alkyl or substituted C 1 -C 14 alkyl. The alkyl, alkenyl, alkynyl, dienyl, and trienyl groups, which may be represented by R 1 , R 2 , R 3 , R 4 , and R 5 , may be straight- or branched-chain aliphatic hydrocarbon radicals containing up to about 22 carbon atoms and may be substituted, for example, with one to three groups selected from C 1 -C 6 -alkoxy, carboxyl, C 1 -C 15 aminocarbonyl, C 1 -C 15 amido, cyano, C 2 -C 15 -alkoxycarbonyl, C 2 -C 15 -alkoxycarbonyloxy, C 2 -C 15 -alkoxycarbonyloxyaryl, C 2 -C 15 -alkanoyloxy, hydroxy, aryl, substituted aryl, heteroaryl, substituted heteroaryl, thiol, thioether, and halogen. The terms “C 1 -C 6 -alkoxy”, “C 2 -C 15 -alkoxycarbonyl”, “C 2 -C 15 -alkoxycarbonyloxy”, and “C 2 -C 6 -alkanoyloxy” are used to denote radicals corresponding to the structures —OR 6 , —CO 2 R 7 , —OCO 2 R 7 , and —OCOR 7 , respectively, wherein R 6 is C 1 -C 6 straight or branched, substituted or unsubstituted alkyl and R 7 is C 1 -C 14 straight or branched, substituted or unsubstituted alkyl. The terms “C 1 -C 15 -aminocarbonyl” and “C 1 -C 15 amido” are used to denote radicals corresponding to the structures —NHCOR 8 , —CONHR 8 , respectively, wherein R 8 is C 1 -C 15 straight or branched, substituted or unsubstituted alkyl. The term “C 2 -C 15 -alkoxycarbonyloxyaryl” is used to denote radicals corresponding to the structures —Ar—OCOOR 9 , wherein R 9 is a C 1 -C 14 alkyl or substituted C 1 -C 14 alkyl. The aryl groups which may be present as substituents on R, R 1 , R 2 , R 3 , R 4 , and R 5 may include phenyl, naphthyl, or anthracenyl and phenyl, naphthyl, or anthracenyl substituted with one to three substituents selected from C 1 -C 6 -alkyl, substituted C 1 -C 6 -alkyl, C 6 -C 10 aryl, substituted C 6 -C 10 aryl, C 1 -C 6 -alkoxy, halogen, carboxy, cyano, C 1 -C 15 -alkanoyloxy, C 1 -C 6 -alkylthio, C 1 -C 6 -alkylsulfonyl, trifluoromethyl, hydroxy, C 2 -C 15 -alkoxycarbonyl, C 2 -C 15 -alkoxycarbonyloxy, C 2 -C 15 -alkanoylamino and —O—R 10 , —S—R 10 , —SO 2 —R 10 , —NHSO 2 R 10 and —NHCO 2 R 10 , wherein R 10 is phenyl, naphthyl, or phenyl or naphthyl substituted with one to three groups selected from C 1 -C 6 -alkyl, C 6 -C 10 aryl, C 1 -C 6 -alkoxy and halogen. The heteroaryl radicals which may be present as substituents on R, R 1 , R 2 , R 3 , R 4 , and R 5 include a 5- or 6-membered aromatic ring containing one to three heteroatoms selected from oxygen, sulfur and nitrogen. Examples of such heteroaryl groups are thienyl, furyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, thiadiazolyl, oxadiazolyl, tetrazolyl, pyridyl, pyrimidyl, benzoxazolyl, benzothiazolyl, benzimidazolyl, indolyl and the like. The heteroaryl radicals may be substituted, for example, with up to three groups such as C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, substituted C 1 -C 6 -alkyl, halogen, C 1 -C 6 -alkylthio, aryl, arylthio, aryloxy, C 2 -C 15 -alkoxycarbonyl, C 2 -C 15 -alkoxycarbonyloxy, and C 2 -C 6 -alkanoylamino. The heteroaryl radicals also may be substituted with a fused ring system, e.g., a benzo or naphtho residue, which may be unsubstituted or substituted, for example, with up to three of the groups set forth in the preceding sentence. The term “halogen” is used to include fluorine, chlorine, bromine, and iodine. Examples of alkyl carbonates include, but are not limited to, structure 2 resveratrol tris(alkyl carbonate), structure 3, hydroxytyrosol tris(alkyl carbonate), structure 4, 4-hydroxybenzyl alcohol di(alkyl carbonate), and structure 5, an ester of 4-(alkoxycarbonyloxy)-2-phenylethanol. The novel process of our invention comprises the reaction of alcohol 6: with a chloroformate, bromoformate, or dicarbonate to produce the alkyl carbonate of Formula 1. The process is carried out without solvent or in an inert solvent chosen from cyclic or acyclic ether solvents, such as, diethyl ether, diisopropyl ether, tert-butyl methyl ether, or tetrahydrofuran; aromatic hydrocarbons, such as, benzene, toluene, or xylene; aliphatic or alicyclic saturated or unsaturated hydrocarbons, such as, hexane, heptane, cyclohexane, or limonene; halogenated hydrocarbons, such as, dichloromethane, dichloroethane, dibromoethane, tetrachloroethylene, or chlorobenzene; polar aprotic solvents, such as, acetonitrile, dimethyl formamide, or dimethyl sulfoxide; or mixtures thereof. In one embodiment of the invention, the no solvent is utilized. In another embodiment, dichloromethane, toluene, or mixtures thereof are utilized. The process may be carried out at a temperature between about −100° C. and about 100° C. In another embodiment, the process may be carried out at a temperature between about −100° C. and the boiling point of the solvent. Other temperature ranges are from about 0° C. and 60° C. and from about 0° C. to about 50° C. The amount of chloroformate, bromoformate or dicarbonate may be between about 0.85 and about 20 equivalents for each hydroxyl group on the compound of Formula 6. In another embodiment, the amount of chloroformate, bromoformate or dicarbonate may be between about 1 and about 10 equivalents or between about 1 and about 1.5 equivalents for each hydroxyl group being derivatized on the compound of Formula 6. The reaction can be run in the presence of an acid acceptor. Examples of acid acceptors include, but are not limited to, trialkylamines with between 3 and 15 carbon atoms or substituted or unsubstituted pyridines. The process may also be run in the presence of a catalyst. The catalyst may be a hypernucleophile such as N,N-dialkylaminopyridines or alkoxypyridines. The pressure for the reaction can range between about 1 torr to about 10 atm pressure. Another range is from about 200 torr to ambient pressure. Carbonates of the present invention show an unexpected propensity to undergo enzymatic hydrolysis. This is particularly surprising, as analogous phenolic esters either do not cleave or are hydrolyzed very slowly under these enzymatic conditions. For example, both the tris(butyl carbonate) and the tris(methyl carbonate) of resveratrol (2, where R is n-butyl or methyl, respectively) undergo hydrolysis of the carbonate to afford dicarbonates, monocarbonates, and the parent triphenol upon treatment with a lipase in a biphasic mixture of toluene and aqueous pH 7 buffer. In the absence of the enzyme there is no observed hydrolysis. In contrast, the tripalmitate ester of resveratrol showed minimal hydrolysis under the same conditions. The anti-aging properties of the parent ingredients are likely linked to their behavior as antioxidants due to the phenolic substructures, so any derivatives of the ingredients will need to be cleavable in the skin to be efficacious. The enzymatic results indicate that the carbonates should be much more effective than the corresponding esters. The parent phenols are insoluble in most organic solvents outside of methanol. The carbonates, in contrast, show a much broader solubility profile, which may help formulation and penetration into the skin. In addition, the parent phenols are somewhat unstable, and tend to turn brown upon storage. This is likely due to oxidative instability of the phenols, and the carbonate derivatization should improve upon this instability. The alkyl carbonate product of the process may be isolated using methods known to those of skill in the art, e.g., extraction, filtration, or crystallization. The alkyl carbonate product of Formula 1 may be purified if necessary using methods known to those of skill in the art, e.g., extraction, chromatography, distillation, or crystallization. The alkyl carbonates according to the present invention can be used in compositions, such as cosmetic compositions, skin care compositions and the like. The compositions can be useful, for example, for reducing skin roughness, fine lines, and wrinkles, improving photo-damaged skin, regenerating skin, reducing skin hyper-pigmentation, and reducing irritation and/or inflammatory reaction in skin. Typical cosmetic and/or skin care compositions of the invention contain at least 0.001% by weight of the carbonates according to the present invention. For example, the compositions can contain from about 0.001% to about 20.0% by weight or from about 0.01% to about 10.0% by weight of the carbonates according to the present invention. Lower concentrations may be employed for less pronounced conditions, and higher concentrations may be employed with more acute conditions. Suggested ranges also depend upon any adjunct ingredients employed in the compositions. The cosmetic and skin care compositions of the invention may also contain other skin conditioning ingredients in addition to carbonates. Such compositions may also contain other skin ingredients such as retinol, retinyl esters, tetronic acid, tetronic acid derivatives, hydroquinone, kojic acid, gallic acid, arbutin, α-hydroxy acids, and fatty acid esters of ascorbic acid. Such other ingredients are known to those of skill in the art. Typically, topical application to skin sites is accomplished in association with a carrier. Where employed, the carrier is inert in the sense of not bringing about a deactivation or oxidation of active or adjunct ingredient(s), and in the sense of not bringing about any adverse effect on the skin areas to which it is applied. For example, the compounds according to the present invention are applied in admixture with a dermatologically acceptable carrier or vehicle (e.g., as a lotion, cream, ointment, soap, stick, or the like) so as to facilitate topical application and, in some cases, provide additional beneficial effects as might be brought about, e.g., by moisturizing of the affected skin areas. Many preparations are known in the art, and include lotions containing oils and/or alcohols and emollients such as olive oil, hydrocarbon oils and waxes, silicone oils, other vegetable, animal or marine fats or oils, glyceride derivatives, fatty acids or fatty acid esters or alcohols or alcohol ethers, lecithin, lanolin and derivatives, polyhydric alcohols or esters, wax esters, sterols, phospholipids and the like, and generally also emulsifiers (nonionic, cationic or anionic). These same general ingredients can be formulated into a cream rather than a lotion, or into gels, or into solid sticks by utilization of different proportions of the ingredients and/or by inclusion of thickening agents such as gums or other forms of hydrophilic colloids. The novel processes provided by the present invention are further illustrated by the following examples. Example 1 Preparation of Resveratrol Tris(Methyl Carbonate) (Formula 2, R=Me) Resveratrol (15 g; 65.7 mmol) was combined with dichloromethane (80 mL), and pyridine (18.8 g; 236 mmol; 3.6 equiv) was added dropwise. Methyl chloroformate (26.2 g; 278 mmol; 4.2 equiv) were added, and the reaction mixture was heated to reflux for 1 h, at which point HPLC analysis indicated five major peaks. Pyridine (6.3 g; 79.6 mmol; 1.2 equiv) and methyl chloroformate (8.8 g; 93.1 mmol; 1.4 equiv) were added and refluxed for 1 h, and this was repeated twice more until a single peak was observed by HPLC analysis. The mixture was diluted with ethyl acetate (250 mL) and washed with 3 M HCl (3×250 mL) and 5% sodium bicarbonate (3×250 mL). The organic solution was dried with sodium sulfate and concentrated to afford 26.6 g of crude hydroxytyrosol tris(methyl carbonate) (Formula 2, R=Me). The crude product was crystallized from 160 g of isopropyl alcohol to afford 21.4 g of resveratrol tris(methyl carbonate) (81%) which was >99% pure by HPLC analysis. 1 H NMR (Hydrogen-1 Nuclear Magnetic Resonance) (DMSO-d 6 ) δ 7.66 (d, 2H, J=8.7 Hz); 7.46 (d, 2H, J=2.2 Hz); 7.40 (d, 1H, J=16.4 Hz); 7.27 (d, 2H, J=8.7 Hz); 7.25 (d, 1H, J=16.6 Hz); 7.16 (t, 1H; J=2.1 Hz); 3.86 (br s, 6H); 3.84 (br s, 3H). HPLC (High Performance Liquid Chromatography) (4.6×150 mm Zorbax SB-C8 column [Agilent], 3.5μ thickness, 50:50 methanol:water (containing 0.1% trifluoroacetic acid) for 5 min, gradient to 100% methanol over 1 min, hold at 100% methanol for 11 min, detection at 294 nm): t R 8.65 min (2, R=Me); t R 3.3 min (resveratrol). LCMS: 402 (M + of 2, R=Me) Example 2 Preparation of Resveratrol Tris(Butyl Carbonate) (2, R=n-Bu) Resveratrol (10.0 g; 43.8 mmol) was dissolved in 50 mL (618 mmol; 14.1 equiv) of pyridine. The mixture was diluted with toluene (75 mL) and treated with n-butyl chloroformate (19.15 g; 140 mmol; 3.2 equiv) dissolved in 25 mL of toluene. An exotherm was noted during the addition, and cooling was applied (maximum temperature was 37° C.). The resulting white stirrable slurry was stirred overnight at ambient temperature, at which point HPLC analysis indicated one major product but several minor peaks (assumed to be mono- and di-carbonates). An additional 20% of butyl chloroformate (3.8 g) was added and the mixture was stirred overnight, at which point HPLC analysis indicated >94% of a single peak. The mixture was partitioned between 150 mL of ethyl acetate and 100 mL of water, and the water layer was decanted. The organic layer was washed with 3 M HCl (200 mL) and 5% sodium bicarbonate (100 mL), dried (MgSO4), then concentrated in vacuo with moderate heating to afford 22.96 g (99%) of Formula 2, R=n-Bu. 1 H NMR was consistent with the anticipated structure and HPLC analysis indicated 97.1% purity with 0.7% resveratrol. 1 H NMR (CDCl 3 ) δ 7.49 (dt, 2H, J=8.7, 2.0 Hz); 7.22 (d, 2H, J=2.1 Hz); 7.19 (dt, 2H, J=8.7, 1.9 Hz); 7.08 (d, 1H, J=16.3 Hz); 7.01 (t, 1H, J=2.2 Hz); 6.97 (t, 1H; J=16.3 Hz); 4.275 (t, 4H, J=6.6 Hz); 4.265 (t, 2H, J=6.7 Hz); 1.8-1.65 (m, 6H); 1.53-1.37 (m, 6H); 0.98 (t, 9H, J=7.5 Hz). HPLC-MS (4.6×150 mm Zorbax SB-C8 column [Agilent], 3.5μ thickness, 50:50 methanol:water (containing 0.1% trifluoroacetic acid) for 5 min, gradient to 100% methanol over 1 min, hold at 100% methanol for 11 min, detection at 294 nm): t R 9.18 min (2, R=n-Bu, M + 528); t R 8.8 min (resveratrol bis[butyl carbonate], M + 428); t R 8.5 min (resveratrol mono[butyl carbonate], M + 328); t R 3.3 min (resveratrol, M + 228). Comparative Example 1 Preparation of Resveratrol Tripalmitate Resveratrol (100 mg; 0.44 mmol) was dissolved in 1 mL of pyridine. Palmitoyl chloride (425 μL; 1.40 mmol; 3.2 equiv) was added with immediate solid formation noted. This mixture was stirred at ambient temperature for 12 h at which point HPLC analysis indicated no resveratrol present. The mixture was partitioned into ethyl acetate and water and the water layer was decanted. The top organic layer was washed sequentially with 1.5 M HCl (10 mL) and 5% sodium bicarbonate (10 mL), dried (MgSO4), and concentrated to afford 0.45 g (99%) of resveratrol tripalmitate. 1 H NMR (CDCl 3 ) δ 7.49 (br d, 2H, J=8.6 Hz); 7.15-6.95 (m, 6H); 6.80 (t, 1H; J=2.0 Hz); 2.55 (t, 6H, J=7.3 Hz); 1.5-1.2 (m, 78H); 0.88 (t, 9H, J=6.5 Hz). HPLC (4.6×150 mm Zorbax SB-C8 column [Agilent], 3.5μ thickness, 50:50 methanol:water (containing 0.1% trifluoroacetic acid) for 5 min, gradient to 100% methanol over 1 min, hold at 100% methanol for 24 min, detection at 294 nm): t R 25.0 min (resveratrol tipalmitate); t R 3.3 min (resveratrol). Example 3 Enzymatic Hydrolysis of Resveratrol Tris(Methyl Carbonate) Resveratrol tris(methyl carbonate) (100 mg; 0.249 mmol) was dissolved in 2 mL of toluene. 2 mL of pH 7 buffer was added followed by 100 mg of Novozym 435 (immobilized Candida Antarctica lipase B). The mixture was stirred vigorously at ambient temperature for 22 h, at which point the HPLC analysis (equal volumes of both layers) indicated 23.75% resveratrol, 52.9% resveratrol mono(methyl carbonate), 15.8% resveratrol bis(methyl carbonate) and 7.0% resveratrol tris(methyl carbonate). After 3 days at ambient temperature HPLC analysis indicated 63.8% resveratrol, 35.1% resveratrol mono(methyl carbonate), 0.6% resveratrol bis(methyl carbonate), and no detectable resveratrol tris(butyl carbonate). A similar reaction run in the absence of enzyme showed no detectable hydrolysis after 3 days. Example 4 Enzymatic Hydrolysis of Resveratrol Tris(Butyl Carbonate) Resveratrol tris(butyl carbonate) (100 mg; 0.189 mmol) was dissolved in 2 mL of toluene. 2 mL of pH 7 buffer was added followed by 100 mg of Novozym 435 (immobilized Candida Antarctica lipase B). The mixture was stirred vigorously at ambient temperature for 1 days, at which point the top layer indicated 41% resveratrol bis(butyl carbonate) and 59% resveratrol tris(butyl carbonate). After 3 d at ambient temperature equal volumes of the top and bottom layers were analyzed by HPLC to indicate 35% resveratrol, 5% resveratrol mono(butyl carbonate), 41% resveratrol di(butyl carbonate), and 19% resveratrol tris(butyl carbonate). Comparative Example 2 Enzymatic Hydrolysis of Resveratrol Tripalmitate Resveratrol tripalmitate (100 mg; 0.11 mmol) was dissolved in 2 mL of toluene. 2 mL of pH 7 buffer was added followed by 100 mg of Novozym 435 (immobilized Candida Antarctica lipase B). The mixture was stirred vigorously at ambient temperature for 3 days to afford minimal hydrolysis with almost no resveratrol according to HPLC analysis: 89% resveratrol tripalmitate, 6.4% resveratrol dipalmitate, and 0.9% resveratrol. Example 5 Preparation of 4-Hydroxybenzyl Alcohol bis(butyl carbonate) 4-Hydroxybenzyl alcohol (1.0 g; 8.06 mmol) was dissolved in 2 mL (24.7 mmol; 3 equiv) of pyridine. Toluene (9 mL) was added to afford a cloudy solution which was cooled in ice-water. Butyl chloroformate (2.42 g; 17.72 mmol; 2.2 equiv) was added and solid formation was immediate. The mixture was stirred at 0° C. for 1 h, at which point HPLC analysis indicated no 4-hydroxybenzyl alcohol and one major peak. The mixture was diluted with ethyl acetate and sequentially washed with water, 1.5 M HCl (20 mL), and 5% sodium bicarbonate (20 mL). The organic solution was dried with magnesium sulfate and concentrated to afford 2.52 g (96%) of 4-hydroxybenzyl alcohol bis(butyl carbonate). 1 H NMR (CDCl 3 ) δ 7.41 (dt, 2H, J=8.7, 2.7 Hz); 7.19 (dt, 2H, J=8.7, 2.6 Hz); 5.14 (s, 2H); 4.26 (t, 2H, J=6.7 Hz); 4.15 (t, 2H; J=6.6 Hz); 1.8-1.6 (m, 4H); 1.52-1.32 (m, 4H); 0.97 (t, 3H, J=7.3 Hz); 0.93 (t, 3H, J=7.3 Hz). HPLC (4.6×150 mm Zorbax SB-C8 column [Agilent], 3.5μ thickness, 3:97 methanol:water (containing 0.1% trifluoroacetic acid) gradient to 40:60 methanol:water (containing 0.1% trifluoroacetic acid) over 20 min, gradient to 100% methanol over 5 min, hold at 100% methanol for 5 min, detection at 294 and 225 nm): t R 27.1 min (4-hydroxybenzyl alcohol bis[butyl carbonate]); t R 8.5 min (hydroxybenzyl alcohol) Example 6 Enzymatic Hydrolysis of 4-Hydroxybenzyl Alcohol bis(butyl carbonate) 4-Hydroxybenzyl alcohol bis(butyl carbonate) (100 mg; 0.308 mmol) was dissolved in 1 mL of toluene. 1 mL of pH 7 buffer was added followed by 100 mg of Novozym 435 (immobilized Candida Antarctica lipase B). The mixture was stirred vigorously at ambient temperature for 1.5 h, at which point HPLC analysis (equal volumes of both layers) indicated 1.5% 4-hydroxybenzyl alcohol, 40 and 14% of each of the 4-hydroxybenzyl alcohol mono(butyl carbonate)s, and 41% 4-hydroxybenzyl alcohol bis(butyl carbonate). Note that the analysis for 4-hydroxybenzyl alcohol is inaccurate due to its insolubility in both toluene and water. After 21 h at ambient temperature HPLC analysis indicated very little mono- and bis-carbonates. A similar reaction run in the absence of enzyme showed no detectable hydrolysis after 3 days. Example 7 Preparation of Hydroxytyrosol Tris(Methyl Carbonate) (3, R=Me) Hydroxytyrosol (1.0 g; 6.49 mmol) was dissolved in 2.3 mL (24.7 mmol; 4.4 equiv) of pyridine. Toluene (9 mL) was added to afford a cloudy solution which was cooled in ice-water. Methyl chloroformate (2.45 g; 25.9 mmol; 4 equiv) was added, and solid formation was immediate. The mixture was stirred at 0° C. for 45 min and allowed to warm to ambient temperature over 6 h, at which point HPLC analysis indicated no hydroxytyrosol and one major peak. The mixture was diluted with ethyl acetate and sequentially washed with water, 1.5 M HCl (20 mL), and 5% sodium bicarbonate (20 mL). The organic solution was dried with magnesium sulfate and concentrated to afford 1.64 g (77%) of 3, R=Me, which was pure by 1 H NMR analysis. 1 H NMR (CDCl 3 ) δ 7.24-7.11 (m, 3H); 4.34 (t, 2H, J=7.0 Hz); 3.905 (s, 3H); 3.90 (s, 3H); 3.77 (s, 3H); 2.96 (t, 2H, J=6.9 Hz). HPLC (4.6×150 mm Zorbax SB-C8 column [Agilent], 3.5μ thickness, 3:97 methanol:water (containing 0.1% trifluoroacetic acid) gradient to 40:60 methanol:water (containing 0.1% trifluoroacetic acid) over 20 min, gradient to 100% methanol over 5 min, hold at 100% methanol for 5 min, detection at 294 and 225 nm): t R .25.2 min (3, R=Me); t R 8.5 min (hydroxytyrosol). Comparative Example 3 Preparation of Hydroxytyrosol Trihexanoate Hydroxytyrosol (1.00 g; 6.49 mmol) was dissolved in 2.3 mL of pyridine (28.4 mmol; 4.4 equiv). The mixture was diluted with toluene (9 mL) and cooled in ice-water. Hexanoyl chloride (2.99 mL; 21.4 mmol; 3.3 equiv) was added with immediate solid formation noted. This mixture was allowed to warm to ambient temperature overnight at which point HPLC analysis indicated no hydroxytyrosol present and one major peak. The mixture was partitioned into ethyl acetate and water and the water layer was decanted. The top organic layer was washed sequentially with 1.5 M HCl (20 mL) and 5% sodium bicarbonate (20 mL), dried (MgSO4), and concentrated to afford 2.86 g (98%) of hydroxytyrosol trihexanoate which contained 1.9% residual hydroxytyosol. 1 H NMR (CDCl 3 ) δ 7.1-7.0 (m, 3H); 4.27 (t, 2H, J=7.0 Hz); 2.92 (t, 2H, J=6.9 Hz); 2.52 (t, 2H, J=7.4 Hz); 2.44 (t, 2H, J=7.4 Hz); 2.28 (t, 2H, J=7.3 Hz); 1.8-1.55 (m, 6H); 1.45-1.25 (m, 12H), 0.97-0.85 (m, 9H). HPLC (4.6×150 mm Zorbax SB-C8 column [Agilent], 3.5μ thickness, 3:97 methanol:water (containing 0.1% trifluoroacetic acid) gradient to 40:60 methanol:water (containing 0.1% trifluoroacetic acid) over 20 min, gradient to 100% methanol over 5 min, hold at 100% methanol for 5 min, detection at 294 and 225 nm): t R .27.8 min (hydroxytyrosol trihexanoate); t R 8.5 min (hydroxytyrosol). Example 8 Enzymatic Hydrolysis of Hydroxytyrosol Tris(Methyl Carbonate) Hydroxytyrosol tris(methyl carbonate) (3, R=Me, 100 mg; 0.305 mmol) was dissolved in 2 mL of toluene. 2 mL of pH 7 buffer was added followed by 100 mg of Novozym 435 (immobilized Candida Antarctica lipase B). The mixture was stirred vigorously at ambient temperature for 24 h, at which point HPLC analysis (equal volumes of both layers) indicated 74% hydroxytyrosol, 1.5% mono- and di-carbonates, and 17% 3 (R=Me). After 48 h at ambient temperature HPLC analysis indicated 92% hydroxytyrosol, 5% mono- and di-carbonates, and 3% 3 (R=Me). A similar reaction run in the absence of enzyme showed no detectable hydrolysis to hydroxytyrosol after 2 days. Comparative Example 4 Enzymatic Hydrolysis of Hydroxytyrosol Trihexanoate Hydroxytyrosol trihexanoate containing 1.9% hydroxytyrosol by HPLC analysis (100 mg; 0.22 mmol) was dissolved in 2 mL of toluene. 2 mL of pH 7 buffer was added followed by 100 mg of Novozym 435 (immobilized Candida Antarctica lipase B). The mixture was stirred vigorously at ambient temperature for 48 h to afford 72.3% hydroxytyrosol trihexanoate, 18.7% 3,4-di(hexanoyl)phenylethanol, and 2.5% hydroxytyrosol. Example 9 Preparation of 4-(n-Butoxycarbonyloxy)-2-phenethyl Linoleate Tyrosol linoleate (4-hydroxy2-phenethyl linoleate) (2.0 g; 4.99 mmol) was dissolved in 2 mL (24.7 mmol; 3 equiv) of pyridine. Toluene (9 mL) was added to afford a cloudy solution which was cooled in ice-water. Butyl chloroformate (2.42 g; 17.72 mmol; 2.2 equiv) was added, and solid formation was immediate. The mixture was allowed to warm to ambient temperature and stirred for 6 h, at which point HPLC analysis indicated <2% tyrosol linoleate and one major peak. The mixture was diluted with ethyl acetate and sequentially washed with water, 1.5 M HCl (20 mL), and 5% sodium bicarbonate (20 mL). The organic solution was dried with magnesium sulfate and concentrated to afford 2.75 g of 4-(n-butoxycarbonyloxy)-2-phenethyl linoleate. 1 H NMR (CDCl 3 ) δ 7.22 (d, 2H, J=8.5 Hz); 7.10 (d, 2H, J=8.5 Hz); 5.35 (m, 4H); 4.27 (t, 2H, J=6.9 Hz); 4.24 (t, 2H; J=6.7 Hz); 2.93 (t, 2H, J=7.0 Hz); 2.77 (t, 2H, J=5.8 Hz); 2.28 (t, 2H, J=7.4 Hz); 2.1-2.0 (m, 4H); 1.8-1.65 (m, 2H); 1.65-1.25 (m, 20H); 0.97 (t, 3H, J=7.3 Hz); 0.89 (t, 3H, J=6.9 Hz). HPLC (4.6×150 mm Zorbax SB-C8 column [Agilent], 3.5μ thickness, 10:90 methanol:water (containing 0.1% trifluoroacetic acid) for 20 min, detection at 225 nm): t R 10.8 min 4-(n-butoxycarbonyloxy)-2-phenethyl linoleate); t R 5.2 min (tyrosol linoleate).
Carbonates of anti-aging ingredients, in particular anti-oxidants and skin illuminating phenol ingredients, have been prepared as derivatives of these ingredients with enhanced physical properties. It has been demonstrated that these carbonates will hydrolyze under enzymatic catalysis to release the parent ingredient. In contrast, esters of the phenolic groups in many cases do not hydrolyze under the same conditions.
2
BACKGROUND OF THE INVENTION [0001] 1. Field of the Invention [0002] This invention relates to a receiving module, and more particularly, to a receiving module applied in a rangefinder. [0003] 2. Description of the Related Art [0004] [0004]FIG. 1 schematically shows a conventional optical rangefinder, disclosed in U.S. Pat. No. 6,441,887. The optical rangefinder 1 includes an emitter 2 , a telescopic system 3 and a receiving system 4 . Referring to FIG. 1, a beam from the emitter 2 passes through the telescopic system 3 , incident on the target. Next, a beam reflected by the target enters the receiving system 4 . [0005] [0005]FIG. 2A schematically shows the rangefinder of FIG. 1, measuring a target at 100 m, and FIG. 2B schematically shows the rangefinder of FIG. 1, measuring a target at 1 m. Referring to FIGS. 1 and 2A, the interval between the receiving system 4 and the telescopic system is about 7 cm, and the distance from target T to the optical rangefinder 1 is around 100 m. The receiving system 4 , target T, and telescopic system 3 form an included angle θ 1 . The included angle 31 is around 0.0007 radians. Referring to FIGS. 1 and 2B, the receiving system 4 , target T, and telescopic system 3 form another included angle θ 2 . The included angle θ 2 is around 0.07 radians. [0006] However, when the included angle increases from 0.0007 radians to 0.07 radians, the reflected beam Br 2 from the target T has difficulty entering the receiving system 4 . In general, by increasing the diameter of the receiving system, the reflected beam Br 2 enters the receiving system 4 easily. However, the reflected beam Br 2 cannot be received by the light sensor even though the reflected beam Br 2 enters the receiving system 4 . [0007] In addition, the U.S. Pat. No. 5,815,251 discloses another range finder using many ways to receive the reflecting beam. However, the complex mechanism is difficult to execute. SUMMARY OF THE INVENTION [0008] To solve the above problems, it is an object of the present invention to provide a receiving module applied in a rangefinder for measuring short range and long distances. [0009] According to the object of the invention, the receiving module includes an object lens, a light pipe and a light sensor. The object lens has an optical axis, and the light pipe has a receiving end, an emitting end and a reflecting surface, respectively connected the receiving and emitting ends. After a beam, not parallel to the optical axis, passes the object lens, the object lens alters the beam to approximately parallel to the optical axis. Next, the beam enters the light pipe via the receiving end and is reflected several times by the reflecting surface. The beam from the emitting end of the light pipe converges on one area, in which the light sensor is located. [0010] The receiving module of the invention is applied in an optical rangefinder, further comprising an emitter and another object lens. [0011] The light pipe comprises a plurality of mirrors, or can comprise a solid rod with a reflecting surface is coated with a reflecting film. When a beam enters the light pipe, the beam is reflected by the reflecting surface and leaves the light pipe from the emitting end. [0012] A detailed description is given in the following embodiments with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS [0013] The present invention can be more fully understood by reading the subsequent detailed description and examples with references made to the accompanying drawings, wherein: [0014] [0014]FIG. 1 schematically shows a conventional optical rangefinder as disclosed in U.S. Pat. No. 6,441,887; [0015] [0015]FIG. 2A schematically shows the optical rangefinder of FIG. 1, measuring a target at 100 m; [0016] [0016]FIG. 2B schematically shows the optical rangefinder of FIG. 1, measuring a target at 1 m; [0017] [0017]FIG. 3 schematically shows beams entering an object lens at different angles; [0018] [0018]FIG. 4 schematically shows a light pipe guiding beams to a convergence area; [0019] [0019]FIG. 5A schematically shows a receiving module of the invention; [0020] [0020]FIG. 5B schematically shows another receiving module of the invention; [0021] [0021]FIG. 5C schematically shows another receiving module of the invention; [0022] [0022]FIG. 6A schematically shows a rangefinder utilizing the receiving module of the invention; [0023] [0023]FIG. 6B schematically shows another rangefinder utilizing the receiving module of the invention; and [0024] [0024]FIGS. 7A to 7 C schematically show all different light pipe types. DETAILED DESCRIPTION OF THE INVENTION [0025] [0025]FIG. 3 schematically shows beams entering an object lens at different angles. As shown in FIG. 3, the distance between point A and the positive lens CV exceeds the distance between point B and the positive lens CV, with the incident angle of the beam 1 a from point A to the positive lens CV less than the incident angle of the beam 1 b from point B to the positive lens CV. According to Snell's law, the beam 1 a travels through the positive lens CV and reaches a point A′ of an optical axis OA of the positive lens CV, and the beam 1 b travels through the positive lens CV and reaches a point B′ of an optical axis OA of the positive lens CV. Thus, beams from different light source reach different points by passing the positive lens CV. The distance between points A′ and B′ is represented as L. [0026] [0026]FIG. 4 schematically shows a light pipe guiding beams to a convergence area. Referring to FIG. 4, the light pipe 10 has a length L, and a receiving end 11 , emitting end 12 , and enclosed reflecting surface 13 , connecting the receiving end 11 and the emitting end 12 . In the invention, the receiving end 11 of the light pipe 10 is located at point B′, and the emitting end 12 point A′. The optical axes of light pipe 10 and positive lens CV are coaxial. [0027] As shown in FIG. 4, the beam 1 a from point A passes the positive lens CV according to Snell's law, and the beam 1 a enters the light pipe 10 via the receiving end 11 . Next, the beam 1 a from point A intersects the optical axis OA at point A′. [0028] As shown in FIG. 4 the beam 1 b from point B passes the positive lens CV according to Snell's law, and intersects the optical axis OA at point B′. The point B′ is located on the receiving end 11 , such that beam 1 b from point B is reflected by the reflecting surface 13 and travels forward in light pipe 10 . Thus, according to the light tracing shown in FIG. 4, the beam 1 b from point B intersects the optical axis OA at point A′ again. Beams emitted from different positions pass the positive lens CV and travel forward in light pipe 10 , and then intersect the optical axis OA in substantially the same position. [0029] [0029]FIG. 5A schematically shows a receiving module of the invention. As shown in FIG. 5A, the receiving module 20 of the invention includes a positive lens 21 , a light pipe 10 and a detector 22 , wherein the positive lens 21 and the light pipe 10 have the same optical axis OA. When two different beams 1 a , 1 b travel through the positive lens 21 and the light pipe 10 , the beams 1 a , 1 b respectively intersect the optical axis OA at two neighboring points, forming an area A′. The detector 22 is located in area A′ to receive beams 1 a , 1 b from different light sources. Referring to FIG. 5A, the light pipe 10 confines the beams from different light sources to the area A′, smaller than the area of the detector for receiving the beams. FIG. 5B schematically shows another receiving module of the invention. As shown in FIG. 5B, the receiving module 20 ′ further includes an aspherical lens 23 located near the emitting end 13 of the light pipe 10 , to reduce area A′, ensuring that detector 22 receives the beams from all ranges. Referring to FIG. 5B, the aspherical lens 23 confines beams from different light source to the area, smaller than area A′ and the area of the detector for receiving the beams. FIG. 5C schematically shows another receiving module of the invention. As shown in FIG. 5C, the receiving module 20 ″ further includes a concave mirror 24 , by which the beams 1 a , 1 b passing the positive lens are reflected. The reflected beams 1 a , 1 b enter the light pipe 10 via the receiving end 11 and propagate forward by reflection in the light pipe 10 . Next, beams 1 a , 1 b from the emitting end 12 of the light pipe 10 are received by detector 22 . In this invention, the surface of the concave mirror is preferably aspherical, and beams from the light pipe 10 can be further confined to a smaller area, ensuring that detector 22 receives the beams from all ranges. [0030] [0030]FIG. 6A schematically shows a rangefinder utilizing the receiving module of the invention shown in FIG. 5B. As shown in FIG. 6A, the optical system of the rangefinder 100 includes an emitting module 30 and receiving module 20 ′. The emitting module 30 includes an emitting device 32 and a collimating lens 31 . After the emitting device 32 emits a beam of narrow-band 1 0 , the beam of narrow-band 1 0 is converted to form a collimated beam 1 1 by passing the collimating lens 31 . The collimated beam 1 1 is incident on a target (not shown), and reflected thereby to form a reflected collimated beam 1 2 . A portion of reflected beam 1 2 enters the receiving module 20 ′ via the positive lens 21 . No matter the distance to the target, the reflected beam 1 2 from the target is confined to one area by the light pipe 10 . Next, the area is reduced by an aspherical lens 23 , and the detector 22 receives the reflected beam 1 2 . FIG. 6B schematically shows another rangefinder utilizing the receiving module shown in FIG. 5C. As shown in FIG. 6B, the optical system of the rangefinder 100 ′ includes an emitting module 30 and the receiving module 20 ″. The emitting module 30 includes an emitting device 32 and the collimating lens 31 . The emitting device 32 emits a beam of narrow-band 1 0 , which is then converted to collimated beam 1 1 by passing the collimating lens 31 , and is incident on a target (not shown), and reflected thereby to form a reflected collimated beam 1 2 . A portion of reflected beam 1 2 enters the receiving module 20 ″ via the positive lens 21 . No matter the distance to the target, the reflected beam 1 2 from the target is confined to one area by the concave mirror 24 and the light pipe 10 . The area can be further reduced by an aspherical lens, with the detector 22 receiving the reflected beam 1 2 . [0031] [0031]FIGS. 7A to 7 C schematically show a variety of light pipes. As shown in FIG. 7A, the area of the receiving end 11 ′ of the light pipe 10 ′ is smaller then the area of the emitting end 12 ′. As shown in FIG. 7B, the area of the receiving end 11 of the light pipe 10 is equal to the area of the emitting end 12 ′. As shown in FIG. 7C, the area of the receiving end 11 ″ of the light pipe 10 ″ is larger then the area of the emitting end 12 ″. In the invention, the light pipe can be a solid rod with a reflecting surface coated with a reflecting film. In addition, the light pipe can be a hollow rod and comprises a plurality of mirrors. [0032] The receiving module of the invention receives beams of different incident angle, for confinement beams to an area not larger than the area of the detector. Thus, the detector receives the beams from different positions. [0033] No matter the distance to the target, the receiving module of the invention applied to the rangefinder receives reflected beams, assuring measurement of distance to the target. [0034] While the invention has been described by way of example and in terms of the preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments. To the contrary, it is intended to cover various modifications and similar arrangements (as would be apparent to those skilled in the art). Therefore, the scope of the appended claims should be accorded the broadest interpretation so as to encompass all such modifications and similar arrangements.
A receiving module applied in a rangefinder. The receiving module, receiving beams of different incident angles, includes a light pipe having a receiving end, an emitting end and a reflecting surface connecting the receiving end and the emitting end. The light pipe also has an optical axis perpendicular to the receiving and the emitting ends. When beams of different incident angles from different positions enter the light pipe, the light pipe confines the beams to a certain area. Using the receiving module of the invention, the rangefinder can measure targets from all ranges.
6
This is a continuation of application Ser. No. 277,173, filed Aug. 2, 1972, and now abandoned. BACKGROUND AND BRIEF DESCRIPTION OF THE INVENTION The use of apparatus to control vehicles along a prescribed path is an art recognized concept. Sometimes apparatus of this nature controls automobile movement to enable same to be worked on such as in automatic car washes. Other types of apparatus have a support surface for the automobile tires with guide rails along the peripheral edges of the supports to define the prescribed path. These path controllers are conventionally used with grease racks and trucker's ramps to facilitate the loading and unloading of automobiles from automobile transport trailers. While the above mentioned guides did tend to direct the vehicle, they could not maintain the vehicle within the desired path since the vehicle tires could obtain sufficient traction to climb over the guides and escape therefrom. Often a vehicle is damaged as a result of such a procedure. Further, the support surface of the ramp or tracks were immobile relative to the guides therefore virtually precluding that the ramp or track path could have a radius or curvature less than the turning radius of the vehicle being moved along the path. Accordingly such apparatus could not facilitate the accomplishment of a sharper turn by an automobile than could be conventionally accomplished by the automobile steering mechanisms. The present invention relates to a method and apparatus for controlling the path of a vehicle. The prescribed path is generally constructed of an entrance ramp and at least one section for each of the advancing wheels, the sections being comprised of a plurality of support rollers. Each of the support rollers will have its axis of rotation substantially parallel to the path and rotatably connected to framework thereby providing an elevated support for the rollers. The framework further serves as a means for mounting guide rollers on the peripheral side portions of the section(s) immediately adjacent the direction of the turn. Stated another way, if the vehicle is negotiating a left hand curve, the left hand section will be provided with the guide rollers on either side thereof. In any event, the guide rollers will be elevated above the support rollers and will likewise have their axis of rotation substantially parallel to the desired path. It is contemplated that a plurality of sections may be combined to define various curves and tortuous paths. In fact, each section may be considered to be a vehicle correlator as the first section meeting the advancing portion of the vehicle acting to essentially "capture" the vehicle and begins the turning process. As the trailing two wheels eventually move on the initial section, the guide rollers operate to preclude the advancing wheels from inadvertently leaving the desired path and the support rollers will then effect a lateral shifting of the trailing end of the vehicle so as to coordinate the turning of the vehicle and to direct same along the path behind the front wheels. One of the principal objects of the invention is to provide a unique method and apparatus for moving a vehicle along a prescribed path. It is a feature of the invention that the method and apparatus provide for the lateral shifting of at least the trailing end of the vehicle as it is moved along the path. Another object of the invention is to provide a uniquely constructed correlator and turn coordinator which enables vehicles to by-pass obstacles and to make optimum use of limited space. A further object of the invention is to provide a correlator and turn coordinator of the character described which utilizes rollers as a support surface for a vehicle riding thereon and providing its own motive force, said rollers operable to effect the lateral shifting and controlled vehicle turning within a prescribed arcuate path. A further object of the invention is to provide a uniquely constructed correlator and turn coordinator of the character described which includes the utilization of novel guide rollers. It is a feature of this object that the guide roller(s) operates to maintain the vehicle within the bounds of the prescribed path and can actually eliminate need to manually steer the vehicle once same is "captured" by the correlator section. Another object of the invention is to provide a vehicle correlator and turn coordinator that is comprised of a plurality of sections having various lengths therein. It is a feature of the object that the sections may be oriented in a number of ways to permit the vehicle riding thereon to negotiate a tortuous path, including 90° turns, in significantly less space than has been heretofore required. Accordingly, a salient feature of the invention is to maximize the utilization of expensive real estate ordinarily associated with car washes, drive-in banks, tractor-trailer loading zones, and any other areas where tight vehicle maneuverability is required on limited space. Another extremely important object of the invention is to provide a rugged, inexpensive, and easy to install vehicle correlator and turn coordinator. A very important feature of this object is that the manufacture and assembly of the portions comprising the correlator and turn coordinator are simplified in order to keep maintenance and repairs at a minimum. These and other objects of the invention, together with the features of novelty appurtenant thereto, will appear in the course of the following description. DETAILED DESCRIPTION OF THE INVENTION In the accompanying drawings, which form a part of the specification and are to be read in conjunction therewith and in which like reference numerals are employed to indicate like parts in the various views: FIG. 1 is a plan view of an arrangement of the present invention; FIG. 2 is an end elevational view taken generally along the line 2--2 of FIG. 1 in the direction of the arrows and with a portion of the framework broken away to more clearly illustrate the roller mounting technique; FIG. 3 is a side elevational view taken generally along the line 3--3 of FIG. 1 in the direction of the arrows; FIg. 4 is an enlarged partial plan view taken generally along the line 4--4 of FIG. 3 in the direction of the arrows; FIG. 5 is a top plan view of another arrangement utilizing the present invention as a means to control the path of the vehicle exiting from a car wash; and FIG. 6 is still another arrangement making use of the subject invention to facilitate the vehicle negotiation of a tortuous path. Referring now more particularly to FIGS. 1-4, the turn coordinator is generally depicted by the numeral 10. As shown in FIG. 1, this turn coordinator provides a path for a 90° left hand turn from the vehicle lubber line entering same. Actually, the turn coordinator will include a left portion 11 and a right portion 12 which are substantially parallel to each other and follow the prescribed path. It should be pointed out that while the turn coordinator is shown as being comprised of two separate portions (11 and 12), the entire width of the path could be constructed without the center median although guide rollers (described infra) would still be needed. As suggested above, the turn coordinator is constructed from a plurality of sections 13. These sections may be thought of as individual turn correlators in that a pair of sections (left and right) serve to capture an incoming vehicle. For example, a section of slightly different construction is shown in communicating relationship with the entrance ramps 14. In section 15, the roller lengths will be substantially equal and curvilinear motion will be imparted to the vehicle. However, it is contemplated that the rollers in correlator sections 13 will be constructed of predetermined but varying length so that a particular increment of the curve is provided by each pair of sections. As illustrated in FIG. 1, sections 13 are constructed of such a length and angulation that a 10° arc is negotiated each time the vehicle passes a particular section. As suggested, the sections 13 do not begin to approximate the curvilinear path until the vehicle has entered into the first capture sections indicated by the numeral 15. These capture sections will be adjacent the exiting portion of ramps 14 on both the left and right portions. The capture sections begin the original locating and correlating of the approaching vehicle so that the roller sections 13 may then substantially take over the steering and shifting of the vehicle as its advancing end portion is accepted and moved thereon. Also, since the left coordinator portion 11 is inside the radius or curvature of the illustrated prescribed path, the sections 13 of correlator portion 12 are larger than the corresponding section 13 of portion 11. Turning now more particularly to the construction of the correlator sections, it may be clearly seen in FIGS. 2, 3 and 4 that the rollers 23 which comprise a supporting portion of each correlator section, are supported on angle framework structurals generally designated by a numeral 20. Each angle which comprises the roller supporting framework will seat on ground level on its lower horizontal flange 20a with its vertical web 20b is spaced apart relationship with the next occurring angle structural 20. As shown in FIG. 2, the vertical web of each angle will be appropriately notched or slotted at 21 and will accommodate one end portion a corresponding roller shaft 22 of support roller 23. For convenience of assembly and to eliminate excessive spacing between the correlator sections, notches 21 in the adjacent angle supports 20 will be staggered so that the roller shafts in the succeeding section will substantially interleave (as seen from above) with the roller shafts of the preceding section (note FIG. 4). The construction of rollers 23 may be tubular steel rotatively mounted on the roller shafts 22 by nylon bushings or bearings located adjacent each roller end portion. These rollers, hereinafter identified by the numeral 23, may be easily laid in place between the vertical webs 20b of the corresponding angles of framework 20. A flat plate 24 may then be placed over the upper surfaces of the vertical adjacent webs 20b to preclude the roller shafts from bouncing out of the slots or notches 21. With this construction, a damaged roller may be easily replaced by simply removing the plate 24 at each end of the roller and lifting the roller out of its normally operative position within the framework. As suggested above, the turn coordinator portion with the inside radius or curvature (the left portion 11 shown in FIG. 1) will have guide rollers defining the boundary limits of the prescribed path. These guide rollers will be supported on each side of each section 13 of the coordinator portion 11 by the flat, vertically oriented, metal guide mount 25 that is bolted or otherwise connected between the adjacent vertical web portions 20b. As shown in FIGS. 2 and 3, the guide mounts extend substantially above the upper surface of the support rollers 23 and are provided at the upper portion thereof with a suitable apperture and/or slot to accept the roller shaft 26 of a guide roller 27. In a similar manner, the guide rollers 28 (FIG. 1) are supported above the upper surface of the support rollers in the capture section 15 and are flared outwardly therefrom to facilitate the driving of the advancing end portion of the vehicle tire therein. Guide roller 28 will be supported between the first guide mount 25 adjacent the entry to the first section 13 of the left hand portion 11. The flared end portions of the guide rollers 28 will have guide mounts 29 (of similar construction to mount 25) supported from the ground level however properly elevating guide roller 28 for utilization with the capture section 15. This guide mount (29) likewise is suitably appertured and slotted to accept the flared guide roller shaft. The above described description illustrates how a plurality of sections, having rollers of proper lengths, may be interrelated to define a curved path and how the rollers are supported above the ground level for free rotation so that both the guide rollers 27 and the support rollers 23 are free to rotate on their bearings about their substantially stationary axes. In the same manner, the flared entrance guide rollers 28 will freely rotate for the purpose of guiding the advancing vehicle tires into the proper path. As will be explained in more detail, the guide rollers preclude the vehicle (if not steered) from climbing over the guide roller level. At the same time, the advancing and trailing wheels of the vehicle will experience a lateral shift due to the rotative presence of the support rollers 23 in both the left and right hand turn track portion 11 and 12. Further, the angle framework 20 provides a rugged, easy to manufacture and simple to assemble support for the rollers requiring only a minimum of advanced planning as to the size of the curve and related roller lengths. Turning now to the additional embodiments shown in FIGS. 5 and 6, it should be stressed that the uniquely constructed correlator sections are utilizable to describe preselected automobile paths other than the 90° turn shown in FIG. 1. For example, the coordinator shown in FIG. 5 is positioned adjacent the exit end of a car wash 30. In this particular embodiment, the car wash will have blowers 31 on each side of the exit end to facilitate in the drying of the automobile as it leaves the car wash. In order to eliminate what seems to be a natural tendency to turn an automobile too tightly and run into blowers 31, the vehicle path coordinator in FIG. 5 is shown as being comprised of at least two sections 13 for both the left and right path portions 11 and 12 respectively. In this embodiment, there is no need for the rollers in the right hand path portion 12 to be longer than the rollers in the left path portion however, the guide rollers, hereinafter identified by the numeral 32 may be located on either the outer peripheral side portions of each section instead of being only on one (either right or left) path portion as described with respect to FIGS. 1-4. As suggested above, the roller sections are constructed substantially identical to the section discussed with respect to FIGS. 1-4 and will include the support frame angles (not shown), guide mounts 32a, and the flared entrance rollers 33 and their associated mounts 33a adjacent the ramps 34. Also, with this structure, an exit ramp 35 will be in communicating relationship with the end extremity of the support sections so that the vehicle may proceed with the turn only after the blowers have been cleared by the vehicle thereby insuring that same will negotiate the path between the blowers without a possible injury to either. In certain instances, a vehicle (more than likely a delivery truck) needs to negotiate a tortuous path around building corners or other obstacles and to be able to back through narrow, crowded city blocks and alleys. The embodiment shown in FIG. 6 facilitates the movement of a vehicle along such a path thereby making certain loading docks, pick up and delivery stations, and counter tops accessible to larger contemporary vehicles for the first time. Again, the coordinator is comprised of a plurality of sections 13 with parallel left and right paths 11 and 12 defining the route to be taken by the vehicle. It is contemplated that the guide rollers 36 will again be located on the left hand path but could conceivably be mounted on either path depending upon the more convenient assembly. Further, the support rollers 23 will be substantially identical in structure and operation, the only difference being in the fact that certain rollers must have a prescribed length in order to create the arcuate vehicle path movement. In this instance, entrance and exit ramps will be available for elevating or lowering the vehicle on the support surfaces of the rollers as will be needed. In operation, the subject method and apparatus first requires that the selection of the path be made. For example, service station car washes have become quite popular and are generally located on extremely valuable real estate at intersections or close to busy highways and streets. In order to add a car wash facility to an existing service station, it is sometimes necessary that an automobile make a 90° turn to enter the automatic car wash facility. Also, lesser turns must sometimes be made within a limited space in order to efficiently utilize existing facilities and this limited space could, without the subject invention, make the addition of a car wash facility totally impossible. In any event, after the path selection has been made, the turn coordinator is laid along the path with the left and right coordinator portions 11 and 12 being in a substantially parallel relationship. Quite obviously, entrance ramps to each path portion will be provided for easy access to the supporting surface thereof. In any event, the initial roller support section with the flared guide rollers acts to capture the advancing end of the vehicle. This, in effect, positions the vehicle on the path and further vehicle movement by its own power and will result in the guiding of the vehicle even though the driver does not steer the vehicle at all. The previous description has generally indicated that the guide rollers 27 (27 in FIG. 1-4) are mounted on the left side of the path portion along each longitudinal edge of the roller support section. As the advancing end of the vehicle contacts a guide roller with one of its wheels, the guide roller will rotate about its axis of rotation and will preclude the advancing vehicle from "climbing" over the guide rail portion. At the same time, the support rollers will effect the lateral shifting of the vehicle both at the advancing wheels and at the trailing wheels when on the support rollers. Since the support rollers permit the shifting of the rear or trailing end of the vehicle in a direction transverse to the axis of rotation thereof, the rear end follows the front end of the vehicle along a path that may have a significantly shorter radius of curvature than that of the vehicle's normal turn. The size of the framework and the length of the rollers are selected so that the vehicle will travel over a prescribed increment of the path. This increment will be determined by factors such as the weight of the vehicle or the load to be carried by the framework, the radius or curvature through which the vehicle is moved, the width and length of the vehicle, and the space limitations in which the vehicle is being moved. In determining the distance between the left coordinator portion 11 and the right coordinator portion 12, the variations in the track width of different types of vehicles travelling over the prescribed path and the radius of curvature will be considered. Further, the rollers used for guiding the vehicle through the path may have been optimum height above the support rollers. If it is contemplated that very heavy trucks must negotiate a particular path, the guide rollers will be placed somewhat higher than would be the normal location for most passenger automobile vehicles. However, in any case, when the vehicle tire or wheel attempts to "climb" the guides, the rollers will roll and will not provide sufficient support or a frictional track to permit the tires of the vehicle to climb over same. From the foregoing, it will be seen that this invention is one well adapted to attain all the ends and objects herein set forth, together with other advantages which are obvious and which are inherent to the structure. It will be understood that certain features and subcombinations are of utility and may be employed without reference to other features and subcombinations. This is contemplated by and is within the scope of the claims. As many possible embodiments may be made of the invention without departing from the scope thereof, it is to be understood that all matter herein set forth or shown in the accompanying drawings is to be interpreted as illustrative and not in a limiting sense.
A vehicle path controller has a plurality of cylindrical support rollers arranged in section(s) with each roller axis (of rotation) substantially parallel to and along the prescribed path. An entrance ramp is positioned adjacent the initial roller section and facilitates the driving of the vehicle onto same. The rollers are rotatably connected to framework and are conveniently arranged in two separate paths, one path for the left wheels and one path for the right wheels. Guide rollers are also connected to the framework but have an axis of rotation elevated with reference to the vehicle support rollers. The method of controlling the movement of a vehicle along a prescribed path comprises the steps of: Moving a vehicle on said prescribed path having a plurality of rollers supporting substantially the weight of the vehicle, Guiding the advancing end of the vehicle on said roller path, and Laterally shifting the trailing end of the vehicle on said roller path to maintain said vehicle movement along a prescribed path.
1
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention generally relates to buffer circuitry and, more particularly, to a tag buffer integrated circuit with testing capabilities. 2. Description of the Related Art A buffer is a circuit device which is basically a synchronizing element between two different forms of other circuit devices. A tag buffer is a special type of buffer used in an electrical system architecture to store informative "tags." Tags are used to give an indication to the overall system as to where data or instructions are located. A tag buffer includes several components: a storage device, such as a random access memory (RAM), generally having address, data and control signal inputs and outputs; a comparator circuit; a parity generator; and a parity checker or detector. FIG. 1 indicates a typical tag buffer system architecture, e.g., as commercially available in the Am10469/100469 parts manufactured by Advanced Micro Devices, Inc., Sunnyvale, Calif. A common use for a tag buffer is in an integrated circuit memory system. A typical system is shown in FIG. 2. As depicted, a computer system may have both a main memory and a cache memory. The cache memory is a small but very fast supplementary computer memory between the main memory and the central processing unit (CPU). The system is generally designed to use the cache to give the effect of a larger and faster main memory. The cache memory is transparent to the user whose program need not address the cache. The cache is generally controlled to be loaded with the addressed word plus words from adjacent memory locations. Since programs are usually sequential in nature, such a block of words is very likely to be entirely in the cache. In this manner, often-used data or instructions can be in the cache, relieving the CPU from constantly having to access the main memory. Hence, operations can be performed much faster. Tag buffers are used both in address translation cache and data cache applications. The key function of a tag buffer is to compare the internal data bits of a memory with external data bits. An equality of the internal and external data is then confirmed or denied by an output signal from the tag buffer. Referring to FIG. 1, a tag buffer might have nine internal data bits and one output bit. For example, address tags are stored in the tag buffer storage device. The external data, viz., a tag word on inputs D, are compared to the internal data. Each tag word is composed of eight bits of data and one bit of parity (in practice, the word can be expanded to any desired width). An output of a digital logic HIGH (MISS signal) from the comparator component could be used to indicate that the word sought by the CPU is not in the cache; similarly, an output of a digital logic LOW (MATCH or HIT signal) could be used to indicate the word is in the cache. Parity is generated internally (eliminating system parity generation). During a COMPARE cycle, the eight bits of data are monitored for odd parity by the parity checker. It is difficult to test the functionality and switching characteristics of a device such as the tag buffer which includes a multi-bit storage component because its content cannot be read out through the input/output pins. Therefore, a tag buffer which includes a designed-in method for testing and built-in test facilities is needed. SUMMARY OF THE INVENTION It is an object of the present invention to provide a tag buffer having integrated test facilities. It is another object of the present invention to provide a tag buffer system which is capable of testing its own functionality using commercially available testing devices. It is yet another object of the present invention to provide a method for testing the functionality of data and parity bit memory locations in a tag buffer. It is a further object of the present invention to provide a forced-parity-error functionality testing method for a tag buffer. It is also an object of the present invention to provide a signature mechanism in a tag buffer, testing whether an original memory row has been replaced by a redundant memory row. In a broad aspect, the present invention provides a method of testing the content functionality of each of the memory locations in a tag buffer having a plurality of inputs and a plurality of outputs. A predetermined pattern of data bits is written into the memory array. The data inputs are then disabled. The data input to one particular location is enabled and the content of that location is read. A comparison to the known pattern tells whether that location is functioning according to the operational specifications of the tag buffer. Each location, including the locations used to store the parity bit of data, can be tested accordingly. In an alternative embodiment, the present invention is also designed with a "signature" function; i.e., the ability to test whether any addressed rows are replaced by redundant rows. Other objects, features and advantages of the present invention will become apparent upon consideration of the following detailed description and the accompanying drawings, in which like reference designations represent like features throughout the FIGURES. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic block diagram of a typical tag buffer system architecture as is applicable to the present invention; FIG. 2 is a schematic block diagram of a typical cache system in which a tag buffer is commonly used; FIG. 3 is a schematic logic diagram of the present invention as shown in FIG. 1; FIG. 4 is a table which defines the logic level input and output parameters during the various operational cycles of the present invention as shown in FIG. 3; and FIG. 5 is a table which defines the logic level input and output conditions during the various test facility modes of the present invention as shown in FIG. 3. DETAILED DESCRIPTION OF THE INVENTION Reference is made now, in detail, to a specific embodiment of the present invention which illustrates the best mode presently contemplated by the inventor for practicing the invention. Alternative embodiments are also briefly described as applicable. As shown in FIG. 1 and in FIG. 3, the tag buffer 2 includes a storage array 4. In the Am10469/100469 commercial embodiments, the array 4 is a static RAM (SRAM) having 512 rows and 9 columns for a total of 4608 bit locations. In the context of the tag buffer storage, this can be thought of as 512 words which represent "tags" identifying data or instructions. A typical SRAM includes an address decoder, buffers, and control signal and reset function logic circuits. To facilitate the description of the present invention, these conventional subcomponents of the SRAM, being structurally and functionally well known in the art, have been omitted from the FIGURES and description. The device operates with digital logic in which a digital logic HIGH or LOW signal is defined by a functional product specification as particular voltage levels referenced to a system biasing voltage level, Vcc. The RAM 4 has nine address inputs 6 for receiving an address comprising a series of digital logic bits, A 0-8 . The nine address inputs are decoded to select one of 512 memory locations; e.g., row 16 of FIG. 3, which has nine bits, used to identify a specific location for writing digital logic data, D, into, or comparing data out of, that specific location. The RAM 4 also has eight data inputs 8 for receiving the data bits D 0-7 which make up an eight bit word. For the purpose of describing this embodiment, an application of the commercial embodiment in an address translation function is described. Hence, the eight bit word on inputs 8 would be an address "tag" stored in the RAM cells, M 0 -M 7 . Coupled to each of the data inputs 8 is a comparator circuit 17 and a parity generator circuit 10 via discrete electrical connection lines designated 19 and 11, respectively. During a COMPARE cycle, the comparator 17 compares the eight bits of data stored in the addressed memory array 4 row 16 with the eight bits of input data D 0-7 for equality. To ensure the quality of the tag words, a parity bit is stored along with each tag word. The parity generator 10 of the present embodiment generates odd parity; if there is an even number of "ones" in the data inputs 8, the parity will be designated by a HIGH at the parity generator output 12. The parity generator output 12 is input to the parity bit location 14 of the particular row 16 of the RAM array 4 being addressed. Three other signals complete the inputs to the RAM 4. The WRITE ENABLE signal, /W, input 18 in the present embodiment must be at a digital logic LOW signal level to cause data to be written into the location selected by the address inputs 6. When /W is a digital logic LOW signal, data on inputs 8 will be written into the array 4 at the location specified by the address on inputs 6. To read data out, /W has to be a digital logic HIGH signal. The RESET signal, /R, input 20 in the present embodiment must be at a LOW signal level to reset a dedicated data bit (512×1 of the RAM cells) to zero. The CHIP SELECT signal, /S, input 22 when set LOW in the present embodiment activates the tag buffer 2 for a COMPARE, WRITE or RESET activity. A HIGH on this input will disable the tag buffer 2 and force the outputs in the present embodiment to a LOW, allowing for vertical expansion of the tag buffer. The RAM 4 has nine outputs 24. Eight of the outputs 24 are coupled via discrete electrical connection lines to the comparator circuit 17; these outputs 24 correspond to the data bits D 0-7 . The other output 25 is coupled from the selected parity bit location 14 to an input of parity checker circuit 26. The eight data bit outputs 24 are also coupled to discrete inputs 27 of the parity checker circuit 26. The tag buffer 2 has two outputs. The first output 28 is from the parity checker 26. The output signal, PE, will be HIGH if the nine bits of data read out from the RAM array 4 do not constitute odd parity during a COMPARE cycle. In other words, the parity checker detects if the eight bits of data stored in row 16 and the one bit of parity out of location 14 in the RAM 4 are consistent with the odd parity implementation in the present embodiment. The output 28, PE, will be HIGH if there is a parity error during a COMPARE cycle (even parity) or LOW if there is no parity error (odd parity). The other output 30 is from the comparator 17. The output signal, MISS, will be a HIGH if there is a mismatch between the data-in, D 0-7 , and the data-out from the selected storage location during a COMPARE cycle. The MISS signal at output 30 will be a LOW when both the data in and stored data are identical. The parity bit in the RAM array 4 is not compared. There are three operational modes, COMPARE, WRITE and RESET. A table defining the signal conditions for these modes is shown in FIG. 4. In the COMPARE mode, the eight bits of data input, D 0-7 , e.g., an address tag, are compared with the content of an addressed memory location for equality. The nine address inputs, A 0-8 , define each memory location in the array 4. In this mode, /W and /R are HIGH and /S is LOW. If the eight bits of data, D 0 -D 7 , inputs 8 are exactly the same as the eight bits of data out of the addressed memory location, e.g., row 16, M 0 -M 7 , comparator output 30 (defined as the MISS signal) will be LOW. If not identical, the MISS signal at output 30 will be HIGH. If the eight bits of data and the one bit of parity 14 out of the RAM 4 are not consistent with the odd parity implementation, the parity checker output 28, signal PE, will be HIGH. In the WRITE mode, eight bits of data, e.g., from a cache system such as shown in FIG. 2, and the one bit of parity are written into the RAM array 4 when both /S and /W are set LOW and /R is set HIGH. The MISS output 30 is forced to a HIGH (i.e., MISS output is associated with the output enable of the data cache, providing or not providing CPU access). PE is forced LOW. In the RESET mode, with /R set LOW, /S set LOW and /W set HIGH, a dedicated section of the array for data storage is reset to LOW. The ninth section, for parity storage, cannot be reset. The PE signal is forced LOW during this mode. The MISS output 30 is forced HIGH. The nine address inputs 6 do not need to be stable during a RESET cycle. The logic diagram for this embodiment of the invention is shown in FIG. 3. The design of the individual components of this embodiment of the tag buffer 2 makes provision for testing the functionality of various components of the tag buffer 2. As will be obvious to a person skilled in the art, the algorithmic functions and conditions defined by the tables in FIGS. 4 and 5 can be implemented in many different circuit designs; e.g., emitter coupled logic (ECL), transistor-transistor logic (TTL), metal-oxide-semiconductor (MOS) logic, complementary MOS (CMOS) logic, or combined technologies (BiMOS). The limitation is that the implementing circuitry conforms to the logic diagram of FIG. 3 and performs the algorithmic functions defined by the tables of FIGS. 4 and 5. FIG. 5, sets out the conditions for each of four test modes. In the first method of testing (FIG. 5, line I), each RAM 4 data cell location, M 0 -M 7 is tested. A known pattern of digital data is written into the RAM 4 from the test equipment in accordance with the WRITE cycle algorithmic parameters as defined in FIG. 4, line IV. The data pattern written into the RAM array 4 can be all digital 1's, all 0's, or a mixed pattern. Each memory cell can be checked for functionality when set to either representative signal level. CHIP SELECT, /S, is set to a LOW, /W and /R to a HIGH, putting the tag buffer into the COMPARE mode. The first location address (or any particular row of memory cells to be tested) is input on A 0-8 . The first data bit location to be tested at that address, D n , is activated by putting a LOW on the input 8. All other inputs 8 to that address are raised to a third state, "3RD STATE." In the commercial embodiment, 3RD STATE=Vcc+1/2 V BE , where V BE is the base-emitter voltage of the individual transistors used in the individual memory cells. Thus all of the RAM locations at that address except the bit location to be tested for functionality are disabled. As a result of the circuitry logic, instead of providing the operational MISS signal, the output signal from the comparator output 30 will be the content of the tested location. If functional, the bit which falls out, Q n , will be the same as the bit of known data from the previously written pattern. This sequence is repeated for each of the memory locations in the RAM array 4, testing each of the locations or any individual location which is functionally suspect. In other words, when any data input is in the 3RD STATE, the corresponding array cell is disabled. Referring to FIG. 3, for example, to read the content of location M 7 (specified by A 0 -A 8 ), D 0 -D 6 are set into the 3RD STATE and D 7 is set into the LOW state. The data previously written into M 7 appears on the comparator output 30. In the second test mode, the functionality of the parity circuitry and parity bit locations 14 in the RAM 4 is tested. A predetermined data pattern is written into the RAM 4 (as described above for the first test mode). In this test mode, a pattern is written into the RAM 4 which will cause the parity generator 10 to put a data bit representing odd parity into each of the parity bit locations 14, such as M p depicted in FIG. 3. The input conditions to test the parity bit location 14 (defined by address A 0 -A 8 ) are set forth in line II of the table in FIG. 5. CHIP SELECT, /S, is set to a LOW and WRITE ENABLE, /W, is set to a HIGH. Rather than setting the RESET, /R, input 20 to a LOW which would put the device into the RESET mode or to a HIGH for a COMPARE mode (FIG. 4, lines III and II, respectively), /R is set to the 3RD STATE. Instead of providing the operational signal output from the parity checker 26, the odd parity bit stored in the addressed location 14 falls out through the parity checker output 28. Referring briefly to FIG. 3, for example: when the input conditions are set, the data bit in M p , in the row specified by A 0 -A 8 , passes through the parity checker output 28. By toggling the address inputs 6, each location can be checked. As stated above, in the commercial embodiment used for an example of the best mode in this specification, under normal operation the parity generator 10 generates an odd parity bit which is stored in M p . It is also desirable to test the parity circuitry and each parity bit location 14 by forcing a parity error, viz., writing a data bit representing even parity into M p . The input conditions for a third test mode are defined in line III in the table of FIG. 5. The predetermined test pattern in the array is the same as for the second test mode, viz., any pattern which generates odd parity for the parity bit locations 14. Once /S, /W, and /R are set to put the device into a WRITE cycle (compare with FIG. 4, line IV), input A 8 is set to the 3RD STATE and even parity is written into the bottom half of M p . This is then manifested by a PE signal HIGH appearing at the output 28 of the parity checker 26. Although not always the case, it is common for storage arrays 4 to include a redundancy scheme; i.e., redundant rows which can be used to repair rows having defects which would affect the performance of the tag buffer 2. In the commercial embodiment of the present invention, four redundant rows which can functionally replace up to four defective rows are provided. The user may wish to determine whether any particular address accesses a row which is an original array row or directs the array to operate from one of the redundant rows. In the fourth test mode, the commercial embodiment of the present invention provides a "signature" test to make such a determination. The input parameters for this fourth test mode are set forth in line IV of FIG. 5. When /S is set to the 3RD STATE, a HIGH on the comparator output 30 indicates that the row specified by A 0 to A 8 has been replaced by a redundant row. Again, by changing the row address bits, each row can be tested accordingly. Using the present invention, such testing as described in each mode can be performed using commercially available test equipment such as the XINCOM 5588H. Said testing can be programmed to be performed sequentially or individually. The foregoing description of the preferred embodiments of the present invention has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations will be apparent to practitioners skilled in this art. Similarly, any method steps described might be interchangeable with other steps in order to achieve the same result. The described embodiment was chosen in order to best explain the principles of the invention and its practical application, to thereby enable others skilled in the art to understand the invention for various embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims appended hereto and their equivalents.
A tag buffer having built-in testing capabilities is disclosed. In a single-chip, integrated-circuit design which includes a SRAM, a parity generator and checker, and a comparator, a method and capability of testing the functionality of the SRAM and parity components is defined. For an embodiment in which the SRAM component includes a redundancy scheme for replacing a defective memory array row, a test for determining whether a redundant row has been used is also provided.
6
[0001] The present invention relates to directionally solidified nickel-base superalloys alloys having improved heat treat characteristics, good high temperature longitudinal and transverse creep strength properties, good hot corrosion resistance and resistance to oxidation. The invention also relates to the use of the alloys in the fabrication of turbine components, particularly large turbine buckets and turbine blades for aircraft engines. BACKGROUND OF THE INVENTION [0002] It is known to employ nickel base superalloys in the fabrication of aircraft engine components. To be acceptable, such alloys must exhibit good castability with no heat treat cracking, good high temperature longitudinal and transverse creep strength properties and good hot corrosion resistance. [0003] One such nickel base superalloy employed as a turbine blading material in aircraft engines is single crystal (SC) Rene N4 alloy. A form of SC Rene N4 is described in U.S. Pat. No. 5,154,884 as a nickel-base superalloy composition comprising, by weight, 7-12% Cr, 1-5% Mo, 3-5% Ti, 3-5% Al, 5-15% Co, 3-12% W, up to 10% Re, 2-6% Ta, up to 2% Cb, up to 3% V, up to 2% Hf, the balance being essentially nickel and incidental impurities. U.S. Pat. No. 5,399,313 describes a modified version of SC Rene N4 as comprising, by weight, 9.5-10.0 Cr, 7.0-8.0 Co, 1.3-1.7 Mo, 5.75-6.25 W, 4.6-5.0 Ta, 3.4-3.6 Ti, 4.1-4.3 Al, 0.4-0.6 Cb, 0.1-0.2 Hf, 0.05-0.07 C and 0.003-0.005 B, the balance being nickel and incidental impurities. [0004] Typically, aircraft engine blades are small, on the order of a few inches long, and weigh a few ounces, or a few pounds at most. Power turbine buckets, by contrast, are typically up to about 36 inches long, and weigh up to about 40 pounds. It has been found that use of single crystal alloys for such large parts is impractical. A need exists for a superalloy for use in the fabrication of large turbine blades which exhibits good castability with no heat treat cracking, good high temperature longitudinal and transverse creep strength properties and good hot corrosion resistance. The present invention seeks to satisfy that need. SUMMARY OF THE INVENTION [0005] The present invention is directed to an alloy and high temperature heat treatment for buckets fabricated from nickel base superalloys that will allow the buckets to be used for extended periods, typically up to about 72,000 hours in a power turbine. It is has been found that such an extended turbine life can be achieved if approximately 60-80% solutioning of the gamma-prime precipitates in the alloy occurs. The gamma-prime precipitates provide the strengthening phase for the alloy. Moreover, it has been discovered according to the invention that adjusting the level of boron in the alloy of the invention to within the range of about 70-130 ppm, generally about 80-130 ppm, more usually about 80-100 ppm (about 0.0080-0.01 weight %), for example about 90 ppm (about 0.009 weight %), results in a reduction in the incidence of heat treat cracking in the cast buckets. [0006] In a first aspect, there is provided a nickel base superalloy suitable for the production of a large, sound, crack-free nickel-base superalloy gas turbine bucket suitable for use in a large land-based utility gas turbine engine, comprising or consisting essentially of, by weight percents: [0007] Chromium 7.0 to 12.0 [0008] Cobalt 5.0 to 15.0 [0009] Carbon 0.06 to 0.10 [0010] Titanium 3.0 to 5.0 [0011] Aluminum 3.0 to 5.0 [0012] Tungsten 3.0 to 12.0 [0013] Molybdenum 1.0 to 5.0 [0014] Boron 0.0080 to 0.013 [0015] Rhenium 0 to 10.0 [0016] Tantalum 2.0 to 6.0 [0017] Columbium 0 to 2.0 [0018] Vanadium 0 to 3.0 [0019] Hafnium 0 to 2.0 and [0020] Remainder nickel and incidental impurities. [0021] A typical nickel base alloy of the invention comprises or consists essentially of, in weight percent: [0022] Chromium 9.50-10.00 [0023] Cobalt 7.00-8.00 [0024] Aluminum 4.10-4.30 [0025] Titanium 3.35-3.65 [0026] Tungsten 5.75-6.25 [0027] Molybdenum 1.30-1.70 [0028] Tantalum 4.60-5.00 [0029] Carbon 0.06-0.10 [0030] Zirconium 0.01 max (no min) [0031] Boron 0.008-0.010 (also expressed as 80-100 parts per million (ppm)) [0032] Iron 0.20 max (no min) [0033] Silicon 0.20 max (no min) [0034] Manganese 0.01 max (no min) [0035] Copper 0.10 max (no min) [0036] Phosphorus 0.005 max (no min) [0037] Sulfur 0.003 max (no min) [0038] Columbium 0.40-0.60 [0039] Oxygen 0.002 max (no min) [0040] Nitrogen 0.0015 max (no min) [0041] Vanadium 0.10 max (no min) [0042] Hafnium 0.10-0.20 [0043] Platinum 0.15 max (no min) [0044] Rhenium 0.10 max (no min) [0045] Rhenium+Tungsten 6.25 max (no min) [0046] Magnesium 0.0035 max (no min) [0047] Palladium 0.10 max (no min) [0048] Nickel Remainder [0049] In a further aspect, there is provided a method of making a cast and heat treated article such as a large power turbine bucket of a nickel-base superalloy of the invention, wherein the article is heated in an argon atmosphere or in vacuum to develop 60-80 percent solutioning of gamma prime precipitate, followed by cooling to room temperature. Typically, the article is heated to a temperature of about 2260° F.-2300° F., but at least about 25° F. below the incipient melting temperature of the superalloy. The article may be cooled by a furnace cool at a cooling rate of about 35° F./minute to 2050° F., followed by gas fan cooling at nominally 100° F./minute to 1200° F., and then any cooling rate to room temperature. [0050] In yet a further aspect, the invention provides an article, such as a large turbine bucket, produced according to the method of the invention. [0051] In a further aspect, there is provided a gas turbine engine containing an article of the present invention. [0052] The alloy of the invention exhibits several advantages. First, at 90-130 ppm boron the alloy of the invention has better castability (for large turbine buckets) than SC Rene N4 at 30-50 ppm boron. Secondly, at 90-130 ppm boron in DS form the alloy of the invention has an improved yield over SC Rene N4 at 30-50 ppm boron. In regard to “yield”, SC Rene N4 implies one grain per part. SC Rene N4 is typically used to make small turbine blades. As small parts go, it is possible to have a true “single crystal.” However, for large components, it is difficult to actually produce a part with only one grain. Thus, “yield” for a SC part would be near zero (i.e. it is not possible to fabricate any). By changing the composition of SC Rene N4 primarily by adding more boron, it is possible to make a multi-grained DS component. This multi-grained DS component is designed to accommodate many grains across the cross-section of the part. Made in this manner, the “yield” increases to 80-100%. [0053] Thirdly, at 90-130 ppm boron, the alloy of the invention has nominally equivalent mechanical properties (in the longitudinal direction) to the SC Rene N4 at 30-50 ppm boron. Fourthly, at 90-130 ppm boron, the alloy of the invention has better transverse creep properties than SC Rene N4 at 30-50 ppm. Fifthly, at 90 ppm boron, the alloy of the invention has better resistance against heat treat cracking than either the SC Rene N4 at 30-50 ppm boron or the 130 ppm boron DS alloy of the invention. The alloy with 130 ppm boron has a lower melting point (approx. 2301° F.) than DS Rene N4 or DS Rene N4 with 90 ppm boron (m.p. approx. 2315° F.), or SC Rene N4 which has a melting point near 2334° F. (Melting points: DS Rene N4 with 130 ppm boron—2301° F.; DS Rene N4 with 90 ppm boron—2315° F.; SC Rene N4 with 30-50 ppm boron—2334° F.). BRIEF DESCRIPTION OF THE DRAWINGS [0054] The invention will now be described in more detail with reference to the accompanying drawings, in which: [0055] [0055]FIG. 1 is a series of plots showing the effect of different processing conditions on crack length in a MS7001 H turbine bucket; and [0056] [0056]FIG. 2 is a regression plot showing creep strength as a function of temperature; [0057] [0057]FIG. 3 is a regression plot showing transverse creep strength (%) as a function of boron content (ppm); [0058] [0058]FIG. 4 is plot showing creep elongation as a function of test temperature; [0059] [0059]FIG. 5 is a plot showing the effect of varying amounts of boron on incipient melting of SC or DS Rene D4; [0060] [0060]FIG. 6 shows a third and fourth stage bucket fabricated from an alloy of the invention; and [0061] [0061]FIG. 7 is a gas turbine engine showing the location where buckets of the invention are used. DETAILED DESCRIPTION OF THE INVENTION [0062] It has been found, according to the invention, that increasing the boron from about 30-50 ppm in the SC Rene N4 specification to no greater than 130 ppm boron, along with several changes in part configuration, including bucket shape, essentially eliminates casting cracks in large turbine buckets. The additional boron may create a “M 5 B 3 ” phase where M is Ni or Ni 5 B 3 eutectic phase in the grain boundaries and elsewhere within the alloy matrix (as determined by Auger Spectrometry and Microdiffraction analyses), and the melting properties of the alloy have been attributed to the presence of a “M 5 B 3 ” boron phase. The presence of this eutectic phase lowers the incipient melting point (the point at which the metal starts to melt) from 2334° F. to 2301° F. (as determined by Differential Thermal Analysis (DTA)). Thus, after application of a 2320° F. heat treatment (normal for SC Rene N4), the DS alloys begin to melt at locations within the eutectic pools where the boron as Ni 5 B 3 is concentrated. Many of these eutectic pools are in the grain boundaries, and can be more segregated than those eutectic pools elsewhere within the grains. When the eutectic melting starts and the bucket cools back down to room temperature, a linear imperfection defined as a crack may be created. These cracks, called heat treat cracks, may be several inches long but may not be visible to the unaided eye. The heat treat cracks may be found by use of fluorescent penetrant inspection (FPI), a nondestructive inspection technique. [0063] The inventors have carried out work to determine parameters with respect to the boron content of the alloy. It has been found that boron at 30-50 ppm in the alloy of the invention is not particularly suitable for castability of large buckets. At this level of boron, a 2320° F. heat treatment fully solutions the gamma-prime phase and provides optimum longitudinal mechanical properties for long bucket life. However, at this low level of boron, the transverse creep properties are less than optimum for large buckets. [0064] In contrast, boron at 130 ppm in the alloy has been found to be suitable for castability, but is not particularly suitable for a full solution heat treatment. The melting point of such an alloy is reduced to about 2301° F., and the highest heat treatment that may be reliably applied is 2280° F. if melting is to be avoided. Heat treatment at a temperature of 2280° F. provides only about 60-80% solutioning of the gamma-prime phase, but this is generally acceptable for a full-life bucket. Thus, the gamma-prime phase in the 130 ppm boron material cannot be fully solutioned because the alloy starts to melt before full solutioning can be achieved. [0065] The transverse creep properties are acceptable with this higher level of boron of 130 ppm. However, at this level of boron, a 5% failure rate for heat treat cracking has been observed. [0066] It has been found that a level of boron of about 80-100 ppm, i.e. about 90±10 ppm, is optimum for castability. In order to improve the longitudinal creep properties for an improved margin for bucket life, an increase in the percent gamma-prime solutioning over about 60-80% is desired. This may be possible due to the increase in melting temperature for the intermediate (about 90 ppm) boron level. In addition, this 90 ppm level of boron provides a greater margin against heat treat cracking, and increases the yield during the solution heat treatment operation. [0067] Castability experiments have been performed using the procedure described in U.S. Pat. No. 4,169,742 (herein incorporated by reference). A master “lean” heat of DSN4 was formed, where B and Zr were removed, but otherwise the remaining elements (except for C and Hf) were the same as in SC Rene N4 as described above. A three-level, four-factor designed experiment (DOE) was then carried out. Castability was examined using the aforementioned castability test with the grain boundary strengthening elements (& Ti) at the following levels (Zr was not varied but kept at the lowest level), as shown in the Table below: Weight Percent of Elements at the 3 levels Desired for DOE Experiment Element Low Level Medium Level High Level Carbon 0.06 0.10 0.14 Hafnium 0.25 0.45 0.65 Boron 0.0075 (75 ppm) 0.01 (100 ppm) 0.015 (150 ppm) Titanium 3.37 3.50 3.65 [0068] It has been determined that castability is improved if Hf and Ti are run at their highest levels, but this also depends upon the B content. The differences between C and B could not be fully ascertained because this was not a full factorial experiment (which would have been 3×3×3×1×3 or 81 experiments), and due to the limited ranges of carbon (0.14%−0.06%=0.08%) and boron (0.015%−0.0075%=0.0075%) versus ranges for hafnium (0.65%−0.25%=0.45%) and titanium (3.65%−3.37%=0.28%). [0069] Hafnium (Hf) is known to cause casting defects known as “bands”, which are transverse linear indications as determined during FPI examination. It has been determined that 0.75% Hf causes bands in low or high boron DS Rene N4 (boron 30-50 ppm—or 80-130 ppm), whereas 0.25 weight % Hf and 0.45 weight % Hf resulted in no bands. From the standpoint of acceptable transverse creep ductility, the lower level of Hf in production buckets is not allowed to fall below 0.15 weight %. Thus, for DS Rene N4, Hf is generally maintained in the range of about 0.15-0.45 weight %. [0070] Experiments have been carried out using controlled amounts of boron and hafnium added to a baseline N4 master heat to determine their effect on castability, expressed as total inches of crack length. The master heat composition was, by weight, 0.04%C, 9.77% Cr, 7.49% Co, 5.92% W, 1.51% Mo, 4.21% Al, 3.37% Ti, 0.45% Nb, 4.71% Ta, 0.16% Hf, 0.00% B, less than 0.005% Zr, balance Ni. The results for thin wall castings (about 60 mils thick) and thick wall castings (about 120 mils thick) are shown in the chart below. The least amount of cracking (expressed as inches of crack) is best. “Inches of Crack Length from Castability Test” Other heats made by doping master lean heat [0071] The chart above shows that thin wall versus thick wall data are comparable, and that best castability is observed for DS Rene N4 with 40 ppm (0.004%) boron and no Hf, OR 130 ppm (0.013%) boron and 0.45% Hf, indicating there is a “saddle point” in the data. No Hf is not considered to be acceptable as it may decrease transverse creep ductility. It has been found that castability of the 90 ppm boron alloy with 0.15% Hf is improved over the castability of 130 ppm boron material with 0.15% Hf. Higher Hf levels may create transverse “bands” or dross. Banding as noted earlier is a known casting flaw, and “dross” is a nonmetallic inclusion caused by a chemical reaction between dissolved oxygen in the metal and free hafnium in the metal which combine to form a stable oxide such as HfO 2 (hafnium oxide). In either case, lower Hf (typically 0.15-0.45 weight %) is desirable in creating defect-free castings. [0072] The method of the invention includes a ramp heat treatment up to the solution heat treatment temperature plus the post-solution heat treatment cooling rate down to room temperature. Four factors are important to achieving reduced heat treatment cracking. Each has been investigated at two levels, as discussed below. [0073] HIP temperature (2175° F. or 2225° F.); [0074] solution heat treat temperature (2270° F. or 2290° F.); [0075] post-solution heat treatment temperature cooling rate (slow furnace cool at about 35° F./minute, or fast gas fan cool at about 150° F./minute, both followed by gas fan cooling from a temperature of about 2050° F.); and [0076] solution heat treatment atmosphere (vacuum or argon gas). [0077] HIP or “hot isostatic pressing” is a means by which internal porosity in the casting can be closed by the application of external pressure. This is achieved in a HIP vessel. The porosity is closed by the application of temperatures in the range of 2175° F.-2225° F. and 15,000 psi for an alloy like SC or DS Rene N4. [0078] A heat treat temperature of 2290° F. was chosen as the highest temperature possible for the solution heat treatment. The temperature of 2290° F. was reached using part of a RAMP4 cycle to 2290° F., which is set forth in the Table which follows: Typical RAMP4 Solution Heat Treatment Cycle to 2300 F. Hold Heating Ramp Rate Temp. Hold Time Rate Purpose/Results 25 F./minute 1400 F.  10 mm. — Stabilize, and begin introducing 800 microns of argon gas. Not used if already running in a 100% argon atmosphere. 25 F./minute 2225 F.   8 hour Increase to homogenize 25 F./hour 2250 F.   4 hours Increase to homogenize 30 F./hour 2280 F.   2 hours Increase to homogenize 10 F./hour 2290 F.   2 hours Increase to homogenize 10 F./hour 2300 F. 0.5 hours Cool to RT Achieve final gamma-prime solutioning [0079] This heating cycle was chosen because there was no evidence of melting or heat treat cracking using a variety of bucket or ingot sizes. For the 2290° F. solution cycle, that part of the RAMP4 cycle above (including up to 2290° F./2 hours) was chosen. A temperature of 2290° F. was chosen because previous work by the inventor showed that at 2300° F., recrystallized grain (RX) defects could form in DS Rene N4, and to avoid the RX grains the temperature would have to be lowered. Since it is only possible to control the temperature to within 10° F., a temperature of 2290° F. was chosen as the highest practical heat treatment temperature. [0080] The second solution heat treatment temperature was 2270° F. This was based upon metallography photographs showing the percent of gamma-prime solutioning, and was considered to be the lowest acceptable temperature capable of providing a full-life bucket. [0081] The results are set forth in FIG. 1. Heat treating at 2270° F.±10° F. was equivalent to heat treating in the range of 2260-2280° F., and heat treating at 2290F±10° F. was equivalent to heat treating in the range of 2280-2300° F. [0082] A reason that it is difficult to determine what causes heat treat cracking is because the buckets cannot be examined at the solution heat treatment temperature to see if they are cracked. It is necessary to cool the buckets down to room temperature for examination. In addition, the section size of the bucket has some effect on residual stress, which further complicates the heat treat cracking issue. [0083] The HIP temperature was probably not significant because it is well below the incipient melting temperature. Furthermore, the HIP cycle is also a thermal cycle and therefore can provide some homogenization to the DS Rene N4. In this case, the 2225° F. cycle would provide more homogenization than the 2175° F. cycle. But based upon the experimental analysis, it was shown the amount of homogenization provided by either HIP cycle is inadequate to influence the heat treat cracking. [0084] In addition to the previous HIP and solution heat treat cycles, the cooling rate was believed to have an effect on heat treat cracking. To investigate this, two cooling rates were employed. The first rate was produced from a gas fan cool in the range of 100-150° F./minute, which is available on most vacuum furnaces. The second rate was selected because it was used during development trials, specifically from Ramp 4 heat treatment where gas fan cooling was not available—only natural cooling was available (called furnace cooling). Furnace cooling is achieved by just turning off the furnace and letting it cool naturally. In this case, the range was measured to be 35-75° F./minute. [0085] Finally, the furnace atmosphere was felt to be important. Two atmospheres are commonly available. The first is a vacuum atmosphere with some argon backfill, in the range of 400-800 microns. The second atmosphere that is commonly employed (and was used in RAMP 4 heat treat) was 100% argon (not a vacuum). [0086] The furnace environment during the heat treat experiment was determined to be a minor factor. Initially, it was thought a vacuum or partial vacuum environment could cause heat treat cracking by volatilizing the grain boundary elements. In this instance, during a vacuum heat treatment, some elements with a low vapor pressure can be removed from the alloy, possibly leaving void spaces such as along a grain boundary (which could be interpreted as a crack). However, neither atmosphere (vacuum with partial pressure argon or 100% argon) had a significant effect on the heat treat cracking of the DS Rene N4 buckets. [0087] [0087]FIG. 1 shows that the cooling rate has the greatest influence on the heat treat cracking, followed closely by the solution heat treatment temperature (the greater the slope, the larger the effect). The other two factors—HIP temperature and furnace atmosphere—are considered to be minor factors. Thus, the slower cooling rate and the lower solution heat treatment temperature afforded the best results (least amount of heat treat cracking). [0088] When the alloy is DS Rene N4 alloy with 130 ppm boron, the optimum heat treatment includes a HIP cycle at 15,000 psi for 4 hours in the range of 2175-2225° F. followed by a solution heat treatment temperature in the range of 2270° F. to 2290° F., followed by a furnace cool of about 35° F./minute to about 2050° F. and gas fan cooling to less than 1200° F., to prevent heat treat cracking. [0089] The solution temperature had the largest effect on heat treat cracking, and is generally 2280° F.±10° F. (i.e. 2270° F.-2290° F.), more usually 2280° F. This provides for a lower incidence of heat treat cracking while still achieving adequate gamma-prime precipitate solutioning. [0090] The cooling rate is generally in the range of 25-45° F./minute, for example 35° F./minute. The gas fan cooling may be initiated when the temperature reaches approximately 2050° F.±50° F. [0091] The furnace atmosphere may be 100% argon, or vacuum plus argon partial pressure (400-800 microns). Vacuum plus argon partial pressure (400-800 microns) is generally employed. The use of this small amount of argon helps reduce the vaporization (depletion) of chromium during the heat treat cycle. [0092] From this 130 ppm boron group, 1 cracked bucket occurred out of 19 total, or a 5.2% failure rate, due to heat treat cracking. Part of the reason for this is the small margin of error between the heat treat temperature (2280° F.) and the incipient melting point of this alloy (2301° F.). The temperature difference between heat treat temperature and melting point is 2301−2280° F.=21° F. This small margin is less than the error of thermocouples, which would approach 1% of the actual temperature, or at 2280° F. it would be 22.8° F. This means the actual heat treat temperature could exceed the true melting point of the alloy, without the furnace operator's knowledge. If that happened, it would cause incipient melting, which in the presence of residual stress may lead to heat treatment cracks. This is compared to a margin of 54° F. for the 40 ppm boron material between the heat treat temperature and the potential for incipient melting and heat treat cracking (2334° F.−2280° F.=54° F.) [0093] The margin for temperature error with a 2280° F. heat treatment is shown in the Table below. Incipient Aim Heat Melting Point Treat Margin for Temp. DSN4/GTD444 (° F., on Temperature Error during Heat Alloys heating) (° F.) Treatment (° F.) DSN4 w/31 ppm 2346 2280 66 Boron DSN4 w/36 ppm 2344 2280 64 Boron DSN4 w/40 ppm 2334 2280 54 Boron DSN4 w/90 ppm 2311 2280 31 Boron DSN4 w/130 ppm 2301 2280 21 Boron [0094] The advantage in going to an intermediate level of boron, such as in the 80-100 ppm range, is in the margin between incipient melting (when the alloy starts to melt) at the 2280F heat treat temperature. For example, at 130 ppm B, there is only 21° F. between the incipient melting point and the 2280° F. heat treatment. This is not an acceptable range, because the error due to the thermocouple (TC) alone is 22.8F (1% of 2280F). But at 90 ppm B the range between incipient melting and the heat treat temperature has increased to 31° F. Therefore, after accounting for 22.8° F. of TC error, there is still 8.2° F. of temperature margin (31° F.−22.8° F.) between the incipient melting point and the 2280° F. heat treat temperature. While 8.2° F. of margin is not a lot, it is an equivalent margin when compared to other high-technology SC or DS alloys. [0095] Buckets from 90 ppm boron heats were successfully heat treated at 2280° F. with 0% failure rate due to heat treat cracking. For the 90 ppm boron material, the melting point was determined to be 2311° F. Thus, with a heat treat temperature of 2280° F. the temperature difference between the heat treat temperature and the melting point is 2311−2280° F.=31° F. The temperature difference between the heat treat temperature and the incipient melting point is greater than the thermocouple error (1% of 2280° F. or 22.8° F.), so there is less opportunity for unknowingly heat treating the buckets above their incipient melting point, causing heat treat cracking. [0096] It has been found that the amount of boron influences the incipient melting point of the alloy, i.e. less boron is better. The amount of boron additionally influences the transverse creep ductility, i.e. more boron is better (although boron does not influence the longitudinal creep ductility). Moreover, a higher solution temperature leads to more gamma prime solutioning, and more gamma prime solutioning leads to more longitudinal creep life. However, the solution temperature influences the transverse creep ductility, whereby a lower temperature is better. [0097] Thus, optimization of the alloy requires transfer functions (equations) that describe these features in terms of controllable factors. Additionally, creep strength and casting yield are not measured in similar units. Therefore, the transfer function is expressed as a percentage of the best case for heat treat yield (100%) and creep strength (100%). The transfer function generation is described below. [0098] Heat treat yield is a function of two variables, boron content and solution heat treatment temperature. If the B content is too high, incipient melting or heat treat cracking occurs at segregated areas in the casting, resulting in scrap. If the solution heat treatment temperature is too high, incipient melting and recrystallization (RX) limit yield. Recrystallized grains result from a phase transformation where residual strains in the material on heating cause the formation of strain-free grains with little or no strength, i.e. critical defects. The following spreadsheet shows the data used to generate Heat Treat Yield Transfer Function Equation 1: Heat Treat Yield Boron (B) (Percent) Temp. (F.) Content (ppm) 100 2280 40 50 2292 130 50 2310 40 90 2280 130 0 2327 40 0 2310 130 [0099] Regression with the data leads to the following regression equation: Heat Teat Yield=5448−2.34(Temp)−(0.340)*(Boron content)  Eq. 1 [0100] This is the first transfer function for yield. [0101] A statistical analysis was conducted for the data, resulting in the following standard tables: Predictor Coef StDev T P VIF Constant 5448.0 671.8 8.11 0.004 Temp −2.3353 0.2907 −8.03 0.004 1.1 B −0.3398 0.1117 −3.04 0.056 1.1 [0102] S=11.59 R-Sq.=95.6% R-Sq. (Adj)=92.6% [0103] (R-Sq=R 2 or R squared; adj means Adjusted) [0104] The next transfer function is for longitudinal creep strength. This is a function of gamma-prime precipitate solutioning versus the solution heat treatment temperature, as the only way to get 100% creep strength is to fully solution the material. The following is data relating the percent of full creep strength versus the heat treat temperature for DS Rene N4: Creep Heat Treat Strength Temperature (Percent) (F.) 100 2320 90 2300 60 2280 40 2215 [0105] The longitudinal creep strength is in percent of maximum obtainable, and the heat treatment temperature (t) is the solution heat treatment temperature in degrees F. [0106] The data was used to solve for Equation 2 (see the Regression Plot in FIG. 2). The curve has the correct dependency of creep strength on solution heat treatment temperature. It will be noted that as-cast DS Rene N4 has about 40% of the possible creep strength and that solution heat treatment of DS Rene N4 at 2320° F. gives 100% creep strength. This is the second transfer function. [0107] A further important feature of the alloy is creep strength transverse (transverse creep strength) to the grain boundaries. This is important in the tip shroud and other areas where loading is not in a radial direction on he part. The following data was extracted for transverse creep strength: Percent of Transverse Creep Boron Content Strength. (ppm) 50 40 100 80 80 130 90 100 [0108] This information created a non-linear regression plot as shown in FIG. 3. Equation 3 is: Y=− 40.7431+2.9113 X− 1.54 E− 02 X 2 [0109] The three transfer functions (equations) can be solved simultaneously using an optimization spreadsheet shown below: MULTIPLE RESPONSE OPTIMIZATION [0110] The solutions with respect to Heat Treat Yield, Longitudinal Creep and Transverse Creep Strength were: Needs Heat Treat Yield 1 1 2 2 3 3 Longitudinal Creep Strength 2 3 1 3 1 2 Transverse Creep Strength 3 2 3 1 2 1 Optimize B ppm 40 40 94.5 94.5 40 94.5 Temp F 2280 2280 2296 2280 2296 2280 [0111] A “1” means optimization on this need first, followed by “2” and finally “3”. [0112] This results in an optimized alloy with a boron content of 94.5+/−10 ppm and a heat treatment temperature of 2280±20° F. [0113] [0113]FIG. 4 is plot showing creep elongation as a function of test temperature. FIG. 5 is a plot showing the effect of varying amounts of boron on incipient melting of SC or DS Rene N4. [0114] [0114]FIG. 6 shows a third and fourth stage bucket fabricated from an alloy of the invention. FIG. 7 is a gas turbine engine showing the location where buckets of the invention are used. [0115] 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 appended claims.
A nickel base superalloy suitable for the production of a large, crack-free nickel-base superalloy gas turbine bucket suitable for use in a large land-based utility gas turbine engine, comprising, by weight percents: Chromium 7.0 to 12.0 Carbon 0.06 to 0.10 Cobalt 5.0 to 15.0 Titanium 3.0 to 5.0 Aluminum 3.0 to 5.0 Tungsten 3.0 to 12.0 Molybdenum 1.0 to 5.0 Boron 0.0080 to 0.01 Rhenium 0 to 10.0 Tantalum 2.0 to 6.0 Columbium 0 to 2.0 Vanadium 0 to 3.0 Hafnium 0 to 2.0 and remainder nickel and incidental impurities.
2
CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This application is a continuation-in-part of U.S. patent Ser. No. 13/450,172 entitled “Apparatus for Treating Fluids, filed Apr. 18, 2012, which is a continuation-in-part of U.S. patent application Ser. No. 13/019,113, entitled “Transportable Reactor Tank”, filed Feb. 1, 2011, now U.S. Pat. No. 8,906,242, issued Dec. 9, 2014, which is a continuation-in-part of U.S. patent application Ser. No. 12/765,971, entitled “Improved Reactor Tank”, filed Apr. 23, 2010, now U.S. Pat. No. 8,721,898, issued May 13, 2014, which is a continuation-in-part of U.S. patent application Ser. No. 12/399,481, entitled “Enhanced Water Treatment for Reclamation of Waste Fluids and Increased Efficiency Treatment of Potable Waters”, filed Mar. 6, 2009, now U.S. Pat. No. 7,699,988, issued Apr. 20, 2010, which is a continuation-in-part of U.S. patent application Ser. No. 12/184,716, entitled “Enhanced Water Treatment for Reclamation of Waste Fluids and Increased Efficiency Treatment of Potable Waters”, filed Aug. 1, 2008, now U.S. Pat. No. 7,699,994, issued Apr. 20, 2010, which in turn is a continuation-in-part of U.S. Provisional Patent Application No. 60/953,584, entitled “Enhanced Water Treatment for Reclamation of Waste Fluids and Increased Efficiency Treatment of Potable Water”, filed Aug. 2, 2007, the contents of which are hereby expressly incorporated by reference. FIELD OF THE INVENTION [0002] This invention related to the field of fluid treatment and, in particular, to an improved treatment apparatus for destroying aerobic and anaerobic bacteria in fluids used in oil and gas recovery and conditioning of said fluid for reuse without generating a reuse waste stream. BACKGROUND OF THE INVENTION [0003] The Applicant has worked extensively with some of the foulest waters imaginable. In many such instances the treatment of such fluids can be extremely expensive. For example, the global direct costs to oil companies for treating water used in oil and gas recovery surpassed $20 billion in 2007, with expenses skyrocketing in the following years. [0004] While the instant invention can be used on most any fluid that is contaminated, it is especially suited for water contaminated with aerobic or anaerobic bacteria, or waters that benefit from the reduction in dissolved or suspended solids or conditioning thereof. Aerobic bacteria, often called a slime forming bacteria, produces a polysaccharide bio-film that often adheres to the shale and inhibits the flow of gasses. Anaerobic bacteria can be include an acid producing bacteria such as APB that grows on metal and secretes acid producing corrosion, or SRB which is a sulfate reducing bacteria that produces hydrogen sulfide and has the potential to create a dangerous situation and literally shut down a well. [0005] The produced water example will highlight a major problem with contaminated water, which is produced waters are the byproduct associated with oil and gas production and contain both natural and manmade contaminants. The US Department of Energy (DOE) has called produced water “by far the largest single volume byproduct or waste stream associated with oil and gas production.” The DOE further terms its treatment a serious environmental concern and a significantly growing expense to oil and gas producers. While the instant cavitation reactor has a beneficial use with most any water treatment problem, the produced water problem highlights the effectiveness of the system. [0006] In 2007, the world's oil and gas fields produced 80 billion barrels of water needing processing. The average is now almost nine barrels of produced water for each barrel of oil extracted. And the ratio of water to hydrocarbons increases over time as wells become older. That means less oil or gas and more contaminated water as we attempt to meet rising global energy needs. [0007] The discharge of produced water is unacceptable unless treated. Currently it is necessary to introduce chemical polymers to flocculate the slurry and further treat the volatile organic compounds (VOC's) which are emitted as gases from certain solids or liquids. The VOC's are known to include a variety of chemicals some of which may have short or long term adverse health effects and is considered an unacceptable environmental discharge contaminant. Unfortunately, the use of polymers and a settling time is so expensive that economically it becomes more conducive to treat the waste off-site which further adds to the cost of production by requiring off-site transport/treatment or shipped to a hazardous waste facility where no treatment is performed. [0008] The applicants have developed an enhanced fluid treatment system which employs the use of a cavitation reactor. The instant invention advances the developed processes of oxidizing heavy metals, converting oil sheens to inert CO 2 and water, precipitating certain cations or conditioning thereof, and oxidizing organics at a well site. Further, the system may treat numerous other fluid related problems providing both an economic and environmental benefit. [0009] There are many gas fields, most notably in North America, that contain enormous amounts of natural gas. This gas is trapped in shale formations that require stimulating the well using a process known as fracturing or fracing. The fracing process uses large amounts of water and large amounts of particulate fracing material (frac sands) to enable extraction of the gas from the shale formations. After the well site has been stimulated, the water pumped into the well during the fracing process is removed, referred to as flowback fluid or frac water. [0010] Water is an important natural resource that needs to be conserved wherever possible. One way to conserve water is to clean and recycle this flowback or frac water. The recycling of frac water has the added benefit of reducing waste product, namely the flowback fluid, which will need to be properly disposed. On site processing equipment, at the well, is the most cost effective and environmentally friendly way of recycling this natural resource. [0011] It takes from 1 million to 4.5 million gallons of fresh water to fracture a horizontal well. This water may be untreated water available from local streams, ponds, wells or may be treated water purchased from a municipal water utility. Water is typically trucked to the well site by tanker trucks, which carry roughly five thousand gallons per trip. For instance, if approximately 300 five thousand gallon tanker trucks are used to carry away more than one million gallons of flowback water per well, the amount of fuel consumed in addition to the loss of water is unacceptable. For a 3 well frac site these numbers will increase by a factor of three. [0012] The present invention provides a cost-effective onsite cavitation reactor that combines ozone, hydrodynamic cavitation, acoustic cavitation and electro-precipitation for enhanced water treatment. The treatment apparatus is sized and configured to optimize the amount of water to be processed. The treatment system is compact, transportable and self-contained, including both the processing equipment and the power supply to the run the system. It is also configured to be compact in overall size to facilitate its use a remote well sites. The treatment device is also readily transportable such that it can be moved from well site to well site. SUMMARY OF THE INVENTION [0013] The instant invention is directed to an improved treatment apparatus that introduces high intensity acoustic energy and ozone into a conditioning container to provide a mechanical separation of materials by addressing the non-covalent forces of particles or van der Waals force. The invention further discloses hydrodynamic cavitation of the ozone and effluent prior to entry into the treatment apparatus to improve to improve the mixture of effluent with ozone. The ultrasound transducers used to provide the acoustic energy strategically located within the treatment apparatus to accelerate mass transfer as well as electrodes to break down contaminants at a faster rate. [0014] Thus an objective of the invention is to provide a high capacity compact and improved cavitation reactor to treat fluids, the fluids are subjected to ozone saturation and flash mixed with hydrodynamic cavitation and ultrasonic transducers or varying frequencies to initiate flotation of oils and suspended solids and the conversion of ozone to hydroxyl radicals. [0015] Yet still another objective of the invention is to disclose the use of a cavitation reactor that can be used in treatment of most any type of fluid by providing an effective means to destroy aerobic and anaerobic bacteria “on the fly”, and provide a reduction in contaminants. [0016] Still another objective of the invention is to provide an improved cavitation reactor that eliminates the need for biocide and anti-scalant chemical typically employed in frac waters. [0017] Still another objective of the invention is to provide a process to reduce scaling tendencies without the aid of acid, ion exchange processes, or anti scaling chemicals to allow reuse of the same flowback water without generating a waste stream. [0018] Yet another objective of the invention is to employ a process for lowering scaling tendencies in flowback or produced water, as demonstrated by dynamic tube-blocking tests. [0019] Another objective of the invention is employ nano-cavitation imploding bubbles to provide the liquid gas interface that is instantaneously heated to approximately 900 degrees Fahrenheit which oxides all organic compounds through sonoluminescence. [0020] Still another objective of the invention is to provide an improved cavitation reactor for an on-site process that will lower the cost of oil products by reducing the current and expensive processes used for off-site treatment of waste fluids. [0021] Another objective of the invention is to provide an improved cavitation reactor for on-site process that will extend the life of fields and increase the extraction rate per well. [0022] Still another objective of the instant invention is to teach the combination of ultrasonic and hydrodynamic agitation in conjunction with ozone introduction into a closed pressurized generally cylindrically shaped container whereby the cavitations cause disruption of the materials allowing the ozone to fully interact with the contaminated flow back water for enhancement of separation purposes. In addition, anodes in the outlet line provide DC current to the flowback water to drive the electro precipitation reaction for the hardness ions present with the flowback water. [0023] Still another objective is to teach a process of enhanced ozone injection wherein ozone levels can be made more effective. [0024] Another objective of the invention is to provide a cost effective and environmentally friendly process and apparatus for cleaning and recycling frac water at the well site using transportable equipment. [0025] Other objectives and advantages of this invention will become apparent from the following description taken in conjunction with the accompanying drawings wherein are set forth, by way of illustration and example, certain embodiments of this invention. The drawings constitute a part of this specification and include exemplary embodiments of the present invention and illustrate various objects and features thereof. BRIEF DESCRIPTION OF THE DRAWINGS [0026] FIG. 1A is a top view of the main reactor of the treatment system. [0027] FIG. 1B is a side view of the main reactor of the treatment system. [0028] FIG. 2 is a sectional view of the main reactor taken along line A-A shown in FIG. 1A . [0029] FIG. 3 is an exploded view of the main reactor. [0030] FIG. 4 is a pictorial view of the main reactor and a schematic view of the flow treatment downstream of the main reactor. [0031] FIG. 5 is a perspective rear end view of the treatment system mounted on a skid. [0032] FIG. 6 is a perspective front end view of the treatment system mounted on a skid. [0033] FIG. 7 is a left side view of the treatment system mounted on a skid. [0034] FIG. 8 is a top view of the treatment system mounted on a skid. [0035] FIG. 9A is a perspective view of the skid mounted treatment system including the suction intake manifold and associated inlets. [0036] FIG. 9B is a perspective view of the suction intake manifold and associated inlets. [0037] FIG. 9C is a sectional view of the suction intake manifold and associated inlets. [0038] FIG. 10A is a perspective view of one of the ozone mixing arrangements including a fluid inlet pump, ozone injection device, a flash reactor, a static mixer and a discharge nozzle on the left side of the main reactor as viewed from the front. [0039] FIG. 10B is a perspective view of one of the ozone mixing arrangements including a fluid inlet pump, ozone injection device, a flash reactor, a static mixer and a discharge nozzle on the right side of the main reactor as viewed from the front. [0040] FIG. 11A is a side view of a one of the flash reactors. [0041] FIG. 11B is a perspective view of one of the flash reactors. [0042] FIG. 11C is a sectional view of one of the flash reactors taken along line A-A of FIG. 11A . [0043] FIG. 12A is a perspective view of one of the inline static mixers. [0044] FIG. 12B is a cross sectional view of one of the static inline mixers. [0045] FIG. 12C is a detailed view of one of the holes in the inline static mixer shown in FIG. 12A . [0046] FIG. 13 is a side view of a trailer assembly including the treatment system, power generator, oxygen concentrator, ozone generator and control systems. [0047] FIG. 14 is a top view of the trailer assembly shown in FIG. 13 . [0048] FIG. 15 is a rear view of the trailer assembly shown in FIG. 13 . [0049] FIG. 16 is a complete P&ID (piping and instrument diagram) of the treatment system annotated with partition lines for FIGS. 17 A through 17 DD which are enlarged views for purpose of clarity. [0050] FIGS. 17A , 17 B, 17 C, 17 D, 17 E, 17 F, 17 G, 17 H, 17 I, 17 J, 17 K, 17 L, 17 M, 17 N, 17 O, 17 P, 17 Q, 17 R, 17 S, 17 T, 17 U, 17 V, 17 W, 17 X, 17 Y, 17 Z, 17 AA, 17 BB, 17 CC, 17 DD are enlarged views of various sections of the treatment as partitioned in FIG. 16 . DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT [0051] FIG. 1A is a top view of the main reactor 1 of the treatment system and FIG. 1B is a side view of the main reactor 1 . The main reactor 1 includes a cylindrical housing 3 which is, by way of example, approximately 16.5 feet long and 2 feet in diameter. A circular end plate 5 is mounted on each end of the cylindrical housing 3 . Located along the length of the cylindrical housing are eighteen ultrasonic transducers 2 A, 2 B, 2 C, 2 D, 2 E, 2 F, 2 G, 2 H, 2 J, 2 K, 2 L, 2 M, 2 N, 2 P, 2 Q, 2 R and 2 S. Each of the ultrasonic transducers is rated at 500 W capacity and is also equipped with a heated plate that is rated at 1000 W. At given flow rates it maintains a ΔT of 40 degrees which enhances the precipitation within the main reactor. Each transducer can produce an acoustic output in the range of 16 to 20 KHz and can be individually adjusted to the desired output frequency. Each transducer includes a diaphragm that is balanced with the help of a pressure compensation system so that a maximum amount of ultrasonic energy is released into the fluid. The transducer assemblies are installed around the periphery of the cylindrical housing 3 creating a uniform ultrasonic environment which helps to increase the mass transfer efficiency of the ozone. The acoustic cavitations generated by the ultrasonic generators also greatly enhance the oxidation rate of organic material with ozone bubbles and ensure uniform mixing of the oxidant with the fluid. Each transducer assembly includes mounting flange that is sized to mate with a flange on the cylindrical housing 3 . A series of ten disc anodes 4 A, 4 B, 4 C, 4 D, 4 E, 4 F, 4 G, 4 H, 4 I and 4 J are positioned along the length of the cylindrical housing 3 . Each of the disc anodes located in the main reactor 1 has a surface area of approximately 50.26 square inches. The current density for these set of disc anodes are 1.5 Amps/square inch. Each circular end plate 5 supports a series of twelve insulated anode electrodes 10 A and 10 B. The twenty four anode rods within the two sets of twelve, 10 A and 10 B, are approximately seven feet in length and each have a surface area of approximately 197.92 square inches with a current density of 0.6315 amps per square inch. The main reactor tank has eight inlets 6 A, 6 B, 6 C, 6 D, 6 E, 6 F, 6 G and 6 H positioned along the length of the cylindrical housing 3 . Also positioned at one end of the cylindrical housing 3 on the upper most side is a pair of outlets 8 A and 8 B. [0052] FIG. 2 is a cross sectional view of the main reactor 1 taken along line A-A as shown in FIG. 1A . As shown therein, cylindrical mono polar cathode screens 12 A and 12 B are each affixed to one of the circular end plates 5 . These cylindrical cathode screens are approximately eight feet in length and promote efficient migration of electrons. The cylindrical screens 12 A and 12 B are negatively charged to facilitate the precipitation of crystals to adhere to the wall of the cylindrical screens 12 A and 12 B. Each series of anode rods 10 A and 10 B are supported within the main reactor 1 by a pair of supports 16 that are each attached to the inner cylindrical wall of the main reactor 1 . Likewise, each cylindrical cathode screen, 12 A and 12 B, is support by one of the two pairs of supports 16 . Cylindrical cathode screen 12 A is electrically connected via connector 14 A and cylindrical cathode screen 12 B is electrically connected via electrical connector 14 B. [0053] FIG. 3 is an exploded view of the main reactor 1 and associated components as described above in FIGS. 1A , 1 B and 2 . [0054] FIG. 4 is a pictorial view of the main reactor 1 and a schematic view of the flow treatment downstream of the main reactor. The output of main reactor 1 is directed via outlets 8 A and 8 B, via connecting flow conduits 9 A and 9 B, to first fluid treatment conduits 20 A and 20 B, respectively. Each first fluid treatment conduit 20 A and 20 B has an inner diameter of approximately ten inches and is approximately seventeen feet in length. Positioned within the first treatment conduits are a plurality of fixed static mixers that are positioned along the entire length of the conduits 20 A and 20 B. Static mixers 30 are a series of geometric mixing elements fixed within the conduit and create hydrodynamic cavitation within treatment conduits 20 A and 20 B. Each of the geometric mixing elements includes multiple orifices which uses the energy of the flow stream to create mixing between two or more fluids/gases. The optimized design of static mixers achieves the greatest amount of mixing with the lowest pressure loss possible. The static mixers 30 are described in more detailed in FIGS. 12A through 12C herein below. Each of the first fluid treatment conduits 20 A and 20 B includes four separate disc anodes 21 A and 21 B, respectively. The disc anodes 21 A and 21 B help to facilitate the production of hydroxyl radicals. The flow exiting first fluid treatment conduits 20 A and 20 B are then directed to second fluid treatment conduits 22 A and 22 B, respectively. Second fluid treatment conduits 22 A and 22 B have an internal diameter of approximately ten inches and are approximately seventeen feet in length. [0055] Similar to the first fluid treatment conduits, second fluid treatment conduits 22 A and 22 B each have static mixers 30 , creating hydrodynamic cavitation, and four disc anodes 23 A and 23 B, respectively. As in the first treatment conduits, the disc anodes 23 A and 23 B help to facilitate the production of hydroxyl radicals. The flow exiting second treatment conduits 22 A and 22 B are directed into third treatment conduits 24 A and 24 B, respectively. The third treatment conduits 24 A and 24 B have an internal diameter of approximately ten inches and are approximately seventeen feet in length. The third treatment conduits 24 A and 24 B each have static mixers 30 throughout their length, thereby creating hydrodynamic cavitations. The flow exiting the third treatment conduits 24 A and 24 B is directed to outlets 26 A and 26 B, respectively. [0056] FIG. 5 is a perspective rear end view of the treatment system mounted on a skid 41 . By mounting the treatment system on a skid platform the equipment can be readily removed and repaired or replaced and then reinstalled into the mobile trailer unit as will be described later. As shown, the fluid treatment apparatus includes two inlets 40 A and 40 B. One side of the apparatus includes four suction pumps 42 A, 42 B, 42 C and 42 D. Each suction pump 42 A, 42 B, 42 C and 42 D fluidly connects the inlet pipe 40 B to an ozone injection apparatus which is described and illustrated in FIGS. 10A and 10B . The treatment apparatus also includes two separate outlets 26 A and 26 B. As shown in this view, one end of the main reactor 1 has electrodes 10 A mounted on a circular end plate 5 . Connecting flow conduit 9 B fluidly connecting main reactor 1 outlet 8 B to first treatment conduit 20 B. First fluid treatment conduit 20 B is in turn fluidly connected to second fluid treatment conduit 22 B. Second fluid treatment conduit 22 B is fluidly connected via connecting flow conduit 25 B to third fluid treatment conduit 24 B. The fluid exits the third fluid treatment conduit 24 B via an outlet 40 B. [0057] FIG. 6 is a perspective front end view of the treatment system mounted on a skid. This view is a side view opposite to that shown in FIG. 5 . As illustrated, this side of the treatment apparatus shows three suction pumps 44 A, 44 B, and 44 C. It should be understood that it is possible to install a fourth pump (not shown) on this side as well as was shown in FIG. 5 . Typically the reactor is configured with seven inlets and associated pumps and ozone injectors and operated with six of the inlets with one inlet held in reserve for use as needed. It should be noted that the system can be configured with up to eight inlets wherein all eight can be simultaneously operated. Each pump, either three or four in number, fluidly communicates with intake pipe 40 A on the intake side of each pump and an ozone injection apparatus on the outlet side of the pump. The flow leaving main reactor 1 passes through connecting flow conduit 9 B and into first treatment flow conduit 20 A which in turn is communicated to second fluid treatment conduit 22 A. The flow leaving second fluid treatment conduit 22 A then passes through connecting flow conduit 25 B and into third fluid treatment conduit 24 B. The fluid exits the third fluid treatment conduit 24 A via an outlet 26 A. [0058] FIG. 7 is a left side view of the treatment system mounted on a skid 41 . This view shows suction pumps 42 A, 42 B, 42 C and 42 D each drawing fluid from intake conduit 40 B and outputting the flow to an ozone injection apparatus which in turn conveys the fluid to the main reactor housing 1 . Also shown in this view is connecting flow conduit 9 B that connects outlet 8 B with first fluid treatment conduit 20 B. Also shown in this view is second fluid treatment conduit 22 B that is fluidly connected to the third fluid treatment conduit 24 B via connecting flow conduit 25 B. The third fluid treatment conduit is connected to outlet 26 B. [0059] FIG. 8 is a top view of the treatment system mounted on the skid 41 . As seen in the figure the first treatment conduit 20 A contains four disc anodes 21 A and first treatment conduit 20 B also contains four disc anodes 21 B. In a similar fashion the second treatment conduit 22 A contains four disc anodes 23 A and the other second treatment conduit 22 B contains four disc anodes 23 B. Connecting flow conduit 25 A fluidly connects second treatment conduit 22 A to the third treatment conduit 24 A and the other connecting flow conduit 25 B connects the second treatment conduit 22 B to the third treatment conduit. [0060] FIG. 9A is a perspective view of the skid mounted treatment system including the suction intake manifold and associated inlets. The suction intake manifold in mounted below the skid 41 . As shown in FIG. 9B the suction manifold 50 includes four inlets 52 , 54 , 56 , and 58 . At the end of the suction manifold 50 is a suction box 60 . As shown in FIG. 9C the suction box 60 includes a mesh screen 62 with 0.5 inch apertures to arrest debris and particulates grater than 0.5 inches in size. The suction box 60 and mesh screen 62 can be accessed from the rear end of the box 60 . The suction manifold 50 is constructed with hydrodynamic static mixer vanes 64 positioned within the manifold between the inlets 52 and 56 and the suction box 60 . The construction of these static mixing devices is described in FIGS. 12A through 12C to follow. Static mixer vanes encourage the homogeneous mixing of the fluid before entering the main reactor 1 . As will be described, the holes formed within the mixing vanes act as orifices and allow varying pressure at multiple locations. The local pressure drops in flow through the manifold produces cavitations bubbles. These cavitation bubbles collapse as the pressure is again raised. The collapse of the cavitation bubbles produces oxidation of organic substances in the fluid. The suction manifold 50 has two outlets 66 A and 66 B. Outlets 66 A and 66 B are sized and configured to mate up with inlet conduits 40 A and 40 B, respectively. [0061] FIG. 10A is a perspective view of one of the ozone mixing arrangements on the left side of the main reactor as viewed from the front and FIG. 10B is a perspective view of one of the ozone mixing arrangements on the right side of the main reactor as viewed from the front. FIG. 10A shows one of the pumps 42 A, 42 B, 42 C or 42 D mechanically connected to an electric motor 70 . The pump has an inlet 71 that draws in fluid from the inlet conduit 40 B. FIG. 10B shows one of the pumps 44 A, 44 B or 44 C mechanically connected to an electric motor 70 . Downstream of the pump is a venturi type mixing device 72 to inject ozone into the fluid flow. By way of example this can be a Mazzie® injector. The venturi type injector has an ozone inlet 73 . An air compressor feeds an oxygen generator which in turn feeds an ozone generator. The output of the ozone generator is then automatically metered into each of the venturi type mixing devices as is shown in FIGS. 17 A through 17 DD. The pressure drop across the venturi is controlled by an automated bypass valve 74 using a PID control loop. Downstream of the venturi type injector is a flash reactor 76 . The flash reactor 76 uses pressure velocity to create turbulence. Higher cavitation energy dissipation is observed in the flash reactor 76 . The turbulence in the reactor 76 creates high shear making the ozone gas bubbles smaller thereby creating a higher mass transfer efficiency. The flash reactor is described in FIGS. 11A-11C described below. Downstream of the flash reactor 76 is an inline static mixer 78 formed from a series of static blades with apertures, as will be described in FIGS. 12A through 12C , positioned within a 4 inch conduit. The static mixer 78 creates hydrodynamic cavitation and produces cavitation bubbles locally at the orifices of the vanes. As these cavitation bubbles implode within the high pressure area, energy is released in the fluid in the form of heat, light, and mechanical vibration thereby destroying/degrading the organic contaminants. Located downstream of the in line static mixer 78 is a converging discharge nozzle 80 . The conduit supporting the discharge nozzle 80 is fluidly sealed to the main reactor 1 and the nozzle itself is positioned within the main reactor. By way of example only, the converging discharge nozzle can be a Mazzie® nozzle N45. The discharge nozzle is used to increase the velocity of the fluid entering the main reactor which means a higher Reynolds Number and hence higher turbulence energy dissipation. The converging nozzle 80 enhances the systems performance with the venturi type injector 72 . The converging discharge nozzle 80 provides a desired back pressure on the venturi type injector 72 and, the dynamic mixing under pressure results in greater mass transfer of the ozone into the fluid and permits a larger dosage of ozone to enter the fluid. [0062] FIG. 11A is a side view of a one of the flash reactors, FIG. 11B is a perspective view of one of the flash reactors and FIG. 11C is a sectional view of one of the flash reactors taken along line A-A of FIG. 11A . Flash reactor 76 is formed as a generally cylindrical housing and has in inlet conduit 82 that is smaller in diameter than outlet conduit 88 . Within the flash reactor housing 76 the inlet conduit 82 is fluidly connected to a slightly curved section of conduit 83 having a reduced portion 84 . Also within the flash reactor 76 is a curved section of conduit 86 that is fluidly connected to outlet conduit 88 . The direction of curvature of conduit section 83 is opposite to that of curved conduit 86 . As the flow of fluid that has been mixed with ozone is passed through the flash reactor 76 the sizes of gas bubbles are reduced to nano size by high shear. The uni-directional and shearing design of the gas/liquid water mixture allows for a rapid dissolution and attainment of gas/liquid equilibrium which results in high mass transfer efficiency with a minimal time. Due to the configuration of the flow paths within the flash reactor 76 there are different areas within the flash reactor where severe velocity and pressure changes take place. These drastic velocity and pressure changes create high shear which reduces the size of the ozone/oxygen bubbles to nano size and also dissolving more gas into the fluid which is under pressure. [0063] FIG. 12A is a perspective view and FIG. 12B is a cross sectional view of one of the static inline mixers. FIG. 12C is a detailed view of one of the holes in the inline static mixer shown in FIG. 12A . The inline static mixers 30 in figure are approximately 10 inches in diameter and are positioned adjacent to one another within the fluid treatment conduits 20 A, 22 A, 24 A, 20 B, 22 B and 24 B. The inline static mixers 64 are positioned adjacent one another within intake manifold 50 , as shown in FIG. 9C , and are approximately 16 inches in diameter. The incline static mixers 78 are positioned adjacent one another as shown in FIGS. 10A and 10B and are approximately 4 inches in diameter. The views shown in FIGS. 12A through 12C are illustrative of the inline mixers 30 , being approximately ten inches diameter. The inline static mixers 64 and 78 are of similar construction to mixer 30 except that the four inch mixer 78 has fewer holes per baffle 96 than mixer 30 and the 16 inch inline mixer 78 has more holes per baffle 96 than the mixer 30 . The holes 90 formed on each of the baffles 96 of the inline static mixers 30 , 64 and 78 are formed as diverging nozzles having an inlet aperture 92 on the upstream side having a diameter that is smaller than the diameter of the outlet aperture 94 on the downstream side of the blade. The inlet aperture and outlet aperture are connected by a conically shaped bore 94 , as shown in FIG. 12C . Static mixers 30 , 64 and 78 are each formed as a series of geometric elements fixed within a conduit wherein each of the baffles 96 of the static mixing elements contains a plurality of holes 90 are formed as diverging nozzles. The static mixers use the energy of the flow stream to create mixing between two or more fluids. The static mixers are designed to achieve the greatest amount of mixing with the lowest possible pressure loss. [0064] The multiple holes in each of the baffles of the static mixers act as localized orifices, dropping the pressure of the fluid locally allowing the formation of cavitation bubbles. As these cavitation bubbles are carried away with the flow, these bubbles collapse or implode in the zone of higher pressure. The collapse of the cavitation bubbles at multiple locations within the treatment system produces localized high energy conditions such as shear, high pressure, heat light, mechanical vibration, etc. These localized high energy conditions facilitate the breakdown of organic substances. The baffles are arranged so that when the fluid is discharged from one baffle, it discharges with a swirling action and then strikes the downstream baffle. The baffles provide a local contraction of the flow as the fluid flow confronts the baffle element thus increasing the fluid flow pressure. As the fluid flow passes the baffle, the fluid flow enters a zone of decreased pressure downstream of the baffle element thereby creating a hydrodynamic cavitation field. Hydrodynamic cavitation typically takes place by the flow of a liquid under controlled conditions through various geometries. The phenomenon consists in the formation of hollow spaces which are filled with a vapor gas mixture in the interior of a fast flowing liquid or at peripheral regions of a fixed body which is difficult for the fluid to flow around and the result is a local pressure drop caused by the liquid movement. At a particular velocity the pressure may fall below the vapor pressure of the liquid being pumped, thus causing partial vaporization of the cavitating fluid. With the reduction of pressure there is liberation of the gases which are dissolved in the cavitating liquid. These gas bubbles also oscillate and then give rise to the pressure and temperature pulses. The mixing action is based on a large number of forces originating from the collapsing or implosions of cavitation bubbles. If during the process of movement of the fluid the pressure at some point decreases to a magnitude under which the fluid reaches a boiling point for this pressure, then a great number of vapor filled cavities and bubbles are formed. Insofar as the vapor filled bubbles and cavities move together with the fluid flow, these bubbles move into an elevated pressure zone. Where these bubbles and cavities enter a zone having increased pressure, vapor condensation takes place within the cavities and bubbles, almost instantaneously, causing the cavities and bubbles to collapse, creating very large pressure impulses. The magnitude of the pressure impulses with the collapsing cavities and bubbles may reach ultra high pressure implosions leading to the formation of shock waves that emanate form the point of each collapsed bubble. [0065] FIG. 13 is a side view of a trailer assembly 100 containing the treatment system. The complete system is packaged in a mobile trailer that is approximately 53 feet in length. At the forward end of the trailer assembly 100 is a 600 KW generator set 102 powered by a diesel engine. The system is capable of a flexible flow rate of 20-70 barrels per minute. It is capable of producing 2520 gal/minute flow rate with a supply water pressure within the range of 10-40 psi. It is also capable of handling a fluid input having a salinity range of 50-200,000 PPM. A plurality of oxygen concentrators 104 are mounted on a vertical wall within the trailer assembly 100 . Also shown in FIG. 13 are an ozone panel 106 and a cooling water chiller 108 . Visible from this side view are inlets 58 , 56 and inlet conduit 40 A. Also shown in FIG. 13 is main reactor 1 , one of the first treatment conduits 20 A, as well as connecting flow conduits 9 A, 25 A and one of the third fluid treatment conduits 24 A. The fluid treatment system is mounted on a skid 41 for ease of removal, repair or replacement, and subsequent reinstallation through rear access of the trailer. The ability to swap out system component modules substantially minimizes system down time and improves the ability to repair the processing equipment in a quick and efficient manner. The main reactor 1 is approximately 16 feet in length. [0066] FIG. 14 is a top view of the trailer assembly shown in FIG. 13 . This view of the trailer assembly 100 show the 600 KW generator set 102 , the oxygen concentrators 104 , the ozone panel 106 and the cooling water chiller 108 . In addition, this view also shows air pumps 110 , main panel 112 , a DC power supply (e.g. 252 KW) to power the treatment system and power distribution panel 116 . The trailer assembly 100 also includes two side access doors 118 and 120 . [0067] FIG. 15 is a rear view of the trailer assembly 100 with the rear access open. As shown the treatment apparatus is supported on skid 41 . Side doors 118 and 120 are shown in an open position. [0068] FIG. 16 is a complete P&ID (piping and instrument diagram) of the treatment system annotated with partition lines for FIGS. 17 A through 17 DD which are enlarged views to provide clarity. FIGS. 17A , 17 B, 17 C, 17 D, 17 E, 17 F, 17 G, 17 H, 17 I, 17 K. 17 K, 17 L, 17 M, 17 N, 17 O, 17 P, 17 Q, 17 R, 17 S, 17 T, 17 U, 17 V, 17 X, 17 Y, 17 Z, 17 AA, 17 BB, 17 CC, 17 DD are enlarged views of various sections of the treatment as partitioned in FIG. 16 . [0069] The theory of operation behind the main treatment is as follows. The mass transfer of ozone in the water is achieved by hydrodynamic and acoustic cavitations. In the pressurized reactor tank 1 , water that has been ozonated is introduced into through seven separate discharge nozzles 80 . Initially the water to be treated is pressurized by six of the seven pumps each of which in turn feeds an ozone injector 72 . The ozonated fluid is then introduced into a flash reactor 76 which is used to reduce the size of the ozone bubbles to enhance the gas mass transfer efficiency. The ozonated fluid is then introduced into a hydrodynamic mixing manifold 78 . The discharge nozzles 80 direct the flow against the inner wall of cylindrical housing 3 of the main reactor 1 . The phenomenon of hydrodynamic cavitations is created as the pressurized water leaves the small orifices within the hydro dynamic mixing manifold 78 . The dissolved ozone forms into millions of micro bubbles which are mixed and reacted with the incoming water. As the water flows through the main reactor 1 the ultrasonic transducers located around the periphery of the main reactor emit ultrasonic waves in the range of 16 KHz and 20 KHz into the flow of water. The main reactor 1 also includes a plurality of disc anodes, 10 in number by way of example, located about the circumference of the main reactor 1 . In addition, there are two groups of anode electrodes 10 A and 10 B that extend longitudinally into the main reactor 1 from the end plates 5 of the main reactor. Each group of the anode electrodes 10 A and 10 B consists of twelve rods approximately seven feet in length. The main reactor 1 also includes a pair of cylindrical cathode screens 12 A and 12 B that likewise extend longitudinally into the main reactor 1 from the end plates 5 to electro chemically treat the fluid with the main reactor. [0070] A sonoluminescence effect is observed due to acoustic cavitation as these ultrasonic waves propagate in the water and catch the micro bubbles in the valley of the wave. Sonoluminescence occurs whenever a sound wave of sufficient intensity induces a gaseous cavity within a liquid to quickly collapse. This cavity may take the form of a pre-existing bubble, or may be generated through hydrodynamic and acoustic cavitation. Sonoluminescence can be made to be stable, so that a single bubble will expand and collapse over and over again in a periodic fashion, emitting a burst of light each time it collapses. The frequencies of resonance depend on the shape and size of the container in which the bubble is contained. The light flashes from the bubbles are extremely short, between 35 and few hundred picoseconds long, with peak intensities of the order of 1-10 mW. The bubbles are very small when they emit light, about 1 micrometer in diameter depending on the ambient fluid, such as water, and the gas content of the bubble. Single bubble sonoluminescence pulses can have very stable periods and positions. In fact, the frequency of light flashes can be more stable than the rated frequency stability of the oscillator making the sound waves driving them. However, the stability analysis of the bubble shows that the bubble itself undergoes significant geometric instabilities, due to, for example, the Bjerknes forces and the Rayleigh-Taylor instabilities. The wavelength of emitted light is very short; the spectrum can reach into the ultraviolet. Light of shorter wavelength has higher energy, and the measured spectrum of emitted light seems to indicate a temperature in the bubble of at least 20,000 Kelvin, up to a possible temperature in excess of one mega Kelvin. The veracity of these estimates is hindered by the fact that water, for example, absorbs nearly all wavelengths below 200 nm. This has led to differing estimates on the temperature in the bubble, since they are extrapolated from the emission spectra taken during collapse, or estimated using a modified Rayleigh-Plesset equation. During bubble collapse, the inertia of the surrounding water causes high speed and high pressure, reaching around 10,000 K in the interior of the bubble, causing ionization of a small fraction of the noble gas present. The amount ionized is small enough fir the bubble to remain transparent, allowing volume emission; surface emission would produce more intense light of longer duration, dependent on wavelength, contradicting experimental results. Electrons from ionized atoms interact mainly with neutral atoms causing thermal bremsstrahlung radiation. As the ultrasonic waves hit a low energy trough, the pressure drops, allowing electrons to recombine with atoms, and light emission to cease due to this lack of free electrons. This makes for a 160 picosecond light pulse for argon, as even a small drop in temperature causes a large drop in ionization, due to the large ionization energy relative to the photon energy. Theory of Operation: Electro-Chemical Oxidation [0071] There are 24 rod anodes and 10 disc anodes on the reactor. On 10″ static pipe mixer there are four disc anodes per pipe releasing DC current in the water. The current density is maintained between 0.6 Amps/in 2 to 1.875 Amps/in 2 during the process. The turbulent flow through the system aids in efficient electrons migration between anode and cathode. These electrodes are non active electrodes where the anode material acts as a catalyst and the oxidation is assisted by hydroxyl radicals that are generated at the electrode surface. [0000] Rod Anode Surface area per Rod = 198 in 2 Current Density = 0.75″ Dia, Total Surface area available for 0.6315 A/in 2 7 ft long. 24 Rod = 4752 in 2 Disc Anodes Surface Area per Disc = 50.2 in 2 Current Density = on the Total Surface area available for 1.5 A/in 2 Reactor 10 Discs = 502 in 2 Disc Anodes Surface Area per Disc = 50.2 in 2 Current Density = on the 10″ Total Surface area available for 1.875 A/in 2 static 16 disc = 803 in 2 mixers [0072] During electro-chemical oxygen transfer reaction Hydroxyl radicals are generated. The platinum electrode which is electro catalytic produces hydroxyl radicals by dissociative adsorption of water followed by hydrogen discharge. In the process the electric potential is maintained higher than 1.23V (which is higher than thermodynamic potential of water decomposition in acidic medium) the water discharge occurs, leading to the formation of hydroxyl radicals. [0073] The production of oxidants can be performed either by a fast and direct reaction involving one electron transfer or by an indirect mechanism assisted by electro generated intermediates (hydroxyl radicals). Classification of Electrochemical Reactions [0074] A general electrochemical process can be summarized in five steps. Firstly; the mass transfer from the bulk solution to the electrode surface takes place. Then, homogeneous or heterogeneous chemical reactions occur in the electrode surface region associated to surface phenomena (adsorption, crystallization). These reactions are followed by the electronic transfer at the electrode surface. Finally, the mass transfer from the electrode surface to the bulk solution occurs. [0075] The electron transfer reaction is influenced by the nature and the structure of the reacting species, the potential, the solvent, the electrode material and the adsorbed layers on the electrode. In order to understand these influences (interactions between reactant and electrode surface), theories have been developed based on two main concepts, which are known as inner sphere and outer sphere electron transfer reactions. Outer Sphere Electron Transfer Reaction: [0076] The term outer sphere is used to describe a reaction, in which the activated complex maintains the coordination sphere originally present in the reactant species (Figure below). During outer sphere reactions, weak interactions between the electrode and the reactant take place. The interaction maintains a distance of at least one solvent layer between the reactant and the electrode surface. In this case, the kinetics of the reaction is not much dependent on the electrode material. [0077] Nevertheless, the electrode material could influence the kinetics, even in the case of outer sphere charge transfer, by affecting the electrical double layer and the Helmotz layer structure. Since outer sphere reactions can be treated in a more general way than inner sphere processes, for which specific chemistry and interactions are important, the theory of outer sphere electron transfer is much more developed. Among the large outer sphere systems, Fe(CN)6 3− /Fe(CN)6 4− and IrCl6 2− /IrCl6 3− reactions are the most frequently used. [0078] A reaction is described in terms of inner sphere when the reactants share a ligand in the activated complex. Therefore, both, the reactant and the product species, as well as the activated complex, are involved in very strong interactions with the electrode surface (specific adsorption). This kind of reaction implies multistep electron-transfer reactions. Production of Hydroxyl Radicals: [0079] The electrochemical production of hydroxyl radicals and their role in electrochemical oxygen transfer reactions depend on the electrode material used. The mechanism of hydroxyl radical's formation depends also on the electrical potential. These radicals are then more or less strongly adsorbed at the surface. The mechanism of the water activation reaction implies to deal with two different mechanisms depending on the potential; via either the dissociative adsorption of water or the electrochemical water discharge. Formation of OH Radicals Via the Dissociative Adsorption of Water: [0080] Platinum is a typical electro catalytic material. This type of material implies the formation and the breaking of bonds between species and adsorption sites. On this electrode material, the electrochemical oxygen transfer reaction occurs as follows eq.1: [0000] RH+H 2 O→RO+3H + +3 e −   Eq.1 [0081] At a potential lower than the thermodynamic one for water discharge to O 2 , the water activation is described by the Equation 2, followed by Equation 3. These reactions take place at a low potential (about 0.4 V vs Std. Hydrogen Electrode) and lead to the strong adsorption of hydroxyl radicals on the platinum surface. Dissociation adsorption of water [0000] (H 2 O) ads →(H  ) ads +(HO  ) ads   Eq.2 Hydrogen Discharge [0000] (H  ) ads →H + +e −   Eq. 3 [0084] Once the hydroxyl radicals are produced, the reaction with an organic compound RH can occur via two possible mechanisms: Eley-Rideal (Equation 4) or Langmuir-Hinshelwood (Equation 5): [0000] RH+(HO  ) ads →RO+2H + +2 e −   Eq. 4 [0000] (RH) ads +(HO  ) ads →RO+2H + +2 e −   Eq. 5 [0085] In the first mechanism (Eley-Rideal), only hydroxyl radicals are strongly adsorbed, while for Langmuir-Hinshelwood, both hydroxyl radicals and organic compounds are strongly adsorbed at the electrode surface. The adsorption of the organic compound is performed by the first step of the inner sphere electron transfer anodic reaction (RH→(RH) ads). [0000] Pt+H 2 O→Pt−(OH) ads +H aq + +e −   Eq.6 [0086] FIG. 20 illustrates a reaction scheme of the possible methanol electro oxidation process at Pt electrodes. Electrochemical Formation of OH Radicals Via Water Discharge [0087] When the potential is higher than the thermodynamic one for water decomposition, the formation of hydroxyl radicals is performed in one step via the electrochemical water discharge. [0000] H 2 O→HO  +H + +e −   Eq. 7 Redox Potential of OH Radicals: [0088] The formation of free hydroxyl radicals in aqueous solution necessitates a high anodic potential. OH − radicals appear as the strongest oxidant with a potential of 2.65 V vs Std. Hydrogen Electrode in acidic medium. Other references estimated the OH − redox potential between 2.6 and 2.8 V [34-37]. [0089] OH − radicals are highly oxidizing and widely used for water treatment. Following table summarizes the redox potential of some chemical systems known to treat water. [0000] Oxidant Redox potential F 2 3.03 HO □ 2.80 O □ 2.42 O 3 2.07 H 2 O 2 1.78 Cl 2 1.36 Table shows a Redox potential of some chemical systems used for water treatment. Electrochemical Fenton Process: [0090] The Fenton reaction, involving both ferrous iron and hydrogen peroxide can be used electrochemically according to two processes: cathodic and anodic Fenton processes. [0091] In cathodic process, Fe (II) can be produced by the reduction of Fe (III) at the cathode or by oxidation of ozone. [0000] Fe 3+ +e − →Fe 2+   Eq. 8 [0092] H 2 O 2 may be also formed by the reduction of O 2 at the cathode: [0000] O 2 +2H + 2 e − →H 2 O 2   Eq. 9 [0093] The cathodic process takes place at neutral pH. The main advantage of this technique is the continuous production of Fe(II) and hydrogen peroxide. [0094] In the anodic Fenton process, an iron electrode is used as anode and plays the role of source of ferrous ions. The reaction occurs under acidic pH conditions and with a high current efficiency. [0000] Fenton reaction: [0095] This method is probably the oldest and the most used technique to produce hydroxyl radicals. In 1894, H. J. H. Fenton reported that ferrous ions strongly promote the oxidation of malic acid by hydrogen peroxide. Subsequent works have shown that the combination of ferrous molecules and H 2 O 2 produces an effective oxidant of a wide variety of organic substances such as phenols and herbicides. This mixture was called “Fenton's reagent”. [0096] Hydrogen peroxide is not a strong oxygen transfer agent, but the oxidation of organics is improved in the presence of Fe 2+ ions because the reaction leads to the formation of highly oxidizing OH radicals according to Fenton's mechanism. The first step is the initiation reaction, in which the ferrous ions are oxidized by H 2 O 2 : [0000] Fe 2+ +H 2 O 2 →Fe 3+ +OH − +HO    Eq. 10 [0097] The radical chain reactions lead to the oxidation of the organic compounds, either by hydrogen abstraction reaction, redox reaction or electrophilic addition. The parameters of the reaction are optimized in order to favor the addition of OH group and the abstraction of hydrogen. An excess of H 2 O 2 or Fe 2+ might be detrimental because these species can react with some of the intermediates like OH radicals: [0000] Fe 2+ +HO  →Fe 3+ +OH − [0000] H 2 O 2 +HO  →H 2 O+HOO    Eq. 11 & 12 Ozone Water System [0098] Ozone is firstly produced by electric discharge of water and is decomposed in basic medium according to a chain reaction: [0000] HO − +O 3 →O 2 +HO 2 −   Eq. 13 [0000] HO 2 − +O 3 HO 2  +O 3 −   Eq. 14 [0000] HO 2  ⇄H + +O 2 −   Eq. 15 [0000] O 2 − +O 3 →O 2 +O 3 −   Eq. 16 [0000] O 3 − +H + →HO 3    Eq. 17 [0000] HO 3  →HO  +O 2   Eq. 18 [0000] HO  +O 3 →HO 2  +O 2   Eq. 19 Sonolysis of Main Reactor: [0099] Ultrasound is known to produce cavitations in liquid media. Cavitations bubbles are generated during the rarefaction cycle of the acoustic wave. The sonolytical cleavage of water H 2 O→HO  +H  reactive OH radicals. [0000] H 2 O→HO  +H    Eq. 20 [0100] The free radicals may further precede some secondary reactions to produce hydrogen peroxide or water. [0101] On the main Ozonix reactor there are 18 Ultrasonic transducers installed at different orientation. The finite element simulation of the sound field in the main reactor was carried out to prediction of the cavitational activity in terms of sound pressure field distribution by solving the wave equation using finite element method. [0102] Pressure field distribution is obtained using COMSOL Multiphysics. The wave equation can be given as: [0000] ▽  ( 1 ρ  ▽   P ) - 1 ρ   c 2  δ 2  P δ   t 2 = 0 Eq .  21 Where [0103] ρ=is the density of the liquid medium c=is the speed of the sound in liquid medium The solution of this equation using finite element gives the spatial variation of the acoustic pressure in the reactor. The transient analysis gives the real time sound pressure field in the reactor without making the assumption of harmonic pressure variation. [0104] In a preferred embodiment, the cylindrical cathode screens 12 A and 12 B and the 18 ultrasonic transducers are constructed and arranged so that the acoustic cavitation waves that are generated contact the cathodes. The reaction on the cathodes changes the crystalline structure of the hardness ions and renders them a solid. [0105] The acoustic cavitation waves pulse clean the cathodes thereby allowing control of the precipitation reaction of calcium carbonate in order to avoid super saturation of the fluid. The reactor generates a crystalline calcium carbonate that is non reactive at the pressures and temperatures that occur in hydraulic fracturing. The ultrasonic transducers are constructed and arranged to allow seed crystals to grow to a predetermined size and then pulsed into an inert solid that remains in the fluid. The inert crystals prohibit interference with friction reducers, eliminate scale and do not bind pumps. The result is generation of a fracturing fluid that reconditions flowback water, produced fluids and petroleum industry waste water for re-use in a wellbore for hydraulic fracturing without generating a waste stream or requiring scale inhibiting chemicals. [0106] It is to be understood that while certain forms of the invention is illustrated, it is not to be limited to the specific form or process herein described and shown. It will be apparent to those skilled in the art that various changes may be made without departing from the scope of the invention and the invention is not to be considered limited to what is shown and described in the specification and drawings.
The treatment apparatus is pressurized and operates on a continuous flow of fluids which are subjected to hydrodynamic waves, acoustic ultrasonic waves in combination with injected ozone and electro chemical treatment. The treatment system provides a cost efficient and environmentally friendly process and apparatus for cleaning and recycling fluids as contaminated as frac water, used to stimulate gas production from shale formations, as well as other types of fluids having various levels of contaminants such as aerobic and anaerobic bacteria and suspended solids. The calcium carbonate scaling tendency is reduced to an acceptable level without the use of acids, ion exchange materials, or anti scaling chemicals which is of economical and environmental significance and benefit. The treatment apparatus is modular in construction and compact in overall configuration. The treatment apparatus and associated equipment and electrical power generator is sized and configured to be mounted within a truck trailer body.
8
This is a continuation of application Ser. No. 930,954 filed Nov. 12, 1986, now abandoned, which is a continuation of application Ser. No. 539,120 filed Oct. 5, 1983, now abandoned. BACKGROUND OF THE INVENTION The invention relates to a granular body and a method of manufacturing it, especially of SiO 2 for an article having a nonuniform refractive index. Enlongated glass bodies can be used as so-called preforms for the production of optic fibers having nonuniform transverse refractive indices, preferably in the visible spectrum or in the short infrared wavelength range, for communication. In addition, such bodies can also be used for the production of glass rods or glass plates which have lens-like properties. For optic fibers used for communication, the refractive index in the cross section of the fiber is greater at the core of the fiber than in the peripheral part thereof. In the case of the so-called monomode fibers and the so-called stepped index fibers, the refractive index transition between the axial or core area and the peripheral area or "cladding" is abrupt. Optical waves which propagate away from the core of the fiber are reflected back into the core at this abrupt transition. In the so-called multimode fibers, the refractive index gradually decreases from the core to the peripheral area, preferably in an exponential manner. In this case, waves which do not propagate parallel to the axis of the fiber are gradually turned toward the axis by a kind of lens effect to remain captive in the core or axial region. For the rods and plates with lens-like properties mentioned above, a gradual reduction of the refractive index from the center of the body to the margin is prescribed, and again it should be exponential. Light rays passing through a parallel-sided plate of such glass are increasingly deflected toward the center such that the plate behaves optically like a lens. In both applications, but especially in communications fibers because of the length of glass through which the rays must propagate, the precision of the glass must be very high with the absorption and scatter of the optical rays reduced to a minimum. Consequently, in the production of the fibers, the utmost purity must be achieved since residual absorption is due mostly to the presence of foreign substances. Moreover, the profile of the refractive index must follow the prescribed form very closely. The desired properties can be achieved, for example, by the use of high-purity fused silica as the basic material with other materials added to it, such as titanium dioxide, germanium oxide, fluorine, boron trioxide, and phosphorus pentoxide, to vary the refractive index of refraction. It has been found advantageous to use more than one dopant to achieve the desired properties. In this manner, for example, the internal tension due to a dopant can be adjusted to a desired level. It has also been found that the useful signal bandwidth of the fibers can be influenced to a great extent by precise control of the refractive index profile. For this purpose it can be advantageous to use refractive index profiles other than the exponential. For example, a step at the margin of an exponential index profile of the core has proven practical. In the known processes, as disclosed, for example, in German Patent 2,715,333 or Offenlegungsschrift 2,313,203, it is possible in a simple manner only to produce cylindrically symmetric refractive index profiles, resulting in fibers of circular core cross section and circular fiber cross section. Although such fibers are suitable for communication, they have certain disadvantages. For example, they have no preference for a particular polarization of the light which they transmit. This is due to the wave-guiding nature of the optical fibers. A preference for certain polarizations is then produced by fortuitous tension distributions in the fiber, but these fluctuate rapidly and to a very great degree in practical operation, due to external influences, such as acoustic or mechanical influences. It is also desirable to produce fibers with multiple cores, so that a plurality of communication channels can be contained in a single fiber. It has been possible to produce such fibers heretofore only from materials, such as low-melting glasses, and by methods, such as the multiple-crucible process, which do not result in the low attenuations necessary for communications. The production of optic fibers is normally accomplished by first producing an elongated glass body having a refractive index profile that is similar to that which the later optic fibers are to have. This elongated glass body is then drawn at high temperature in to a fiber, while, due to the high viscosity of the material during the drawing process, the radial profile of the refractive index is largely preserved. It is generally known that vitreous silica is used as the basic material for high quality communication fibers. It is also known that, theoretically, still greater bandwidths and still less attenuation can be achieved with other materials. These include, for example, a mixture of germanium oxide and antimony oxide or a whole series of known fluoride glasses. Also, optic fibers of more or less high attenuation can be produced from various crystals, plastics, and still other types of glass. The method of the invention is to be suitable for the use of all these materials equally. SUMMARY OF THE INVENTION An object of the present invention is a process for the production of enlongated granular bodies, especially of SiO 2 , to serve as preforms for optic fibers or other optic components having a varying refractive index which will allow great freedom of geometric configuration, which will be independent of special properties of the glass or other substances, which uses a minimum of high temperature processes, and which can produce large preforms in a continuous process of low manufacturing cost. To these and other ends, a process controls the geometric distribution of the substances which will determine the optic properties of an article made from a granular body by controlled feeding of grains of these substances into the shape of a granular body. It is possible in this manner to achieve any desired cross-sectional configuration of the desired substances, and thus their optic properties. The shape of the granular body is then stabilized during or after the controlled-feeding of the grains so that the geometric distribution of the grains determining the future optic properties will not be altered. In a subsequent process, when the substances are glasses, a transparent glass body may be formed from this shape-stabilized granular body by heating in such a way that grains form a single glass body with the geometrical configuration of the substances of the granular body reduced proportionally during the vitrification process owing to the high viscosity of the glasses. It can be advantageous to compress the shape-stabilized granular body so as to form a porous, solid compact prior to the formation of the glass body. It is furthermore advantageous to subject the shape-stabilized granular body or porous compact to at least one gas treatment by which undesired substances such as water, for example, can be removed from the body while it is still granularly permeable to gas. Metal impurities can also be reduced and desired substances, such as hydrogen or helium for example, incorporated into the material in this way. According to the present invention, first, starting substances are produced which, in vitrified or finished form, will have a uniform refractive index for each different substance. These substances are produced either directly in the finely granular form of grain diameters ranging from about 0.1 micrometer to about 1 millimeter in which they are to be used, or first a solid is produced from which the grains can be formed by grinding. The following procedure has proven to be especially desirable for the production of preforms based on fused silica (SiO 2 ). Silica is prepared in finely granular form by the pyrolysis of silicon tetrachloride. These fine silica particles are collected and used in this form. The process of causing silica particles produced by pyrolysis to grow axially or radially into a rod on a rotating support has also proven advantageous. This rod is then crushed in a ball mill after removal of the support. For the practice of the invention, for one example, grains of one substance may consist of high-purity silica, and grains of another substance may contain, in addition to silica, one or more dopants, such as germanium oxide, titanium oxide, fluorine, or the like, in at least the highest concentration that is to be achieved in the glass body. These two granular substances are stored in separate hoppers. The grains of the different substances are taken from the hoppers at a specific rate through controllable shutters and poured onto a support. The pouring is performed such that a given distribution of the grains of the different substances results. In this manner, the refractive index profile that is achieved by the subsequent vitrification is already latent in the granular body. The granular body, which in itself is loose, is held together or defined while it is being poured. A fused silica tube surrounding the granular body has proven practical for this. After the granular body has been formed, this body, which is permeable to gases, is subjected to chemical treatment, preferably in a gas atmosphere. Chlorination for a period of two hours at 800° C. has proven to be a good method for the removal of undesired hydroxyl ions from a body having a diameter of 60 mm. It is advantageous to compress the granular body, to such an extent that its shape will be stable without additional support. This compression has the additional advantage of increasing the density of the body, thereby reducing the amount of shrinkage that will occur when the glass body is formed. In the case of grains of fused silica produced by pyrolysis, an isostatic compression at a pressure above 500 bar, and preferably above 2,000 bar, has proven practical. The resultant porous compact is easy to handle, but is still completely permeable to gases. If desired, it can be subjected to additional chemical treatments in a gaseous atmosphere while in this state. The finely porous compact is then converted to a dense glass body. This is performed preferably by drawing the elongated, finely porous compact slowly through an annular kiln surrounding it. Upon vitrification, a shrinkage in volume occurs, but this has no effect on the distribution of the components which determine the refractive index. If desired, the vitrification process can also be performed directly on the shape-stabilizer granular body without compressing it. It is evident that the particular nature of the starting materials has nothing to do with the practice of the process. In the case of fused silica, for example, it is possible also to use grains obtained by grinding rock crystal or from high-purity quartz sand. It is also possible to use grains produced by grinding vitreous fused silica. In this case, the high purity of the material is not achieved as easily as in the case of pyrolytic method described above, yet the compacts thus obtained are of sufficient quality, for example, for the production of components having a lens-like action. It is also evident that the described method can be used for materials other than fused silica, as long as these materials can be prepared in finely granular form and can be combined into a solid body, for example, by a vitrification process. One special advantage of the process lies in the freedom it affords in the configuration of the geometric distribution of the grains and hence in the geometric arrangement of the refractive index profile of the glass body formed from the granular body. The method is not limited to the production of cylindrical fibers with cylindrical cores. BRIEF DESCRIPTION OF THE DRAWINGS Preferred embodiments which illustrate but do not limit the invention will now be described with reference to drawings in which: FIG. 1 is an embodiment of a granular glass body made by the method: FIG. 2 is another embodiment of a granular glass body made by the method; FIG. 3 is another embodiment of a granular glass body made by the method; FIG. 4 shows, diagramatically, one apparatus for the method; FIG. 5 shows, diagramatically, another apparatus for the method; FIG. 6 shows, diagramatically, the method using a portion of the apparatus of FIG. 5; FIG. 7 shows, diagramatically, another apparatus for the method; and FIG. 8 shows, diagramatically, apparatus for forming a glass fiber from the granular glass body. DESCRIPTION OF THE PREFERRED EMBODIMENTS Granular bodies are represented in perspective in FIGS. 1, 2 and 3, grains 10 having been poured into a core region about the axis of the body and grains 16 poured around the core (cladding material). The core has a rectangular cross section in FIG. 2, and a circular cross section in FIG. 1. In FIG. 3, there are several cores of grains 10 spaced about the axis of the granular body. An arrangement suitable for the production of the granular bodies of FIGS. 1 and 2 which are preforms for a stepped index of refraction is represented in FIG. 4. A cylindrical or tubular quartz supporting body 2 is mounted on a base 1 and another quartz tube 3 is centered inside of quartz tube 2 and can be raised by means of a rack 4 driven by a pinion 5 to define the boundaries of the grains 10 and 16. Grains 10 of one substance which, after vitrification, will have the desired refractive index for the core of a stepped index fiber are in one hopper 7. In another hopper 11 are grains 16 of another substance which, after vitrification, will have the desired refractive index for the cladding of the stepped index fiber. The grains 10 are fed or poured through a feed tube 17' into the quartz tube 3 to form, rising from the base 1, the core. Grains 16 are poured through a feed tube 17" and, through an annular spreading spreading means 14 represented diagrammatically in the figure as a multiple-spout funnel driven about the cylinder axis 19 by means of a belt 18 powered by a motor 15, are uniformly spread around so that the cladding material 16 builds up on the support 1. As long as the quartz tube 3 remains on the floor of the support 1, the materials 10 and 16 are completely separated from one another. As the depth of the materials increases, the quartz tube 3 is elevated, so that the materials 10 and 16 will come in direct contact with one another. It is possible in this manner to build up a step profile at a high rate and a small investment in apparatus. When the quartz tube 3 is raised, a certain amount of intermixing will occur at the boundary surface between the materials 10 and 16. This can be kept at an acceptable level by providing a sharp edge at the bottom of the quartz tube 3 and by providing that the tube 3 will be raised concurrently with like build-up of materials 10 and 16. To achieve this, the drives for the different mechanisms controlling the system are programmed through a common control unit 6. The uniformity of the pouring can be improved if periodical mechanical forces in the form of acoustical jogging or vibration act on the granular body while it is being poured. For this purpose the base 1 can be acted upon by an acoustical vibrator or by a jogging mechanism (not shown). The rate at which the grains 10 and 16 are fed from the hoppers 7 and 11 is controlled by means of valves or shutters 9 and 13. It is easy to see that, in the system of FIG. 4, not only cylindrically symmetrical bodies can be produced, but also those of other geometrical profiles. For example, by replacing the cylindrical quartz tube 3 with a tube of rectangular cross section, the granular body can be made with a rectangular core, as represented in FIG. 2. Granular bodies can also be made with multiple cores as represented in FIG. 3 with the system of FIG. 4. For this purpose a plurality of quartz tubes are disposed within the quartz tube 2. The variability of the process of the invention with regard to the geometry of the granular body, especially its cross section, has the advantage that certain defined polarizations can be achieved in fibers with oval or, better, with a rectangular cross section. The circumferential shape of the granular body can be made rectangular, too, so that the position of the plane of polarization will be well defined. This is not easily achievable by the methods of the prior art. It is characteristic of the granular bodies that can be made with the system represented in FIG. 4 that in particular areas of the cross section only grains of one or the other substance are to be found. Consequently, stepped index profiles can be produced, but not profiles of continuously varying refractive index, known as graded index profiles. A system represented in FIG. 5 is appropriate for the production of such profiles. This diagrammatic representation shows a system for producing granular bodies of cylindrical shape; it is also suitable, however, for the production of granular bodies of any shape. A base 1' is set in rotation by a motor drive 20'. In one hopper 7' are grains of one substance 10, and in another hopper 11' are grains of another substance 16. By means of variable shutters 9' and 13', the grains are fed into a common feed line 23 through tubes 21 and 22, and are mixed together. A pouring nozzle 24 is moved horizontally under program control through a mechanical drive 25 by means of a controller 27 controlling the motor 26. The grains emerging from the open end of the pouring nozzle are thus deposited on the base 1' along a narrow spiral path. Then, as the base 1' continues to rotate and the pouring nozzle 24 moves back and forth horizontally as indicated by the arrow 37, the material is laid down in layers. The movement of the pouring nozzle is controlled such that, with the material being poured at a constant rate, its depth will be constant all across the base. In other words, the granular body is built up in spiral layers. During each movement of the pouring nozzle 24, the composition of the layer it is forming can be varied in a controlled manner by the operation of the shutters 9' and 13', and it is thus possible to produce any desired proportions in which grains of both substances can be deposited in the same unit of area. The system represented in FIG. 5 is thus suitable for the production of graded index preforms. In FIG. 5 there is shown another system for shape-stabilizing the granular body while it is being made. The support 1' is continuously lowered during the pouring operation (by means not shown), so that the open end of the pouring spout 24 is always at the same height above the surface of the body. A band 31 is unwound from a supply roll 34 and laid continuously about the body to form a wound supporting body to define it at its circumference as it is built up. The controlling of the feed rates by the shutters 9' and 13', the horizontal movement of the pouring spout 24 by the drive 25, 26, the rotation of the support 1' by the drive 20 and its lowering, and the wrapping of the body in the supporting tape are controlled by a common process controller 27. By the use of a computerized process controller 27, it is easily possible to make allowance for the time lag between the mixing of the components 10 and 16 and the pouring itself. It is also possible in this manner to set the apparatus up for any desired refractive index profile. Fundamentally it is possible by suitable programming of the system shown in FIG. 5 to produce any desired cross sectional distribution of the grains in the granular body, including, for example, multiple cores such as those represented in FIG. 3. In the case of complex cross sectional geometric distributions, however, it is advantageous to pour the material onto a stationary table and to move the pouring spout across the body with a bidimensional operating means. The pouring process itself is represented in detail in FIG. 6. The surface 33 of the granular body 32 which is defined by hand 31, rotates about an axis 35. The cross section of the pouring spout 24 is very small in proportion to that of the body 32, and, with its horizontal movement in the direction of the arrow 37, it pours a layer along a spiral path. To keep the layer depth constant during each pass, the horizontal velocity must be adapted to the pouring rate according to its position. The doping profile is determined by the momentary proportion of the grains 10 and 16. The shape of the granular body can be defined during its formation in many different ways. Two preferred embodiments are represented in FIGS. 4 and 5. Another preferred step consists in solidifying the body at its periphery while it is being created. This is done by local heating with a flame, or in an especially well-defined manner with a focused laser beam. When the local heating is sufficient, the grains vitrify in the peripheral region and adhere to one another. The result is a supporting vitreous shell, but one which does not impair the permeability of the entire body to gases. Another advantageous method of shape-stabilization is to spray the circumference of the granular body with a cement which hardens rapidly and produces a self-supporting shell in the outer circumferential area. It is preferable to select a cement which will be destroyed without leaving any residue during the high-temperature processes which follow. Organic cements are suitable for this purpose, such as epoxy resins or glues on the basis of a thermoplastic. Another possibility for shape stabilization consists in stabilizing the entire granular body during the pouring process. This is accomplished by local heating with a flame, or better with a laser beam, such that the individual grains vitrify at the poured surface and adhere to one another without thereby appreciably impairing the permeability of the entire body to gases. Another advantageous system for the practice of the method of the invention is represented in FIG. 7. On a support 1", which is set in rapid rotation by a drive 20", there is placed a tube 2' as the supporting body. By means of a pouring spout 24' which can be moved in two coordinate directions by the drives 44 and 45, premixed grains 47 are fed in a controllable ratio of admixture. The rotational speed of the revolving table is selected such that grains deposited on the inside surface of tube 2' will be held in place by centrifugal force. The granular body is then built up in layers by the upward and downward movement of the pouring spout. The area directly about the axis of rotation, where the centrifugal force becomes low, is defined in the case of a graded index preform by an internal supporting tube (not shown) which is removed after the granular body has been transformed to a porous solid. The remaining cavity collapses when a glass body is formed from the porous body. In like manner, a tube or rod of high-purity fused silica can be used as the internal supporting body for the preparation of a stepped index profile preform. In this case the support is not removed when the glass body is formed. With the arrangement shown in FIG. 7, an especially high pouring rate can be achieved, since the ratio of admixture of the grains changes only slowly during the pouring, because in the movement of the pouring spout 24' in the direction of the axis of the body the ratio of the substance remains constant, while in the radial movement it changes in very small steps. After the pouring it is advantageous to stabilize the shape of the granular body and then compress it to form a porous compact. Isostatic compression is particularly suitable for this purpose. In the example given above, in which fused silica is used n the form of glass particles produced by pyrolysis, it has been found that, by the isostatic compression of the shape-stabilized granular body at a pressure of more than 2000 bar, a stable, finely porous compact is formed, which can be handled without special precautionary measures. Both the shape-stabilized granular body and porous compact are permeable to gases and therefore their properties can be modified by chemical treatment with gaseous substances. A chemical treatment of great practical importance in the case of fused silica is treatment for reduction of the hydroxyl content, since hydroxyl ions limit the transmission of the optic fibers in the infrared spectral range. For this purpose, it has been found desirable to expose the porous compacts or shape-stabilized granular bodies to an atmosphere of chlorine gas or helium-chlorine gas mixture in a closed vessel at temperature of 600° to 900° C. for one to five hours, depending on the size of the body and the hydroxyl content desired in the glass body. It is thus possible to lower an initial hydroxyl content of about 200 ppm to less than 0.1 ppm. When the glass body is formed from the finely porous compact or the shape-stabilized granular body, the gases present in them must be able to escape to a sufficient extent to enable a bubble free glass mass to be formed. Bubble-free melting is facilitated if, prior to the vitrification process, a thorough outgassing of the finely porous solid or shape-stabilized granular body takes place. A heat treatment of these bodies in a vacuum at temperatures of 100 to 400° C. has been found effective for this purpose. The duration of this heat treatment is determined by the size of the bodies and the vacuum. It has furthermore been found beneficial to saturate the porous compact or shape-stabilized granular body with a protective gas like helium or hydrogen right after the degassing, because the gas content of any bubbles that might be produced in the vitrification due to the presence of residual traces of these gases can be made to diffuse out of the bodies by thermal after-treatment of the latter. For vitrification, the shape-stabilized granular body or the finely porous solid body is passed through an annular kiln 62, such as the one represented diagrammatically in FIG. 8, in the direction of the arrow 64. This causes the diameter of the body to shrink, but produces no change in the pattern or geometric distribution of the glass-forming substances. Between the porous body 61 and the vitreous body 63 there forms a softening front, which is to be as well-defined as possible so as to permit gaseous inclusions to escape. This requirement is fulfilled by the annular kiln 62. In the case of a glass body of fused silica, the vitrification temperature amounts to 1500° to 1750° C. The glass body 63 may still contain a few small bubbles and/or voids after melting. If provision has been made by appropriate pretreatment as described above so that any bubbles present contain only gases which can easily diffuse through the vitreous body at higher temperatures (e.g., helium and hydrogen in silica), the gas can easily diffuse out of these bubbles through the surrounding glass body upon appropriate heat treatment. In this manner, after such treatment the only remaining voids will be those which will vanish entirely when the glass body is drawn to smaller diameters. A tested alternative to vitrification in an annular kiln is vitrification by hot isostatic compression. Since in this process there is no possibility for the gases included in the porous body to escape from the preform, care must be taken to see that only those gases are present in the porous body which can diffuse through the glass during subsequent heating. The process of the invention itself is largely dependent on the size of the grains. For practical reasons, it is necessary that the grains be free-flowing. However, this is the case over a wide range of grain diameters, and free flow can be assisted, for example, by jogging or sonic vibration. To prevent any undesirable granulation from impairing the optic properties when the granular body is vitrified, the grain size for the practice of the method of the invention is chosen in the range from 0.1 micrometers to 1 millimeter. Grains with a diameter distribution between 0.1 micrometer and 100 micrometers have proven especially desirable. In the applications thus far described for the method of the invention, the aim has been to prepare preforms which later will be used to produce optic fibers whose optic properties will be uniform over the entire length of the fiber. For use in communications terminals and in measuring instruments, it is furthermore important to have optic components, especially optic fibers, available whose optic properties, i.e., their wave guiding properties, vary within a given length. An example of practical importance is couplers, which consist of two cores situated close together within a single fiber, between which a crossover takes place on account of their close proximity, at least one transverse dimension of a core decreasing along the fiber, while the dimension of the other core increases along the fiber. While fibers or optic components in general in which the refractive index geometry varies longitudinally are very difficult or impossible to make by known methods, they can be made by the method of the invention without any particular difficulty. All that is necessary is to control the programming in relation to the depth of the grain deposit. FIGS. 4 and 5 show for the sake of simplicity systems in which the grains are fed to the granular body through one pouring device or, as in FIG. 4, through two pouring devices. It is obvious that more than one or two pouring devices can be used simultaneously. For example, in a system similar to that of FIG. 4 for the production of multiple cores, instead of one inner casing tube 3, a number of inner casing tubes can be used which is equal to the number of the cores that are to be formed. In arrangements similar to FIG. 5, it can be advantageous to use two pouring spouts, one of which covers the cladding area and the other the core area of the granular body to be formed. Since in the cladding area only grains of one composition need to be deposited, but the amount to be laid down in very much greater than it is in the core region, this uncritical process can be performed with a spout of a high rate of delivery. It is furthermore possible to shift several pouring spouts of identical function parallel to one another in order in this manner to attain a higher pouring rate than with a single pouring spout. It will be understood that the specification and examples are illustrative but not limitative of the present invention and that other embodiments within the spirit and scope of the invention will suggest themselves to those skilled in the art.
A granular body, from which an article having a nonuniform refractive index may be formed, has grains of two substances which have different refractive indicies in a geometric distribution in the granular body corresponding to the geometric distribution of the substances required for the nonuniform refractive index of the article and a way of shape-stabilizing the granular body. A method of making the granular body comprises controllably feeding the grains into the geometric distribution in the granular body and shape-stabilizing it. Preferably the granular body is compressed into a porous compact which holds itself together and is treated with a gas to achieve desired optic properties in the article.
2
CROSS REFERENCE TO RELATED APPLICATION This application is a continuation-in-part of prior U.S. patent application Ser. No. 14/261,928, filed Apr. 25, 2014, the disclosure of which is expressly incorporated herein in its entirety by reference. FIELD OF THE INVENTION The present invention relates to the clamping and supporting of tubing used to transport fluids, chemicals, oils and gases in industries, such as oil and gas drilling; and production and refining, where such tubing is commonly used. Other industries using tubing include shipping, military installations and equipment, food production installations, manufacturing sites, etc. In addition, the present invention is utilizable in corrosive environments, such as marine environments, where minimum contact between tubing, and the clamps that support the tubing, is preferable in order to reduce the accumulation of moisture contacting the tubing at the support area, which contact creates a risk of pitting and corrosion of the tubing. DESCRIPTION OF RELATED ART Clamping systems of the prior art include solutions for solving or reducing the problems associated with electrolysis and corrosion of tubing. However, the greater the contact area between the clamping supports and the tubing, the more the contact area is likely to collect and hold moisture. Vibration isolating and insulating materials are conventionally provided between the contact surfaces of the clamp supports and the tubing. However, such additional insulating materials hold moisture. Further, spacers, such as metallic spacers, are used with conventional clamping systems to space apart a series of tubes in a row. However, all such spacers and other adjuncts constitute additional parts in the manufacture and assembly of the clamps. Accordingly, such configurations are disadvantageous with respect to the economical and efficient implementation of such clamps in clamping systems for supporting tubing of various types of materials and sizes typically found in industrial installations and that exist in potentially corrosive environments. BRIEF SUMMARY OF THE INVENTION It is an object of the present invention to provide a clamp or an arrangement of clamps in a clamping system that provides minimum contact between the tubing support surfaces of the clamp and the tubing to allow for ventilation which minimizes electrolysis and corrosion of the tubing while offering a compact clamping system permitting uniform configurations of a variety of tubes with equal or different diameters. The clamps enable a number of tubes to be secured and supported within the same clamping system using one or more grooves of equal or unequal size (when supporting multiple tubes of the same OD) formed in the clamp support bodies in order to enable the tubes to seat properly with tubing engaging surfaces of the clamps and which surfaces have a minimum contact area. Embodiments of the present invention provide a corrosion reducing minimum contact clamp comprised of cylindrically shaped bodies made from a metallic, composite or plastic material for forming upper and lower clamp support bodies for securing an individual row of tubes or a rectangular array of tubes, including one or more spaced-apart tubing accommodating grooves of a shape having spaced groove inner and outer edges that form conical frustums. The grooves can be of equal or unequal size within the same clamp support bodies in order to enable tubes of different sizes or multiple tubes of the same size to be accommodated and properly seated side by side within the same tubing clamp. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1A illustrates a side view of a cylindrical clamp support body according to an embodiment of the present invention and having one groove with spaced inner and outer edges that define chamfered contact areas with the tubing to be supported. FIG. 1B illustrates an end view of the cylindrical clamp support body according to FIG. 1A . FIG. 1C illustrates a side view of a cylindrical clamp support body according to an embodiment of the present invention and having multiple grooves of the same dimensions with spaced inner and outer edges that form chamfered contact areas supporting tubing of substantially the same outer diameters. FIG. 1D illustrates an end view of the cylindrical clamp support body according to FIG. 1C . FIG. 1E illustrates a side view of a cylindrical clamp support body according to an embodiment of the present invention and having multiple grooves of different dimensions with spaced inner and outer edges that form chamfered contact areas supporting tubing of respectively different outer diameters. FIG. 1F illustrates an end view of the cylindrical clamp support body according to FIG. 1E . FIG. 1G illustrates a side view of a clamp comprised of upper and lower clamp support bodies according to the embodiment of FIG. 1A , having a tube clamped between them and being supported by the groove with chamfered surfaces. FIG. 1H illustrates a side view of a clamp comprised of upper and lower clamp support bodies according to the embodiment of FIG. 10 , having tubes clamped between them and being supported by the grooves with chamfered surfaces. FIG. 1I illustrates a side view of a clamp comprised of upper and lower clamp support bodies according to the embodiment of FIG. 1E , having tubes of respectively different diameters clamped between them and being supported by the grooves with chamfered surfaces. FIGS. 2A and 2B are detailed views of the cylindrical clamp support body according to the embodiment of the invention shown in FIG. 1E showing the base, chamfer angles and depth of grooves of the clamp body. FIG. 3A illustrates a side view of a cylindrical clamp support body according to another embodiment of the present invention and having one groove with chamfered surfaces that form contact areas with the tubing to be supported. FIG. 3B illustrates an end view of the cylindrical clamp support body according to FIG. 3A . FIG. 3C illustrates a side view of a cylindrical clamp support body according to another embodiment of the present invention and having multiple grooves of different dimensions with chamfered surfaces that form contact areas supporting tubing of respectively different outer diameters. FIG. 3D illustrates an end view of the cylindrical clamp support body according to FIG. 3C . FIG. 3E illustrates a side view of a clamp comprised of upper and lower clamp support bodies according to the embodiment of FIG. 3C and a middle clamp support body of FIG. 1E respectively supporting rows of tubes with mixed outer diameters clamped between the clamp support bodies and supported by the respective grooves with chamfered surfaces, secured by fasteners as part of a clamping assembly or system. FIG. 3F illustrates a side view of a clamp comprised of upper and lower clamp support bodies according to the embodiment of FIG. 3A supporting a tube clamped between the clamp support bodies and supported by the respective grooves with chamfered surfaces and secured by fasteners. FIG. 3G illustrates a side view of a clamp according to another embodiment of the invention comprised of an upper clamp support body without any grooves and a lower clamp support body of the embodiment of FIG. 3A having grooves supporting a tube clamped between the upper and lower clamp support bodies, and secured by fasteners. FIG. 4A is an end view of a cylindrical clamp support body in accordance with another embodiment of the present invention. FIG. 4B is a side elevation view of the cylindrical clamp support body of FIG. 4A . FIG. 4C is a top plan view of the cylindrical clamp support body of FIG. 4A . FIG. 5A is an end view of another preferred embodiment of a cylindrical clamp support body in accordance with the present invention. FIG. 5B is a side elevation view of the cylindrical clamp support body of FIG. 5A . FIG. 5C is a top plan view of the cylindrical clamp support body of FIG. 5A . FIG. 6A is an end view of another preferred embodiment of the cylindrical clamp support body in accordance with the present invention. FIG. 6B is a side elevation view of the cylindrical clamp support body of FIG. 6A . FIG. 6C is a top plan view of the cylindrical clamp support body of FIG. 6A . FIG. 7A is an end view of a clamp utilizing two of the cylindrical clamp support bodies in accordance with FIG. 4A . FIG. 7B is a side elevation view of the clamp depicted in FIG. 7A . FIG. 8A is an end view of a clamp in accordance with the present invention and utilizing one of the cylindrical clamp support bodies depicted in FIG. 4A and a cylindrical clamp rod. FIG. 8B is a side elevation view of the clamp depicted in FIG. 8A . FIG. 9A is an end view of a clamp utilizing two the cylindrical clamp support bodies depicted in FIG. 5A in accordance with the present invention. FIG. 9B is a side elevation view of the clamp depicted in FIG. 9A . FIG. 10A is an end view of a clamp in accordance with the present invention and utilizing one of the cylindrical clamp support bodies depicted in FIG. 5A and a cylindrical clamp rod. FIG. 10B is a side elevation view of the clamp depicted in FIG. 10A . FIG. 11A is an end view of a clamp in accordance with the present invention and utilizing two of the cylindrical clamp support bodies of FIG. 6A . FIG. 11B is a side elevation view of the clamp depicted in FIG. 11A . DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1A shows a first preferred embodiment of a clamp support body of right circular cylindrical shape, generally at 1 , and having a single circular groove 2 with features of a wedge and having groove outer edges 3 and groove inner edges 7 which are spaced apart from each other at a radial outer portion of the groove. Each pair of spaced outer and inner groove edges 3 ; 7 cooperate to form one of two mirrored right conical frustums 4 , each such conical frustum 4 having a frustum width “f”. The right conical frustums 4 each formed by the groove edges 3 ; 7 on one of the two sides of the groove 2 each form a wedge and are the contact surfaces for tubing, when clamped. The wedge shape prevents the tubing from shifting to either side. The conical frustums 4 , each formed by one pair of the groove edges 3 ; 7 , are each a truncated conical surface that comes in contact with the tubing, which is typically of circular shape, resulting in a minimal contact area of the clamp and tubing. A groove depth 5 of groove 2 provides a space between a circular groove base 22 of the groove 2 and the tubing. This space is required to allow ventilation for drying any liquids that might be present or which might accumulate as a result of the installation environment. In one embodiment of the present invention, a distance 8 from a longitudinal axis of symmetry “a” of the clamp support body, to the circular groove base 22 of the groove 2 , which groove 2 itself has the depth 5 , as shown in FIG. 1B , is not less than 0.125 inch. Overall, the length 9 of the clamp support body is not less than 1.25 inches, for example. The outer edge 3 of the right conical frustum 4 is shown having a circumference which is equal to that of the surface of greatest circumference 14 of the clamp and is the outer edge 3 of the groove 2 . In the following description, a tube is used as an exemplary application. However, the present invention may be used with any cylindrical type body, such as a pipe and the like. FIGS. 1C and 1D show a clamp support body of right circular cylindrical shape 1 ′ that is consistent with the features of the clamp support body 1 shown in FIG. 1A , except for having multiple spaced-apart grooves 2 for clamping and supporting more than one tube of equal diameter. FIGS. 1E and 1F show a clamp support body of right circular cylindrical shape 111 having multiple circular grooves 2 of identical size and dimension in each of a first series of grooves 6 and a second series of grooves 60 , which form a multiple series 70 of spaced-apart grooves 2 . All the grooves 70 have inner and outer edges 3 ; 7 defining wedges formed as right conical frustums 4 in an alternating arrangement. In one embodiment of the present invention, the distance 8 from the longitudinal axis of symmetry “a” of the clamp support body to the greatest depth of the second series of grooves 60 , each of which has a depth 5 ′, is shown in the side view and is not less than 0.125 inch. The configuration of grooves shown in FIGS. 1E and 1F allows for the clamping of multiple sized tubes in the same row and side by side. The first series of grooves 6 have circular groove base 22 . The second series of grooves 60 have bases 220 which are arcuate in the direction of the longitudinal axis “a”, as in FIGS. 1E, 2A and 2B , for example. FIG. 1G illustrates two clamp support bodies, generally at 1 and each with a cylindrical shape having molded shape surfaces and being held together by assembly hardware, generally at 12 , such as bolts 50 and nuts 52 , and clamping a single tube 13 as part of a clamp assembly. FIG. 1H illustrates two clamp support bodies of right circular cylindrical shape 1 1 held together by assembly hardware, generally at 12 , and consisting of bolts 50 and nuts 52 , and clamping multiple tubes 13 of equal diameter. FIG. 1I illustrates three clamp support bodies of right circular cylindrical shape 111 held together by assembly hardware, generally at 12 , such as bolts 50 and nuts 52 , and clamping multiple series of tubing 13 of unequal diameter in a same row and in a rectangular array as part of a clamp assembly or clamp system. FIG. 2A illustrates the embodiment of the present invention shown in FIG. 1E in which the greatest width 23 of each groove, measured from its outer edges 3 connecting to the surface 14 with the greatest circumference of the clamp, is not less than 0.177 inch. Proportionate spacing 25 between grooves 2 forms a tightly spaced arrangement that allows for the tubing 13 to be arranged as compactly as possible while providing adequate spacing for ventilation between each tube. FIG. 2B illustrates a clamp support body, generally at 111 , of right circular cylindrical shape showing the grooves 2 having circular groove bases 22 which are even and parallel with the axis of symmetry “a” and which are circular in a cross section. The circular groove bases 22 of the grooves 2 provide more space between tubing and clamp surface as well as a stronger base design when required. In FIG. 2B , the grooves 2 have spaced outer and inner edges 3 ; 7 which define right conical frustums 4 each having a cone angle which may range from 45 degrees to 85 degrees, for example, to accommodate multiple diameters of tubing. The groove bases 220 , which are shown at the right of FIGS. 1E, 2A and 2B , for example are arcuate in the direction of the longitudinal axis “a”. FIGS. 3A and 3B illustrate a clamp support body of right circular cylindrical shape, generally at 40 , which is bisymmetrically segmented by a single plane 17 oriented in line with the cylinder's longitudinal axis of symmetry “a”. The plane 17 defines a quadrilateral base support surface 24 with the clamp support body, generally at 40 , having one symmetrical groove 2 defined by spaced outer and inner edges 3 ; 7 forming two right conical frustum sections 4 . FIGS. 3C and 3D illustrate a clamp support body of right circular cylindrical shape, generally at 42 , and which is segmented by a single plane 17 oriented parallel but offset from the cylinder's longitudinal axis of symmetry “a” to form a series of base support surfaces 26 . The plane 17 in FIG. 3C segments the clamp support body, generally at 42 , into unequal halves unlike the segmentation of the clamp support body, generally at 40 in FIG. 3A , and leaves the circular groove base 22 of the circular groove 2 with the circumference 20 as circular. The clamp is more rigid as a result. In each of the clamp support bodies shown in FIGS. 3A-3D , the cylindrical segment shape of the clamp enables a more compact clamping system. The circumferential length of the grooves' outer edges 3 and the clamps' greatest circumference 14 are equal. The outer edge 3 of the right conical frustum section 4 has a circumference which is equal to the clamp surface area 14 having the greatest circumference of the clamp 6 . FIG. 3E illustrates a stack of clamp support bodies of right circular cylindrical shape with the top and bottom support bodies being segmented by a single plane which is oriented parallel to the cylinder's axis of symmetry, as shown in FIGS. 3A-3C , and the middle clamp support body being un-segmented as, for example, shown in FIGS. 2A-2B . The three clamp support bodies arrange the tubing 13 in a rectangular array with assembly hardware, generally at 12 , bringing them together. The number of tubes 13 clamped in a rectangular array of tubing can be increased by adding one or more clamps on the top or bottom or by increasing the length of the clamp bodies and the number of grooves 1 in those clamp bodies. Optionally, also shown in FIG. 3E are top and bottom backing plates 21 engaged by the fasteners, generally at 12 , and providing for added support. Optionally, a middle clamp support body may comprise two of the segmented clamp support bodies each, such as the segmented clamp support body 42 shown in FIG. 3C , disposed back to back and having a single backing plate 21 therebetween. FIG. 3F illustrates two clamp support bodies of right circular cylindrical shape 1 and each segmented by a single plane oriented parallel to the cylinder's longitudinal axis of symmetry “a”, as depicted in FIG. 3A . These two clamp support bodies are used to clamp and to support a single tube 13 , using the assembly hardware, generally at 12 . FIG. 3G illustrates a side view of a clamp according to another embodiment of the invention in which an upper cylindrical clamp support body 30 without any grooves and a lower clamp support body 40 segmented by a single plane and having a groove 12 , as shown in the embodiment of FIG. 3A , support a tube 13 clamped therebetween. The upper cylindrical clamp support body 30 , without grooves, is a cylindrical rod. The upper backing plate 21 and the lower clamp support body 40 are secured by fasteners, generally at 12 . In this way, a three point support system is provided for supporting the tubing, i.e. using a clamp support body 40 having grooves providing two support points and an upper cylindrical support body 30 providing a third support point. The tubing clamp assemblies of FIGS. 1G, 1H, 1I and 3E can also be modified to include an upper or lower cylindrical clamp support body 30 without grooves in place of a clamp support body having grooves, in order to provide the three point contact support shown in FIG. 3G , with or without the use of additional backing plate(s) 21 as shown in FIG. 3E . Further, for applications in which there are different sized tubing 13 being accommodated in the three point support configuration, the depth of the grooves 2 may be adjusted on the grooved clamp support body to ensure that the top surface of each of the different OD tubes 13 engages the upper clamp body in a straight line, substantially parallel to the longitudinal axis of symmetry “a”. Alternatively, the upper clamp support body may have a step profile where the stepped part accommodates the tubes 13 , each having a different OD, when tubes 13 of different diameters are accommodated together in a row of a three point clamp configuration. Referring now to FIG. 4A , there may be seen, generally at 300 , another preferred embodiment of the cylindrical clamp support body in accordance with the present invention. As were the previously described embodiments, the embodiment of the present invention, as depicted at 300 in FIG. 4A , has a right circular cylindrical shape, similar to the shape of the clamp support body depicted in FIGS. 3A and 3B . The clamp support body, generally at 300 , is longitudinally segmented by a single plane 302 . The plane 302 defines a quadrilateral base support surface 304 . The cylindrical clamp support body, generally at 300 , is defined by spaced ends 306 ; 308 , a plurality of circular grooves 312 , as seen in FIGS. 4B and 4 C and a land 314 which is intermediate the spaced ends 306 , 308 and which divides the cylindrical clamp support body 300 into left and right cylindrical clamp support body sections 316 and 318 , respectively. In the embodiment depicted in FIGS. 4A, 4B and 4C , the left and right cylindrical clamp support sections 316 and 318 are of equal length and the land 314 is equidistant from the left and right cylindrical clamp support body ends 306 and 308 . While that configuration is a preferred one, it will be understood that the lengths of the left and right cylindrical clamp support body sections 316 and 318 are not necessarily equal. One of the sections can be longer or shorter, than the other section. The right circular cylindrical clamp support body depicted generally at 300 in FIGS. 4A, 4B and 4C includes the plurality of grooves 312 . It will be understood that each of these grooves 312 is generally similar to the grooves depicted and disclosed in the various prior embodiments. Each such groove 312 is defined by a groove outer edge 320 and a groove inner edge 322 . These groove edges 320 ; 322 define between them a right truncated conical surface 324 . That right truncated conical surface 324 provides a support surface of minimum contact area to support a tube, generally at 13 , as was discussed previously, and as will be seen in FIGS. 7A and 7B , for example. In the embodiment of the clamp support body depicted generally at 300 in FIGS. 4A, 4B and 4C , the groove base 326 of each of the circular grooves 312 is an annular groove base 326 , generally similar to the annular groove bases 220 depicted at the right of the cylindrical clamp support body 111 depicted in FIG. 1E . While these groove bases 326 could also be circular groove bases, such as the ones depicted at 22 in FIG. 1E , it has been found that the arcuate groove bases, such as the ones depicted at 326 in FIGS. 4A, 4B and 4C provide greater strength for the clamp support body, generally at 300 . The intermediate land, generally at 314 of the cylindrical clamp support body 300 of the embodiment of the present invention depicted at FIGS. 4A, 4B and 4C , has a land surface 328 of greatest circumference, which circumference is essentially the same as the circumferential surface 14 of the previously described preferred embodiments of the present invention. A fastener receiving hole 330 is formed in the intermediate land, generally at 314 , and is the same in function as the fastener receiving holes depicted at 80 in the previously described embodiments of the present invention. The fastener receiving hole 330 extends from the surface of greatest circumference 328 of the intermediate land 314 to the plane 312 and has a hole axis which is generally perpendicular to the plane 302 which defines the quadrilateral base support surface 304 . Turning now to FIGS. 7A and 7B , there may be seen, generally at 340 , a clamp for use to support a plurality of tubes, generally at 13 , which clamp 340 is configured using two of the cylindrical clamp support bodies 300 depicted in FIGS. 4A, 4B and 4C . A top backing plate 342 is placed into engagement with the plane 302 which is now located at an upper portion of the now inverted upper cylindrical clamp support body 300 . A similar bottom backing plate 344 is placed beneath the lower cylindrical clamp support body 300 . Each of these top and bottom backing plates 342 ; 344 is provided with a backing plate fastener receiving hole 346 . These backing plate fastener receiving holes 346 are each formed in their respective backing plate 342 ; 344 to be in alignment with a respective one of the fastener receiving holes 330 which are formed in each intermediate land 314 of each of the two circular clamp support bodies 300 . When the clamp 340 is assembled, as depicted in FIGS. 7A and 7B , suitable assembly hardware 12 , such as a bolt 50 and a nut 52 , can be utilized to secure the two cylindrical clamp support bodies 300 together to clamp a plurality of tubes 13 therebetween. In the embodiment of the present invention depicted in FIGS. 4A, 4B, 4C, 7A and 7B , the primary difference between this embodiment and the previously disclosed and depicted embodiments is the location of the intermediate land 314 intermediate the ends 306 and 308 of each cylindrical clamp support body 300 , and the presence of a fastener receiving hole 330 in each such intermediate land 314 . As compared with the clamps depicted in FIGS. 3E, 3F and 3G , for example, the use of an intermediate land 314 , with its associated fastener receiving hole 330 for each cylindrical clamp support body 300 , makes the assembly of the clamp depicted at 340 in FIGS. 7A and 7B more expeditious than the assembly of a generally similar clamp depicted in FIGS. 3E, 3F and 3G . While not specifically depicted, it will also be understood that it is within the scope of the present invention to provide an embodiment of the cylindrical clamp support body, which is not specifically shown, and which could be provided with fastener receiving holes 80 in one or both ends and which also can be provided with the fastener receiving hole 330 in an intermediate land 314 . Such a cylindrical clamp support body would provide a component of a clamp that would be usable in situations where greater clamping strength than could be provided by either of the clamp embodiments with a fastener hole in an intermediate land, or with fastener holes in one or both of the ends could provide. FIGS. 8A and 8B show another embodiment of a clamp, generally at 350 , which is configured utilizing one of the cylindrical clamp support bodies, generally at 300 , in FIGS. 4A, 4B and 4C . Instead of using two such cylindrical clamp support bodies 300 , as is depicted in FIGS. 4A, 4B and 4C , in the embodiment of the clamp 350 , in accordance with the present invention, as depicted in FIGS. 8A and 8B , one of the components is a cylindrical clamp support body 300 , while the other component is a cylindrical clamp support rod, generally at 352 . In this clamp configuration, the cylindrical clamp support rod 352 has a smooth circumferential outer surface 354 . That smooth circumferential outer surface 354 of the cylindrical clamp support rod 352 is devoid of any grooves, groove edges or chamfered support surfaces. When a tube or tubes 13 are held in this clamp, generally at 350 , they are held using essentially a three point contact, as opposed to the four point contact, as depicted in FIGS. 7A and 7B . The cylindrical clamp support body, generally at 300 , which is the same as each of the cylindrical clamp support bodies depicted in FIGS. 4A, 4B and 4C , provides two points of contact between the clamp support body 300 and a clamped tube 13 . These are the two right truncated conical support surfaces 324 defined by the spaced outer and inner edges 320 ; 322 of each cylindrical groove 312 . The third contact point is provided by the smooth circumferential surface 354 of the cylindrical clamp support rod 352 which forms the second member of the clamp 350 in accordance with the present invention, as depicted in FIGS. 8A and 8B . Other than the absence of the spaced cylindrical grooves 312 , the cylindrical clamp support rod 352 of the embodiment of the present invention, as depicted in FIGS. 8A and 8B , is essentially the same as the embodiment depicted in FIGS. 7A and 7B . The clamp 360 of FIGS. 8A and 8B is less expensive than the clamp 340 of FIGS. 7A and 7B since the cylindrical clamp support rod 352 is less expensive to manufacture. A further preferred embodiment of the cylindrical clamp support body, in accordance with the present invention, is depicted generally at 360 in FIGS. 5A, 5B and 5C . This further preferred embodiment of a cylindrical clamp support body 360 is generally the same as the preferred embodiment depicted at 300 in FIGS. 4A, 4B and 4C . Similar reference numerals will be utilized to identify corresponding features in both. In the cylindrical clamp support body 360 depicted in FIGS. 5A, 5B and 5C , the quadrilateral base support surface 304 of the FIGS. 4A, 4B and 4C embodiment is modified in the FIGS. 5A, 5B and 5C embodiment. The base support surface, generally at 362 of the cylindrical clamp support body 360 of the embodiment depicted in FIGS. 5A, 5B and 5C , instead of being planar, is instead formed with an elongated backing plate receiving channel 364 which extends the length of the cylindrical clamp support body 360 . The cylindrical backing plate receiving channel 364 has a channel width 366 which is less than the overall width 368 of the clamp base surface, generally at 304 . A pair of outer channel flanges 370 are contiguous with the surface of greatest circumference 328 of the cylindrical clamp support body 360 depicted in FIGS. 5A, 5B and 5C . In all other aspects, the cylindrical clamp support body 360 is the same as the cylindrical clamp support body 300 depicted in FIGS. 4A, 4B and 4C . While the overall length of the cylindrical clamp support body 360 is greater than an overall length of the clamp support body 300 , this is not a substantial difference. The cylindrical clamp support bodies, in accordance with the present invention, can be provided in various structural lengths. If necessary, a cylindrical clamp support body can be made shorter by severing the clamp support body in a surface of greatest circumference or in a groove, by accomplishing a generally conventional cutting process. Turning to FIGS. 9A and 9B , there may be seen a clamp, generally at 380 , which is comprised of two of the cylindrical clamp support bodies 360 depicted in FIGS. 5A, 5B and 5C and each utilizing the backing plate receiving channel, generally at 364 . As seen in FIGS. 9A and 9B , the top and bottom backing plates 344 ; 346 respectively are now received in the cooperatively shaped backing plate receiving channels 364 of the two cylindrical clamp support bodies 360 of this preferred embodiment. Once the two cylindrical clamp support bodies 360 have been positioned to engage a number of tubes 13 to be clamped, the top and bottom backing plates 342 ; 344 are placed in their respective channels 364 and suitable fastening hardware, generally at 12 , is used to clamp the two clamp support bodies 360 in place. The provision of the backing plate receiving channels 364 in each of the cylindrical clamp support bodies 360 , in accordance with this preferred embodiment of the present invention, as depicted in FIGS. 5A, 5B and 5C , as well as in FIGS. 9A and 9B , prevents any shifting or rotation of the backing plates 342 , 344 during assembly of the two cylindrical clamp support bodies 360 to form the clamp depicted at 380 in FIGS. 9A and 9B . The seating of the backing plates 342 , 344 , in the associated backing plate receiving channels 364 overcomes any potential for these backing plates 342 ; 344 to possibly rotate or shift out of position during assembly of the two cylindrical clamp support bodies 360 to form the clamp 380 depicted in FIGS. 9A and 9B . FIGS. 10A and 10B depict yet another clamp in accordance with the present invention, generally at 390 , which clamp 390 is generally similar to the clamp depicted in FIGS. 8A and 8B , generally at 350 . In the clamp 390 , which is depicted in FIGS. 10A and 10B , the clamp is configured using one cylindrical clamp support body, such as the one depicted at 360 in FIG. 5A , and using one of the cylindrical clamp support rods 392 , similar to the one depicted generally at 352 in FIGS. 8A and 8B . In this clamp embodiment 390 , the cylindrical clamp support rod 392 is provided with a backing plate receiving channel 394 which is the same, in structure and function, as the backing plate receiving channel 364 discussed in connection with the embodiment of the present invention depicted in FIGS. 5A, 5B, 5C, 9A and 9B . In the embodiment depicted in FIGS. 10A and 10B , as was the situation with the embodiment depicted in FIGS. 8A and 8B , the cylindrical clamp support body, generally at 360 , can be positioned either in the upper or top position, as depicted in FIGS. 10A and 10B , with the cylindrical clamp support rod 392 in the bottom position, or the relative positions of the two components could be reversed. Also, as was discussed above, the overall length of the cylindrical clamp support body 360 and of the cylindrical clamp support rod 392 could be varied in accordance with a number of the tubes 13 that are to be supported and clamped. Also, as was previous discussed, the location of the intermediate land 314 does not have to be centered between the two ends 306 , 308 of the cylindrical clamp support body. As will be discussed in connection with the next preferred embodiment, which is depicted generally at 400 in FIGS. 6A, 6B and 6C , as well as in FIGS. 11A and 11B , if the sizes of tubes 13 to be clamped on one side of the intermediate land 314 are different from the size of the tubes 13 to be supported on the other side of the intermediate land 314 , the location of that intermediate land may be shifted to balance the load that is imposed on the clamp. A still further embodiment of the cylindrical clamp support body in accordance with the present invention is depicted generally at 400 in FIGS. 6A, 6B and 6C . In this embodiment, the cylindrical grooves 402 have a first effective diameter while the cylindrical grooves 404 having a second effective diameter with the cylindrical grooves 404 have a second effective diameter which, in the configuration depicted in FIGS. 6A, 6B and 6C is less than the diameters of the first cylindrical grooves 402 . Since the diameters of the second cylindrical grooves 404 are less, the groove depths of these grooves are greater. Bases 406 of the circular grooves with the reduced diameters 404 are further away from the surface of greatest circumference 14 of the cylindrical clamp body 400 than are the groove bases 408 of the plurality of cylindrical grooves 402 having the larger groove diameter. In other respects, the cylindrical clamp support body depicted generally at 400 in FIGS. 6A, 6B and 6C is essentially the same as a cylindrical clamp support body depicted generally at 300 in FIGS. 4A, 4B and 4C . While the number of circular grooves 312 is less in the FIGS. 4A, 4B and 4C embodiment than is the number of corresponding circular grooves 402 and 404 in the embodiment of the cylindrical clamp support body depicted generally at 400 , this difference is not significant. In each of these embodiments, the overall length of the cylindrical clamp support body and the number of grooves, generally at 312 or at 402 ; 404 that are formed in that clamp support body is a function of intended usage. As has also been discussed above, the intermediate land 314 does not have to be positioned equidistant between the two ends 306 , 308 of the cylindrical clamp support body depicted generally at 400 in FIGS. 5A, 5B and 5C . A clamp which utilizes two of the cylindrical clamp support bodies 400 , depicted in FIGS. 6A, 6B and 6C , is shown generally at 410 in FIGS. 11A and 11B . This clamp, generally at 410 , utilizes two of the cylindrical clamp support bodies 400 , each with cylindrical grooves 402 and 404 of differing diameters. As may be seen in FIGS. 11A and 11B , tubes 13 of differing diameters can be clamped between the two cylindrical clamp support bodies 400 . In the clamp depicted generally at 410 in FIGS. 11A and 11B , the top backing plate 342 and the bottom backing plate 344 are positioned in contact with a quadrilateral base support surface of each of the cylindrical clamp support bodies, generally similarly to the configuration depicted in FIGS. 7A and 7B . It will be understood that each of the cylindrical clamp support bodies 400 that are used to form the clamp, generally at 410 , could also be provided with backing plate receiving channels, such as the ones depicted at 364 in connection with FIGS. 5A, 5B and 5C . Further, it is to be also understood that the clamp, generally at 410 in FIGS. 11A and 11B , could be structured using only one cylindrical clamp support body, generally at 400 , and one cylindrical clamp support rod, such as the one depicted at 352 in FIGS. 10A and 10B , for example. All of these variations are within the scope of the present invention. In accordance with the preferred embodiments of the present invention, the clamp support bodies can be manufactured from metal or plastic cylindrical rods, for example of stainless steel, aluminum or synthetic resin, such as DELRIN™. Teflon or Teflon coatings are also suitable in the manufacture. Using a synthetic resin for the clamp support body prevents dissimilar material contact problems from arising. However, using a material for the clamp support body which matches that of the tubing also prevents dissimilar material contact problems from arising. In some embodiments, the clamp support bodies and the backing plates are manufactured and the holes for accommodating the fasteners, generally at 12 , are drilled in the bodies during assembly of the clamp support bodies. The holes may also be pre-drilled at the time of manufacture of the clamp support bodies. While preferred embodiments of a corrosion reducing minimum contact clamp for supporting and securing tubing, in accordance with the present invention, have been set forth fully and completely hereinabove, it will be apparent to one of skill in the art that changes could be made, without departing from the true spirit and scope of the present invention, which is accordingly to be limited only by the appended claims.
Tubing clamps having a minimum contact area between the tubes and supporting surfaces of clamp support bodies are provided for minimizing the collection and retention of liquids at the supporting surfaces. A minimum spacing is maintained between the tubes supported by the tubing clamps while maintaining sufficient ventilation between the tubes and the clamp support bodies to permit drying of any liquids which contact the tubes and the clamp support bodies at tubing support points. This prevents electrolysis and corrosion which may be caused by liquid retention and by contact between dissimilar metals. The tubing clamps are adapted to secure tubes having differing outer diameters in a single row or in multiple rows, such as in a stacked configuration. The clamps are provided with upper and lower supports, each having matching grooves that have chamfered edges forming the upper and lower tubing contact surfaces. The supports are secured together with fasteners to clamp the tubing therebetween.
5
FIELD OF THE INVENTION [0001] The present invention relates to brake system, and more particularly, to method, apparatus, and program product for controlling a parking brake. BACKGROUND OF THE INVENTION [0002] Most vehicle designs incorporate parking brakes. Typical parking brake configurations continuously employ regular drum brakes on a rear wheel. Parking brakes commonly rely on simple mechanical linkage to engage the brakes. The driver may simply pull a lever which is coupled to a brake cable which actuates the brakes. To release the brake, a button is pressed while lifting and releasing the lever. For these types of parking brakes, there may be a relatively large amount of “play” in the brake cable, i.e., a relatively large range of motion of the lever and brake cable may be required in order to supply sufficient braking force to retain the vehicle in place. This is generally satisfactory, since the drive may simply lift the lever until sufficient force has been applied. [0003] However, in some systems, the parking brake is engaged electronically. The driver may simply depress a pedal, lever, button or other suitable means, which sends a signal to a controller or actuator which engages the brake. [0004] In these type of systems, since the brake is automatically actuated, it is important to know when a target force is being applied to the wheel(s), such that the vehicle is retained in its current position. Some systems accomplish this by using a force sensor which measure the force being applied by the brake. The brake or brake actuator may therefore be controlled using closed loop forced feedback. [0005] However, such sensors add cost to the system. And harsh environmental factors, such as temperature variation and moisture, reduce the reliability and accuracy of the sensors. Additional circuitry may be used to compensate for the drift and sensitivity variations caused by the factors, however, this again adds cost and complexity to the system. [0006] The present invention is aimed at one or more of the problems identified above. SUMMARY OF THE INVENTION [0007] In a first aspect of the present invention, a method for calibrating a brake mechanism having a brake coupled to an actuator is provided. The actuator includes a motor and is controlled through rotations of the motor. The motor includes the steps of initializing the brake mechanism, applying a predetermined power level to the actuator, establishing motor stall and responsively determining a reference motor position, and establishing a home motor position as a function of the second position and a predetermined constant. [0008] In a second aspect of the present invention, a brake mechanism, is provided. The brake mechanism includes a brake operable to restrict movement of a vehicle and an actuator coupled to the brake. The actuator is operable to selectively apply and release the brake. The mechanism further includes a controller coupled to the actuator. The controller is operable to initialize the brake mechanism and apply a predetermined power level to the actuator, to establish motor stall and responsively determine a reference motor position, and to establish a home motor position as a function of the second position and a predetermined constant. [0009] In a third aspect of the present invention, a program product for calibrating a brake mechanism having a brake coupled to an actuator is provided. The actuator includes a motor and is controlled through rotations of the motor. The program product includes program code means for initializing the brake mechanism, for applying a predetermined power level to the actuator, for establishing motor stall and responsively determining a reference motor position, and for establishing a home motor position as a function of the second position and a predetermined constant. [0010] In a fourth aspect of the present invention, a method for providing diagnostics for a brake mechanism having a brake coupled to an actuator is provided. The actuator has a motor and is controlled through rotations of the motor. The method includes the steps of establishing a current motor position, incrementing power to the motor to achieve a target position, and determining the power required to move motor to the target position when the motor has reached the target position. The method also includes the step of determining if the required power is outside of a predetermined range. [0011] In a fifth aspect of the present invention, a brake mechanism is provided. The brake mechanism includes a brake operable to restrict movement of a vehicle and an actuator, having a motor, coupled to the brake. The actuator is operable to selectively apply and release the brake. The mechanism also includes a controller coupled to the actuator and being operable to establish a current motor position, increment power to the motor to achieve a target position, and determine power required to incrementally move the motor has and to determine if the required power is outside of a predetermined range. BRIEF DESCRIPTION OF THE DRAWINGS [0012] Other 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 wherein: [0013] FIG. 1 is a block diagram that illustrates a brake system environment consistent with the principles of the present invention. [0014] FIG. 2 is a graph representing forces incident on the actuator of FIG. 1 versus displacement of the actuator. [0015] FIG. 3A is a first portion of a flowchart that embodies steps suited for implementation within the brake system environment of FIG. 1 . [0016] FIG. 3B is a second portion of the flowchart of FIG. 3A . [0017] FIG. 4 is a second graph representing forces incident on the actuator of FIG. 1 versus distance of the actuator. [0018] FIG. 5A is a first portion of a second flowchart that embodies steps suited for implementation within the brake system environment of FIG. 1 . [0019] FIG. 5B is a second portion of the flowchart of FIG. 5A . DETAILED DESCRIPTION [0020] The block diagram of FIG. 1 illustrates a brake mechanism 10 that is consistent with the principles of the present invention. The brake system 10 employs position control functions to regulate the actuation and release of a brake 20 , such as a parking brake. Generally, a controller 12 may execute a combined load/position algorithm configured to control the movement of an actuator 14 . The actuator 14 is coupled to the brake 20 and may be configured to selectively actuate and release brake 20 in response to a command or command signals. The brake 20 is operable to restrict movement of a vehicle (not shown). As such, the travel of the actuator 14 causes a force to be transferred to the brake 20 . [0021] The algorithm controlling the movement of the actuator 14 includes calibration and diagnostic routines which may account for variations within the brake mechanism 10 and for determining when a target load is being applied by the brake 20 . [0022] In one embodiment, the brake 20 is a disc brake which is directly coupled to the actuator 14 . As such, the travel of the actuator 14 causes a force to be transferred directly to the brake 20 . [0023] In another embodiment, the brake 20 is a drum brake. The actuator 14 is connected to a brake cable (not shown). The brake cable, in turn, is coupled to the brake 20 via a brake lever (not shown). In one embodiment, the brake lever is operable to actuate the drum brakes/calipers of, for example, the rear brake 20 of a vehicle (not shown). The brake is operable to restrict movement of the vehicle. As such, the travel of the actuator 14 causes a force to be transferred to the brake lever via the cable. [0024] An operator may initiate actuation or release of the brake 20 through actuation of a control device 22 , such as a button and/or lever. The control device 22 may transmit an actuation and/or release signal to the controller 12 . The controller 12 may include a computer, central processing unit, microprocessor or other suitable control device. [0025] In general, the controller 12 , in response to the actuation and/or release signal, may initiate processing of a position feedback control program (or program product) resident in the controller 12 . The program may instruct the controller 12 to transmit a command to a motor in the actuator 14 . In addition to the motor, the actuator 14 may incorporate a position sensor, a power screw and a gear set (not shown) for gaining mechanical advantage. In response to the command, the actuator 14 may travel in directions along an axis of the actuator 14 . Alternatively, it will be appreciated that movement of the actuator 14 may occur in any direction corresponding to an increase or decrease of brake force. This movement of the actuator 14 is accomplished according to a position feedback control program. [0026] In the illustrated embodiment, the position feedback control program requires is based on a home position, i.e., the zero force or drag position, at which no force is exerted by the brake 20 . In one aspect of the present invention, the controller 12 implements a calibration routine under power-up, e.g., when the vehicle's engine is started. The calibration routine is aimed at determining the zero force or drag position of the actuator 14 . In the illustrated embodiment, this zero force position is defined in terms of a (rotary) motor position within the actuator 14 . For example, the rotary motor position may be defined in terms of turns (counts) of the motor. [0027] With reference to FIG. 2 , an exemplary force/displacement curve for illustrating operation of the calibration routine is shown. The zero force position is labeled X 2 . The two forces, F REF and F 1 , are within the linear force/displacement region 24 of the actuator 14 . F REF and F 1 are predetermined values. In one embodiment, F REF is defined as the force at which the motor will stall, i.e., rotational velocity equal to zero and F 1 is the defined as approximately the force required to hold the vehicle on a 20% grade. [0028] Generally, the calibration routine determines the home motor position (X 2 ) as a position or count of the motor by establishing the motor position at which the actuator 14 exerts a force equal to F REF and then, using the known nominal characteristics of the actuator 14 , establishing X 2 . [0029] With particular reference to FIGS. 3A and 3B , a method 26 for calibrating and providing start-up diagnostics for the brake mechanism 10 according to an embodiment of the present invention is shown. In a first step 26 , the brake mechanism 10 is initialized and an initial position (X 0 ), i.e., count, of the motor is established. [0030] Next, a predetermined power level is applied to the actuator 14 . In the illustrated embodiment, the actuator 14 is controlled via a pulse width modulated (PWM) signal in a conventional manner. The actual power applied to the actuator 14 will be controlled by the duty cycle of the PWM signal and the supply or bus voltage. Thus, in a second step 30 , the bus voltage is measured. Based on the measured bus voltage, an open loop power value, i.e., PWM duty cycle, is calculated in a third step 32 to achieve the predetermined power level. In a fourth step 34 , the power is applied to the actuator 14 through application of the PWM signal to the motor. [0031] Then, motor stall is established. In a first decision block 36 , if the motor has stalled, i.e., rotation velocity equals zero (as established via the position sensor), then control proceeds to a fifth step 40 . If motor stall has not been established control proceeds back to the first decision block 36 via sixth step 38 . [0032] Once motor stall has been established, the reference position X 1 is determined in the fifth step 40 . [0033] In another aspect of the present invention, the method 26 may perform a diagnostic as a function of X 1 to determine if the brake mechanism 10 has a retained load. In a second decision block 40 , the difference between the initial position (X 0 ) and the reference motor position (X 1 ) is compared with a predetermined minimum value (min). If the difference is less than or equal to the predetermined minimum value, then a signal may be generated in a seventh step 44 , e.g., a flag may be set and/or an indicator light may be turned on. The signal may be indicative of a retained load. [0034] In an eighth step 46 , the home motor position is established as a function of the second position (X 1 ) and a predetermined constant (A 0 ) by the equation: X 2 =X 1 −A 0 . [0035] The predetermined constant, A 0 , is determined as a function of the nominal characteristics of the brake mechanism 10 and is expressed in turns or counts of the motor. [0036] In one embodiment of the present invention, in a ninth step 49 a predetermined number of home position values may be stored, e.g., in a stack, and averaged to determine an average home position value. This average home position value may be used in the position feedback control algorithm used to control the parking brake mechanism 10 in response to user actuation of the control device 22 . After the home position (X 2 ) has calculated, another diagnostic test may be performed. In a tenth step 50 , the controller 12 switches to closed loop position control. In an eleventh step 52 , a target position or target motor position (X 3 ), which in the illustrated embodiment corresponds to F 1 , is determined as a function of at least one of the reference position and the home motor position and a second predetermined constant (A 1 ). For example, the target position, X 3 , may be determined by the equation: X 3 =X 1 +A 1 , where A 1 is a determined as a function of the nominal characteristics of the brake mechanism 10 . [0038] In a twelfth step 54 , command signals are generated to the motor to move to the target position. As discussed above, in the illustrated embodiment, the command signals are PWM signals. In a third decision block 56 , if the target position has not been achieved, control returns to the twelfth step 54 . Otherwise, control proceeds to a thirteenth step 60 . [0039] During the loop defined by the twelfth step 54 and the third decision block 56 , the command signals, i.e., the PWM signal levels required to move the motor from X 3 , are monitored, and if excessive, an error signal is generated. [0040] Once, the target position has been reached, commands signals are generated to the motor to move to the home position, X 2 in the thirteenth step 60 . In a fourth decision block 62 , if the home position has not been achieved, control returns to the thirteenth step 60 . Otherwise, control proceeds to a fourteenth step 64 . In the fourteenth step 64 , a confirmation signal is generated. [0041] In another aspect of the present invention, a steady-state diagnostic algorithm may be provided. With reference FIGS. 5A and 5B , the steady-state diagnostic algorithm or method 66 is implemented only when the brake mechanism 10 is in a steady-state condition. [0042] In a decision block 68 , if a steady-state condition does not exist the method 66 proceeds to a first step 70 and returns to the normal operating mode. In one embodiment of the present invention, a steady-state condition is defined by either a zero position error or zero velocity of the motor. [0043] If the steady-state condition exists, the method 66 proceeds to a second decision block 72 . With reference to FIG. 4 , the current motor position is established using the position sensor and, if the current position (X N ) of the motor/actuator 14 is within the linear operating range 24 of the actuator 14 , then the method proceeds to a second step 74 . F′ 1 is the force corresponding to the X N on the force/position curve. Otherwise, the method 66 proceeds to the first step 70 . [0044] In the second step 74 , the bus or supply voltage to the motor is measured and, in a second step, the command signals to the motor are incremented to increase power to the motor to achieve a target position (X N+M ). In one embodiment, as discussed above, the command signals are in the form of PWM signals. [0045] In one embodiment, the target position X N+M is calculated using the equation: X N+M =X N +M, where M is a number of turns of the motor, e.g., one. [0046] In a fourth step 78 , the duty cycle of the PWM command signals are monitored. In a third decision block 80 , if the commanded or target position has not been reached, then control returns to the third step 76 . Otherwise, the method 66 proceeds to a fifth step 82 . In the fifth step 82 , the power required to move motor to the target position is calculated based on the change in the duty cycle of the PWM command signals. [0047] In a fourth decision block 82 , if the calculated required power (to move from X N to X N+M ) is within a predetermined power range, then control proceeds to a sixth step 86 . If the calculated required power is within the predetermined power range, i.e., is acceptable, this may be indicative of an acceptable home position (see above), acceptable efficiency within the brake mechanism 10 . [0048] If the required power is outside the predetermined power range, then the method proceeds to either of seventh step 88 or an eighth step 90 . In the seventh step 88 , the required power is below the predetermined power range which may be indicative of an improper home position (see above) or other actuator non-compliance. In the eighth step 90 , the required power is above the predetermined power range which may be indicative of a low efficiency in the brake mechanism 10 and/or decreased actuator compliance, due, for example, to reduced brake pad thickness. [0049] Obviously, many modifications and variations of the present invention are possible in light of the above teachings. The invention may be practiced otherwise than as specifically described within the scope of the appended claims.
A method and program product are associated with a brake mechanism. The brake mechanism includes a brake operable to restrict movement of a vehicle and an actuator coupled to the brake. The actuator is operable to selectively apply and release the brake. The mechanism further includes a controller coupled to the actuator. A method, implemented in the controller and program code, initializes the brake mechanism and calibrates and/or performs diagnostics on the brake mechanism.
1
BACKGROUND OF THE INVENTION [0001] 1. Field of the Invention [0002] The present invention relates generally to lifting devices, and more particularly, to a wheelchair lift device including a lift car, and having a protective skirt that restricts access below the lift car. [0003] 2. Description of the Background Art [0004] Under the Americans With Disabilities Act of 1990 (the “ADA”), the U.S. government required that public buildings be accessible to the disabled. For persons requiring a wheelchair for mobility, abrupt changes in floor elevation have to be modified to enable access by wheelchair. The ADA permits vertical lifting devices to be used instead of a ramp. [0005] Lifting devices for the disabled are known in the prior art. For example, U.S. Pat. No. 5,105,915 (Gary) describes a lifting device having a car including fixed sides and short, one-piece ramps at each end. The car is raised and lowered by a pantograph jack including a hydraulic pump driven by an electric motor controlled by switches. The patent also describes several lifting devices of the prior art. Another wheelchair lifting device is disclosed in U.S. Pat. No. 6,182,798 to Brady, et al., and assigned to AGM Container Controls, Inc., the assignee of the present invention. The '798 patent discloses a portable lift device with gates at both ends of the lift car, transparent walls, a loading ramp, a dock plate, a stage height sensor, and numerous safety features. [0006] Another portable lifting device adapted for wheelchairs is disclosed within pending U.S. patent application Ser. No. 11/026,863, filed on Dec. 30, 2004, and published as U.S. Publ. No. 20060182570 (Zuercher, et al.) on Aug. 17, 2006, also assigned to the assignee of the present application. This application discloses a portable wheelchair lift device that includes a lift car that can be raised and lowered, and which provides protective skirting around the front, back, and sides of the lift device to restrict access below the lift car to help prevent injury. [0007] Applicable governmental regulations require that wheelchair lift devices include a safety skirt surrounding the base of the lift to help keep legs, arms and other body parts from being inserted under the lift car. While such safety skirting is helpful in preventing accidents, the safety skirts are often made from rather flexible, yielding material, such as rubber or plastic. If sufficient force is applied laterally inward upon such safety skirts, they readily give way and deform. Accordingly, were a lift attendant, or even a bystander, to fall against the lift device during operation, such person's legs, arms, head, or other body parts could press sufficiently hard against the safety skirting to cause it to deform. If the lift car is being lowered at such time, there is a possibility that such person's leg, arm, head, etc., could become pinched between the bottom of the lift car and the base of the lift device, posing a significant danger. In view of such dangers, applicable governmental regulations now require that such wheel chair lift devices be able to avoid injury to such persons. [0008] In view of the foregoing, it is an object of the present invention to provide a wheelchair lift device suitable for lifting wheelchair-bound users up to the height of stages, platforms, risers and the like in a safe and reliable manner, and comporting with all applicable ADA requirements. [0009] Another object of the present invention is to provide such a lift device having a safety skirt, and which is able to detect instances when the safety skirt is inwardly deformed to the extent of posing a possible danger. [0010] A further object of the present invention is to provide such a lift device which is capable of halting upward or downward movement of the lift car upon detecting that the safety skirt has been inwardly deformed to the extent of posing such danger. [0011] Yet another object of the present invention is to provide such a lift device achieving the aforementioned objectives without significantly increasing the cost or complexity of the lift device. [0012] These and other objects of the present invention will become more apparent to those skilled in the art as the description of the present invention proceeds. SUMMARY OF THE INVENTION [0013] Briefly described, and in accordance with a preferred embodiment thereof, the present invention relates to a lift device for raising and lowering wheelchairs and the like, and including a base for resting upon the ground, a lift car that can be raised and lowered for supporting a user of a wheelchair or the like, and a lift mechanism coupled to the base and to the lift car for selectively raising, or lowering, the lift car relative to the base. A collapsible curtain panel, protective skirt, or safety skirt, has a lower end secured to the base and an upper end secured to the lift car for elevational movement therewith; this safety skirt helps to restrict access to an area located below the lift car when the lift car is raised. [0014] A deformable elongated member has a first end supported generally proximate to the base, and a second end generally supported proximate to the lift car for movement therewith. The deformable member extends lengthwise along a longitudinal axis that is proximate to the protective skirt. When a lateral, inwardly-directed force is applied to the protective skirt, the deformable elongated member is also displaced laterally from its usual longitudinal axis. [0015] A sensor detects lateral displacement of the deformable elongated member relative to its usual longitudinal axis, and generates an electrical signal that indicates such occurrence. The lift device includes a control mechanism responsive to the aforementioned electrical signal generated by the sensor for stopping further movement of the lift car until the problem is resolved. [0016] Preferably, the deformable elongated member is elastic and flexible, allowing lengthwise deformation (extension and retraction) as well as lateral deformation. A preferred example of such deformable elongated member is a tension spring. [0017] The preferred form of sensor for detecting lateral displacement of the deformable elongated member is a microswitch for opening or closing an electrical circuit when a trigger lever of the microswitch is contacted by the deformable elongated member. However, other types of sensors (optical, magnetic, ultrasonic, etc.) may also be used to detect the relative position of the deformable elongated member. [0018] The lift mechanism used to elevate the lift car relative to the base preferably includes a piston rod that is extendable from a hydraulic cylinder. The deformable elongated member preferably extends along a longitudinal axis that is generally parallel to the hydraulic cylinder; preferably, the longitudinal axis of the deformable elongated member also extends generally proximate to the hydraulic cylinder. At least a portion of the protective skirt extends generally proximate to the longitudinal axis of the deformable elongated member. [0019] The hydraulic cylinder has a first end from which a piston rod is extended to raise the lift, as well as an opposing second end. In one instance, the piston rod that extends from the first end of the hydraulic cylinder is secured to the base of the lift device, and the second end of the hydraulic cylinder is secured to the lift car. In an alternate case, the piston rod is secured to the lift car, and the second end of the hydraulic cylinder is secured to the base of the lift device. In either case, the first end of the deformable elongated member can be supported generally proximate to the base, and the second end of the deformable elongated member is supported generally proximate to the lift car. For example, the second end of the deformable elongated member could be supported from the uppermost end of the hydraulic cylinder. Alternatively, the deformable elongated member can simply extend between the first and second ends of the hydraulic cylinder, such that its length remains relatively fixed. BRIEF DESCRIPTION OF THE DRAWINGS [0020] FIG. 1 shows a user entering the lift car from the ground. [0021] FIG. 2 shows a user being lifted in the lift car. [0022] FIG. 3 shows a user entering the lift car from the stage through the stage gate. [0023] FIG. 4 is a perspective, skeletal view of the lift device base, intermediate support rails, and lift car in an elevated position. [0024] FIG. 5 is a cut-away side view of the lift device showing the position of an electric motor, hydraulic pump, hand-operated manual pump, and one of the hydraulic cylinders used to raise the lift car. [0025] FIG. 6 is another perspective, skeletal view of the lift device, similar to FIG. 4 , but adding the hydraulic lift cylinders, lift car gates, and front gate scissors interlock. [0026] FIG. 7 is a schematic drawing of the hydraulic lifting mechanism, including an electric motor, hydraulic gear pump, supplemental hand pump, control valves, and hydraulic cylinders. [0027] FIG. 8 is an electrical circuit schematic illustrating the switches and control circuitry for controlling the operation of the motor and solenoid valve that power the hydraulic lifting mechanism. [0028] FIG. 9 is a perspective view of a height adjustment rail, viewed from above, used to set the predetermined height to which the lift device is elevated. [0029] FIG. 10 is a perspective view of the height adjustment rail shown in FIG. 9 viewed from below. [0030] FIG. 11 is an enlarged view of the second end of the height adjustment rail. [0031] FIG. 12 is an enlarged view of the actuator that slides within the height adjustment rail. [0032] FIG. 13 is an enlarged view of the “two-inch” electrical switch. [0033] FIG. 14 is an enlarged view of the maximum height, upper-stop switch. [0034] FIG. 15 is a side cut-away view of the height adjustment rail mounted within a side panel of the lift car. [0035] FIG. 16 is a top, cross-sectional view of the structure shown in FIG. 15 . [0036] FIG. 17 is a perspective view of the lift device illustrating protective skirting installed thereon. [0037] FIG. 18 is a perspective view of the protective skirt associated with the front gate of the lift car prior to assembly. [0038] FIG. 19 is a perspective view of the protective skirt assembly that surrounds the sides and rear portion of the lift device. [0039] FIG. 20 is a side view of the lower portion of the lift device showing a pair of skirt sensors. [0040] FIG. 21 is a perspective cut-away view of skirt sensor components shown in FIG. 20 . DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [0041] In FIG. 1 , a lift device includes a movable lift car 162 , as well as a lifting mechanism (not shown) that selectively elevates lift car 162 relative to the ground from a lowered position to an elevated position. In FIG. 1 , lift car 162 is shown completely lowered to the floor, and a front (lower landing) gate 164 has been opened for allowing user 166 to roll his wheelchair 168 onto the floor 170 of lift car 162 from ground level. Lift car 162 includes opposing side panels 165 and 167 . Lower landing gate (or front entry gate) 164 preferably includes an electro-mechanical interlock that prevents front entry gate 164 from being opened whenever lift car 162 is more than two inches above the fully lowered position. In addition, a safety skirt 181 completely encloses and protects the area under lift car 162 . [0042] In FIG. 2 , user 166 is being elevated in lift car 162 toward stage height. Front gate 164 , and rear (stage) gate 172 , are both closed and secured during elevation. For safety reasons, both the lower entry gate 164 and upper stage gate 172 are preferably self-closing. [0043] FIG. 3 shows another user 166 ′, already supported on stage floor 174 , entering into lift car 162 . Rear stage gate 172 is opened, and a hinged stage docking plate 176 is lowered to allow wheelchair 168 ′ to roll smoothly onto lift car floor 170 . As stage gate 172 opens, hinged dock plate 176 is automatically lowered into position by a tether (not shown), thereby spanning any small gap between lift car floor 170 and stage 174 . Dock plate 176 rests on stage 174 and provides a smooth transition between lift car floor 170 and stage 174 . When stage gate 172 is closed, dock plate 176 is simultaneously retracted by the aforementioned tether. [0044] FIG. 4 shows the base, intermediate lift support rails, and lift car skeleton used to fabricate the lift device. The hydraulic lifting cylinders, motor, hydraulic pump, and protective skirt, are omitted from FIG. 4 for purposes of clarity. Base 180 includes a pair of opposing, parallel elongated metallic members 501 and 502 that are coupled to each other by cross-braces 503 , 504 and 505 . Brackets 501 and 502 each include apertured brackets 506 and 507 , respectively, for receiving piston rods of the hydraulic lifting cylinders. A pair of U-shaped rails 508 and 509 project upwardly from metallic members 506 and 507 , respectively. Angled braces 510 and 511 are welded to rails 508 and 509 , respectively, and to the opposing ends of metallic members 501 and 502 , respectively. Cross brace 512 extends between, and couples, the upper ends of rails 508 and 509 . Partially visible in FIG. 4 is a roller 514 which pivots upon axle 516 near the upper end of rail 508 . A similar roller (not shown) is installed at the upper end of rail 509 . [0045] Still referring to FIG. 4 , a pair of intermediate lift support rails 518 and 520 are slidingly supported by rails 508 and 509 , respectively, for vertical movement. The aforementioned sliding support of rail 518 is provided by roller 514 , and by a lower roller (not visible) secured by an axle to the lower end of intermediate rail 518 ; this lower roller engages the inner U-shaped walls of rail 508 . Lift car 162 is, in turn, slidingly supported by intermediate lift support rails 518 and 520 . Lift car 162 includes floor 170 extending between opposing side panels 165 and 167 . Again, for purposes of clarity, the front and rear gate entry doors ( 164 and 172 in FIGS. 1-3 ) have been removed for clarity. The upper ends of intermediate lift support rails 518 and 520 are slidingly received within side panels 167 and 165 , respectively. While not visible within FIG. 4 , rollers secured to the upper ends of intermediate lift support rails 518 and 520 , and rollers secured within side panels 167 and 165 , allow the upper ends of intermediate lift support rails 518 and 520 to telescope within, or extend from, the bottoms of side panels 167 and 165 . [0046] FIG. 5 is a side view of the lift device in its lowered position, with the protective skirt and a portion of the side panel cut away for clarity. In addition, the springs and sensors used to detect deformation of the protective skirt have also been omitted from FIG. 5 for clarity. Hydraulic lifting cylinder 50 has its upper end secured to bracket 522 of lift car side panel 165 for selectively raising lift car 162 . The piston rod extending from the lower end of hydraulic lifting cylinder 50 is connected by pin 524 to apertured bracket 507 of base 180 . Also visible within FIG. 5 are electric motor 56 , rotary pump 58 , manual pump 80 (used in the event of an electrical power failure), hydraulic fluid reservoir 526 and hydraulic solenoid valve 68 . With the exception of hydraulic cylinder 50 , all of the aforementioned components fit within side panel 165 of lift car 162 . Lines 528 and 54 pass below base 180 to the opposite side of the lift device for powering the second hydraulic lift cylinder. [0047] FIG. 6 is a perspective view similar to that shown in FIG. 4 , but rotated 180 degrees, and now including the hydraulic lift cylinders 50 and 52 , front gate 164 , and rear gate 172 . Once again, the protective skirt, skirt tension springs, and skirt sensors are omitted from this view for purposes of clarity. Front lift gate 164 includes a stabilizing scissors brace 530 that expands and contracts as lift car 162 is raised and lowered. Scissors brace 530 helps to stabilize lift car 162 when elevated. The lowermost links of scissors brace 530 are coupled to a lower support bar 532 , which is allowed to swivels outward, along with entry gate 164 , when lift car 162 is fully-lowered. Piston rods 51 and 53 are shown fully extended in FIG. 6 . Switch assemblies 534 and 536 are also shown for operating the lift device from outside, or inside, lift car 162 , respectively. The lift car 162 , base support frame 180 , and the hydraulic lifting cylinders 50 / 52 are all preferably formed from ASTM A36, AISI 1018, or AISI 1020 Steel. All transparent windows incorporated within lift car side panels 165 and 167 , and within the front and rear gates 164 and 172 are preferably fabricated from ¼″ thick high impact strength clear thermoplastic material. [0048] FIG. 7 is a schematic diagram of a hydraulic control system that may be used to control the wheel chair lift device in one preferred embodiment. A pair of hydraulic lifting cylinders, including left side cylinder 50 and right side cylinder 52 , are provided to raise and lower the wheel chair lift. In this preferred embodiment, hydraulic cylinders 50 and 52 are of the type generally available from Ram Industries Inc., a Canadian company having a U.S. distribution facility in Minot, N. Dak. Left side cylinder 50 is preferably of the type available from Ram Industries Inc. as Model No. R4505901 (3000 psi operating pressure, 2.5″ bore, 40.5″ stroke, 1.125″ rod), while right side cylinder 52 is preferably a Model No. R4505902 (3000 psi operating pressure, 2.75″ bore, 40.5″ stroke, 1.125″ rod). Cylinders 50 and 52 each include an expansion chamber and a retraction chamber. The expansion chamber of cylinder 50 is coupled by tube 54 to the retraction chamber of cylinder 52 . When the lift is being raised, pressurized hydraulic fluid is forced into the expansion chamber of cylinder 52 , extending piston rod 53 , compressing fluid in the retraction chamber of cylinder 52 , and forcing the compressed fluid into the expansion chamber of cylinder 50 for extending piston rod 51 . Alternatively, when the lift is being lowered, pressurized hydraulic fluid is forced into the retraction chamber of cylinder 50 , retracting piston rod 51 , compressing fluid in the expansion chamber of cylinder 50 , and forcing the compressed fluid through tube 54 into the retraction chamber of cylinder 52 for retracting piston rod 53 . [0049] Still referring to FIG. 7 , electric motor 56 rotates in a fixed direction to rotate the input drive shaft of hydraulic fluid pump 58 . In the preferred embodiment, motor 56 is a one-half horsepower, 120 V AC electric pump motor of the type commercially available from Leeson Electric Corporation of Grafton, Wis. Pump 58 is preferably a close-coupled, hydraulic gear pump of the type commercially available from JS Barnes Corp./Haldex Hydraulics Corporation of Rockford, Ill. under Part No. G 1112H1A109NPG, having a cubic displacement of 0.194 cubic inches. Pump 58 draws hydraulic fluid from inlet 60 via fluid return line 61 and pumps hydraulic fluid out under pressure through check valve 62 . Relief valve 64 is provided as part of pump 58 and can be adjusted to permit a selected amount of pressurized hydraulic fluid to be directed back to fluid return line 61 . [0050] Still referring to FIG. 7 , hydraulic fluid pressurized by pump 58 is supplied via high pressure conduit 66 to the high pressure inlet of a solenoid valve 68 . Solenoid valve 68 also includes a low pressure outlet coupled to return conduit 72 for coupling to fluid return line 61 . Solenoid valve 68 is normally biased (by a spring) to a position for raising cylinders 50 and 52 . In this case, solenoid valve 68 assumes the default crossed-over position shown in FIG. 7 , wherein high pressure inlet line 66 is coupled to line 74 , and low pressure outlet 72 is coupled to line 76 . Preferably, solenoid valve 68 is a 12 VDC solenoid valve with manual override of the type commercially available from Hydac Technology Corporation, Hydraulics Division, of Glendale Heights, Ill., under Part Number WK08Y-01-M-C-N, with electrical coil Part Number 12 DS-40-1836. [0051] In the event of a power failure, motor 56 that powers hydraulic pump 58 will no longer operate. For this reason, hydraulic hand pump 80 is provided in an emergency to raise and lower the lift car without electrical power. Still referring to FIG. 7 , hand-operated fluid pump 80 includes a fluid inlet coupled through a check valve 82 to low pressure return line 72 for receiving unpressurized hydraulic fluid. Pump 80 also includes a high-pressure outlet port for supplying pressurized hydraulic fluid through check valve 84 to high pressure line 66 . A lever can be reciprocated by an operator to raise or lower the lift using such hand-operated pump 80 if motor 56 is suddenly lacking any electrical power. Pump 80 is preferably of the type available from HydraForce, Inc. of Lincolnshire, Ill. under part number HP 10-21B-0-N-B. [0052] As shown in FIG. 7 , pilot-operated check valve 88 couples line 76 to the retraction chamber of hydraulic cylinder 50 . Valve 88 is preferably of the type commercially available from Hydac Technology Corporation, Hydraulics Division, of Glendale Heights, Ill., under Part Number RP08A-01C-NS-15-4. Line 74 is coupled by an over-center, counter-balance, spring-biased valve 90 to the expansion chamber of cylinder 52 . Valve 90 is preferably of the type commercially available from Hydac Technology Corporation, Hydraulics Division, of Glendale Heights, Ill., under Part Number RS08-01-C-N-4-500V. Valve 90 is adjustable to help ensure that cylinders 50 and 52 expand and retract at the same rate. [0053] The electrical schematic of FIG. 8 includes pump motor 56 electrically coupled across 110 Volt power lines 100 and 102 , protected by fuses 101 and 103 , respectively. The housing of motor 56 is coupled by ground line 104 to ground conductor 106 . Element 108 is coupled in series between motor 56 and “hot” power line 100 and represents the contacts of motor relay 110 (also shown in FIG. 8 ) that selectively applies power to motor 56 . The 110 Volt service lines 100 and 102 , and ground conductor 106 , are also coupled to a regulated 12 Volt D.C. power supply 111 . Power supply 111 provides a source of a regulated 12 volt D.C. voltage on line 112 relative to low-power ground line 114 . [0054] The heart of the control system for controlling the lift is an IDEC Smart Relay module 116 commercially available from IDEC Izumi Corporation of Sunnyvale, Calif. under part number FL1C. This module is a compact, expandable, fully programmable, CPU that can replace multiple timers, counters, and relays. As indicated in FIG. 8 , module 116 is coupled to 12 volt D.C. power lines 112 and 114 . Module 116 includes a series of input terminals coupled to conductors designated by reference numerals 118 , 120 , 122 , 124 , 126 , 128 , 130 and 132 . Module 116 also includes output terminals 134 and 136 . [0055] Input terminal 118 is the “UP” terminal; when a “high” voltage is applied to input 118 , module 116 is signaled to raise the lift. Input terminal 120 is the “DOWN” terminal; when a high voltage is applied to input 120 , module 116 is signaled to lower the lift. As will be described in greater detail below, there are three toggle switches (grouped together in FIG. 8 within dashed box 138 ) positioned about lift car 162 for selecting upward or downward movement of the lift car. [0056] Input terminal 122 is coupled in series with two right-side skirt sensor switches 142 and 144 , described in greater detail below. Switches 142 and 144 detect deflection of the protective skirt on the right side of the lift device. Switches 142 and 144 are normally closed to apply a “high level” on conductor 122 . If either switch 142 or switch 142 is opened due to deflection of the protective skirt, then movement of lift car 162 (upward or downward) ceases. [0057] Similarly, input terminal 128 is coupled in series with two left-side skirt sensor switches 156 and 140 , described in greater detail below. Switches 156 and 140 detect deflection of the protective skirt on the left side of the lift device. Switches 156 and 140 are normally closed to apply a “high level” on conductor 128 . If either switch 156 or switch 140 is opened due to deflection of the protective skirt, then movement of lift car 162 (upward or downward) ceases. [0058] Input terminal 124 is the “2 Inch Switch” terminal and is coupled to “2 Inch Switch” 146. When lift car 162 is being raised from the ground, the electrical contacts of switch 146 are closed as the floor of the lift car reaches approximately two inches above the ground. The 2 Inch Switch 146 signals, via input terminal 124 , that the floor of the lift car has raised to approximately two inches above the ground. One of the safety features provided in the preferred embodiment relates to ensuring that the front gate ( 164 in FIG. 6 ) of the lift car is securely locked closed once the floor of the lift car has raised two inches off of the ground. If the floor of the lift car has raised more than two inches off of the ground, but a front gate safety interlock bolt has not engaged, then further elevation of the lift car is prevented. [0059] Input terminal 126 is the “Lockbolt” terminal and is used to signal that the front gate safety interlock bolt, briefly described in the preceding paragraph, is engaged. The electrical contacts of lockbolt switch 148 are closed when the interlock bolt is engaged, but such electrical contacts open if the interlock bolt is not engaged. As mentioned above, safe operation of the lift is ensured by confirming that the front gate safety interlock bolt has engaged, and hence, that the front gate (or lower landing gate) is securely locked, before allowing the lift car to elevate more than a few inches off of the ground. [0060] Input terminal 130 is the “Landing Gate” terminal and is used to detect whether the front landing gate (i.e., front gate 164 in FIG. 6 ) and rear landing gate (i.e., rear gate 172 in FIG. 6 , the gate providing access to an elevated stage) are closed. The electrical contacts of upper landing gate switch 150 open if the rear gate is open, and close when the rear gate is closed. Likewise, the electrical contacts of lower landing gate switch 152 open if the front gate is open, and close when the front gate is closed. When all gates are closed, switches 150 and 152 are closed, and a “high level” signal is conveyed to conductor 130 , allowing lift car 162 to continue movement; if not, movement of the lift ceases. [0061] Finally, input terminal 132 is the “Height” terminal and is used to signal whether or not the lift car has reached a pre-selected height. An electrical height switch 154 can be adjusted, in a manner to be described in greater detail below, to cause its electrical contacts to be open if the lift car is below a desired height, but to close such electrical contacts when the lift car reaches the pre-selected height, thereby signaling relay module 116 to prevent further elevation of lift car 162 . [0062] Still referring to FIG. 8 , output terminal 134 is coupled to one side of solenoid valve 68 , the other side of which is coupled to ground line 114 . Module 116 provides a “low” voltage when it is desired to raise the lift, and provides a “high” (+12 V DC) voltage when it is desired to lower the lift. Referring briefly to FIG. 7 , it can be seen that, depending upon the position of solenoid-controlled valve 68 , the direction in which pressurized hydraulic fluid is directed into hydraulic cylinders 50 and 52 can be reversed by actuating solenoid valve 68 . [0063] As shown in FIG. 8 , output terminal 136 of module 116 is coupled to one side of motor relay coil 110 , the other side of which is coupled to ground line 114 . When module 116 causes output terminal 136 to assume a “high” (+12 V DC) output state, motor relay coil 110 is energized, and the electrical contacts of motor relay 108 are closed to energize pump motor 56 . As is also shown in FIG. 8 , a normally-closed emergency stop button 160 may be positioned inside lift car 162 to shut down the operation of the lift during an emergency. [0064] Referring now to FIGS. 9 and 10 , the preferred embodiment of the height adjustment mechanism, used to adjust the maximum height to which lift car 162 can be elevated, will now be described. A generally U-shaped, elongated rail 540 extends between first and second opposing ends 542 and 544 . Rail 540 is preferably made of metal, and the lower edges of side walls 546 and 548 preferably turn back inwardly inside rail 540 to form two inwardly directed flanges 550 and 552 , as best illustrated in the enlarged end view shown in FIG. 11 . Mounting pins 543 and 545 extend transversely through the first and second ends 542 and 544 , respectively, of rail 540 . [0065] An actuator 554 is slidingly received within rail 540 , and a transverse tab 556 extends from actuator 554 below rail 540 . The features of actuator 554 are best observed in the enlarged view of FIG. 12 . Actuator 554 is preferably formed of plastic, and is ideally machined from Nylon material. As shown in FIG. 12 , the side walls of actuator 554 have opposing slots 558 and 560 formed therein; these slots are slidingly engaged by inwardly directed flanges 550 and 552 of rail 540 for allowing actuator 554 to slide along rail 540 between the first end 542 and the second end 544 thereof, while being captured therein. Mounting pins 543 and 545 prevent actuator 554 from exiting from either end of rail 540 . Transverse tab 556 is secured to the underside of plastic actuator body 554 by a pair of screws 557 and 559 . [0066] Still referring to FIGS. 9 and 10 , a first proximity sensor, in the form of an electrical microswitch 562 , is mounted on rail 540 generally closer to second end 544 of rail 540 than to first end 542 . Switch 562 is preferably similar to those sold under Part No. BZ-2RW82-A2 by Honeywell Microswitch. Switch 562 corresponds to the upper stop switch 154 in the electrical schematic of FIG. 8 . As shown in FIG. 14 , switch 562 includes a lever arm 564 having a cam roller 566 at its distal end. Switch 562 is secured by a pair of screws 568 and 570 to a vertical wall of angle bracket 572 . The upper horizontal wall of angle bracket 572 is adapted to engage the upper, horizontal central wall of rail 540 . [0067] As indicated in FIG. 9 , a series of slots, including slot 574 , are formed along the upper, horizontal central wall of rail 540 . Alternatively, one long continuous slot could be formed in the upper, horizontal central wall of rail 540 , if desired. Similarly, a slot 576 is formed in upper horizontal wall of angle bracket 572 . As will be explained below, maximum elevation height of the lift car is adjusted by moving, and re-tightening, angle bracket 572 relative to rail 540 . Referring to FIG. 14 , a screw 578 extends through a lockwasher 580 from the underside of angle bracket 572 , through slot 576 . Turning to FIG. 9 , the threaded tip of screw 578 is received within a mating lockwasher and nut (collectively designated by reference numeral 582 ). The length of slot 576 , along with the lengths and spacings of slots 574 , permit virtually infinite adjustment of the position of switch 562 along rail 540 . During installation of the lift device, the installer adjusts the position of switch 562 along rail 540 to make the lift car stop so that the floor 170 of the lift car is even with the stage 174 . [0068] Referring jointly to FIGS. 10 , 11 and 12 , a constant force spring 584 is wrapped about a plastic drum 585 for rotation about mounting pin 543 . Constant force spring 584 is similar to the constant force springs often found within tape measures for causing the elongated tape to retract. The free end 586 of constant force spring 584 is coupled with actuator 554 . Constant force spring 584 thereby serves as a biasing member for biasing actuator 554 toward first end 542 of rail 540 , and away from second end 544 of rail 540 . While this biasing force is preferably created by a constant force spring, the biasing force could alternatively be created using the force of gravity, as by attaching a weight, via a cable and pulley, to actuator 554 , or by simply mounting rail 540 at an angle to the horizontal (with first end 542 being the lowermost point) and attaching a weight directly to actuator 554 . [0069] Actuator 554 is disposed generally proximate to first end 542 of rail 540 when lift car 162 is in its lowered position on the ground. A first end of a flexible cable 590 extends into rail 540 from second end 544 and is attached to actuator 554 by anchor 592 . Cable 590 is preferably formed of braided wire of the type known as aircraft cable. As will be described in more detail below, as lift car 162 is elevated, cable 590 pulls on actuator 554 against the biasing force of spring 584 , causing actuator 554 to slide toward second end 544 of rail 540 , and toward switch 562 . As actuator 554 nears switch 562 , tab 556 engages cam roller 566 of lever arm 564 , closing microswitch 562 . The closing of switch 562 corresponds to the generation of an electrical signal that indicates that actuator 554 is proximate to switch 562 , and that the maximum height of the lift car has been achieved. Relay module 116 (see FIG. 8 ) is responsive to this electrical signal for halting any further elevation of the lift car. [0070] It will be recalled that it is also desirable to generate a signal indicating that the lift car has been raised slightly above the ground, e.g., by two inches above the ground. This signal can easily be generated using the height adjustment rail and actuator already described above. Referring again to FIGS. 9 and 10 , a second microswitch 594 is secured to a second angle bracket 596 . Microswitch 594 may be of the same type used for switch 562 . Second angle bracket 596 is adjustably mounted to rail 540 using a screw 598 and nut 599 in the same manner already described above for angle bracket 572 . However, second angle bracket 596 is mounted proximate to first end 542 of rail 540 , between first end 542 and switch 562 . As lift car 162 begins to rise, the tab 556 of actuator 554 engages cam roller 600 (see FIG. 13 ) of switch 594 , closing switch 594 , and signaling that lift car 162 has left the ground. The exact position of switch 594 along rail 540 can be set, as desired, to trigger when the lift car 162 is a fixed number of inches above the ground. [0071] Turning to FIGS. 15 and 16 , height adjustment rail 540 is shown after being mounted within side panel 167 of lift car 162 , via mounting pins 543 and 545 . As shown in FIG. 15 , rail 540 is preferably mounted to extend substantially horizontally, and is secured to side panel 167 of the lift car; accordingly, as lift car 162 rises and falls, rail 540 rises and falls along with it. When lift car 162 is fully-lowered, actuator 554 (and its tab 556 ) are disposed all the way to the right, near the first end 542 of rail 540 , and tab 556 does not yet engage cam roller 600 . The first end of cable 590 is secured to actuator 554 , and the second end of flexible cable 590 is coupled to an anchor point below the second end 544 of rail 540 . This anchor point could be a point on base 180 of the lift. Alternatively, the anchor point can be a location on the lifting mechanism of the lift device, for example, a point on hydraulic lift cylinder 52 . In that event, the second end of cable 590 can advantageously be anchored to hydraulic cylinder 52 by a hose clamp secured about the hydraulic cylinder; the second end of cable 590 is inserted inside the hose clamp, and the hose clamp is tightened. [0072] As shown in FIG. 15 , flexible cable 590 includes a first generally horizontal portion extending generally between actuator 554 and second end 544 of rail 540 , generally parallel to rail 540 . Flexible cable 590 also includes a second portion that extends generally between second end 544 of rail 540 and the anchor point; this second portion of flexible cable 590 extends at a substantial angle relative to rail 540 . If desired, a pulley or roller can be provided on mounting pin 545 to guide cable 590 around the bend. [0073] As lift car 162 elevates, cable 590 pulls actuator 554 from right to left (relative to FIGS. 15 and 16 ), first tripping cam roller 600 and later tripping cam roller 566 to halt further elevation. Once again, while rail 540 is preferably mounted horizontally, as shown in FIG. 15 , it is possible to position rail 540 at an angle to the horizontal, or even vertically, in which case, actuator 554 could be biased away from second end 544 of rail 540 by the force of gravity, as by attaching a weight to actuator 554 . [0074] While rail 540 is preferably mounted to lift car 162 , it is also possible to mount rail 540 to a fixed portion of the lift device (e.g., to a portion of base 180 ). In that event, the second end of flexible cable 590 should be attached to an anchor point above rail 540 ; this anchor point should be one that rises when lift car 162 is elevated, and that anchor point could be a point on the lift car itself. [0075] FIG. 17 shows the lift device partially elevated, and better illustrates the protective skirting that encircles the base of the lift device. As used herein, the term “collapsible curtain panel” is intended to include such protective skirting. Protective skirt 179 raises and collapses as front gate 164 of lift car 162 elevates and lowers, respectively. As shown in FIG. 18 , protective skirt 179 consists of accordion-like flexible plastic pleated fabric; the pleats have vertically aligned holes formed near their opposing ends for slidingly receiving a pair of support rods 606 and 608 . Mounting hardware 610 , 612 , 614 and 616 is used to secure the upper portions of support rods 606 and 608 within the opposing side frame members of front gate 164 . The lower edge of skirt 179 is secured to lower support bar 532 , and the upper edge of skirt 179 is secured to the lower frame member of front gate 164 for elevation therewith. [0076] Referring briefly to FIG. 6 , scissors brace 530 extends upwardly from lower support bar 532 ; scissors brace is hidden from view in FIG. 17 , but extends just behind protective skirt 179 . Scissors brace 530 is sufficiently rigid to support protective skirt against significant inward deformation; thus, even if a bystander leaned against, or fell against, protective skirt 179 , there is little risk of injury to such person as a result of continued elevation, or continued lowering, of lift car 162 . [0077] At the opposite end of the lift device, below stage gate 172 , there is also little risk of injury to others present because the lift device is typically permanently installed so that its rear side abuts a stage or other structure. Accordingly, persons would find it difficult to position themselves adjacent to the protective skirt 603 (see FIG. 19 ) that covers the rear side of the lift device below stage gate 172 . [0078] Referring briefly to FIG. 19 , it will be noted that the protective skirts that shield the rear portion, and two sides, of the lift device can be fabricated as a single structure, again preferably from accordion-like flexible plastic pleated fabric. Protective skirt 604 extends below side panel 165 of lift car 162 , as shown in FIG. 17 . Protective skirt 603 extends below the rear of lift car 162 , and protective skirt 181 extends below side panel 167 of lift car 162 , as shown in FIGS. 1-3 . The upper end 618 of protective skirt 604 is secured to side panel 165 of lift car 162 for movement therewith, and the lower end 620 of protective skirt 604 is secured to base member 502 . [0079] Protective skirt 604 and opposing protective skirt 181 are both accessible to bystanders. While protective skirts 604 and 181 help to prevent arms and legs of bystanders from being poked under lift car 162 , such protective skirts are necessarily flexible to facilitate expansion and retraction as lift car 162 is elevated and lowered. In view of such flexibility, protective skirts 604 and 181 will yield to significant inward pressure, as when a person leans against, or falls against, one of such skirts. A person's body could subsequently become pinched between the lower portion of lift car 162 and the ground if the lift car continued down toward the ground. It is therefore advisable to halt any further movement of lift car 162 if either protective skirt 604 or protective skirt 181 is inwardly deformed. [0080] To prevent further lift car movement when either protective skirt 604 or protective skirt 181 is inwardly deformed, a series of skirt sensors are provided along the opposing sides of the lift device, as will now be described with reference to FIGS. 20 and 21 . For clarity, protective skirt 604 is omitted from FIGS. 20 and 21 . A first deformable elongated, elastic tension spring 630 has a first end 632 engaged with an anchor loop 634 on apertured bracket 507 near base 180 . Second end 636 of elongated spring is secured to a hook or loop 638 anchored to an upper portion of hydraulic lift cylinder 50 by circular hose clamp 640 , generally proximate lift car 162 for movement therewith. Spring 630 extends along hydraulic cylinder 50 facing, and adjacent to, protective skirt 604 . As hydraulic cylinder 50 extends its piston rod to raise lift car 162 , spring 630 stretches and elongates, but the longitudinal axis of spring 630 always extends generally across, and proximate to, protective skirt 604 . If protective skirt 604 were deformed inwardly, as by someone falling against it, and applying a lateral force thereto, the contact between protective skirt 604 and spring 630 also laterally displaces spring 630 . [0081] In FIG. 20 , a microswitch 650 is mounted to hydraulic cylinder 50 by hose clamp 652 . Microswitch 650 is similar to those described above for use with the height adjustment mechanism; preferably skirt sensor switch 650 is a Model No. BZ-2RW8299-A2 from Honeywell Microswitch, including an adjustable pre-travel feature. Microswitch 650 corresponds to one of the skirt sensor switches 142 , 144 , 156 , and 140 described above in conjunction with the electrical schematic of FIG. 8 . Switch 650 is normally “closed” to form an electrical short circuit. The cam roller on the lever arm of switch 650 is positioned just behind spring 630 ; as a result, any significant lateral deformation of tension spring 630 , away from its longitudinal axis, causes switch 650 to “open”, breaking the electrical path. [0082] For added protection, a second tension spring 660 is also secured along hydraulic cylinder 50 . Tension spring 660 has a first end secured to a hook or loop mounted to the lower end of hydraulic cylinder 50 by hose clamp 666 . The upper end 668 of spring 660 is secured to an upper portion of hydraulic cylinder 50 by hose clamp 670 . As shown in FIG. 21 , another microswitch 672 , similar to switch 650 , and including lever arm 674 and cam roller 676 , is mounted to hydraulic cylinder 50 by hose clamp 678 . Cam roller 676 is disposed just behind spring 660 to detect any lateral deflection thereof caused by deformation of protective skirt 604 . When cam roller 676 of switch 672 is contacted by spring 660 , switch 672 opens. As explained above in conjunction with FIG. 8 , when any of the skirt sensor switches open, relay module 116 immediately halts any further movement of lift car 162 until the problem is resolved. [0083] Those skilled in the art will now appreciate that a lift device has been described that is suitable for lifting wheelchair-bound users up to the height of stages and the like in a safe, reliable and repeatable manner, and complying with all applicable ADA requirements. The lift device includes protective skirting about the base of the lift device, while being able to detect instances when the safety skirt is inwardly deformed to the extent of posing a possible danger. Upon detecting such danger, the lift device immediately halts any further upward or downward movement of the lift car until the cause of such problem has been resolved. Moreover, the additional components used to detect lateral deformation of the skirt are relatively inexpensive and do not significantly increase the complexity of the lift device. [0084] While the present invention has been described with respect to a preferred embodiment thereof, such description is for illustrative purposes only, and is not to be construed as limiting the scope of the invention. Various modifications and changes may be made to the described embodiments by those skilled in the art without departing from the true spirit and scope of the invention as defined by the appended claims.
A wheel chair lift device includes a lift car selectively elevated above a base, along with protective skirting covering the region below the lift car. Exposed portions of the protective skirting subject to lateral inward deformation are provided with skirt deformation sensors for detecting abnormal inward deformation of such skirt portions. The skirt deformation sensors include a spring or other elongated deformable member that extends generally parallel and proximate to the portion of the skirt being sensed. A sensor detects that the elongated member has been laterally displaced from its usual longitudinal axis and generates an electrical signal. In response to such electrical signal, the lift device stops further movement of the lift car.
8
BACKGROUND OF THE INVENTION This invention pertains in general to the art of wire or filament manufacture. Specifically, the invention is a wire accumulator for use in a wire or filament manufacturing facility, particularly for a wire or filament having low tensile strength and which is therefore easily broken, such as, for example, an optical fiber. A typical manufacturing facility may include a machine for drawing an optical fiber, a first take-up device downstream of the drawing machine, a tensile strength testing machine for testing the tensile strength of the optical fiber during its travel, and a winding device for winding the optical fiber on a bobbin. Optical fibers are relatively weak filament and are therefore easily broken in the tensile strength testing machine. It is, therefore, usual to provide an accumulator and a second take-up device between the first take-up device and the tensile strength testing machine to facilitate replacement of the, optical fiber without stopping the drawing machine if the fiber is broken. Commonly assigned U.S. application with Ser. No. 502,059 filed on June 7, 1983, now abandoned, is directed to such an accumulator. The invention set forth in this application is a further improvement over this accumulator. Referring now to FIGS. 1-4 there is shown a known accumulator. Optical fiber 1 is drawn into the accumulator at a constant speed from a drawing machine (not shown) by a first take-up device 2, past guide rollers 17 and to a second take-up device 9 via dancer rollers 11 which control the speed of optical fiber on the second take-up device. From second take-up device 9, the fiber is subjected to a tensile strength test by a tensile testing machine 27, and wound by a winder (not shown) downstream of dancer rollers 28 which control the winding speed, as shown by arrows in FIG. 1. The accumulator includes two groups Y and Z of cylindrical accumulating guide rollers 3 and 3' which are rotatably supported on bearings 5 and shafts 6 and 6' secured at equal intervals in a circular array to side plates 7 and 8, and 7' and 8', respectively, as shown in FIGS. 1 and 2. Each guide roller 3 and 3' is formed around its outer periphery with a plurality of grooves 4 which are equally spaced apart from one another at a pitch P. The grooves 4 on the guide rollers 3 or 3' are slightly displaced axially from one guide roller to another, as shown in FIG. 2. A shaft 14 extending through the center of the guide roller assembly Z is rotatably supported by bearings 12 on a stand 10. A variable speed motor 13 is provided at one end of the shaft 14 for driving it, and an arm 15 is secured to the other end of the shaft 14. A guide bar 16 is secured to the outer end of the arm 15. Moving blocks 18 and 18' are slidable transversely along the guide bar 16 as shown in FIG. 3. Guide rollers 17 and 17' for distributing optical fiber to the accumulating guide roller assemblies Y and Z are rotatably carried on the blocks 18 and 18', respectively. A screw shaft 21 is rotatably supported by bearings 20 on the support members 19 and 19' secured to the opposite ends of the guide bar 16 and the arm 15, and extends in parallel to the guide bar 16. The screw shaft 21 has threaded portions 22 and 23 on both sides of the arm 15, and they are fastened to the moving blocks 18 and 18' by nuts. Threaded portion 22 has a right-hand screw, and threaded portion 23 a left-hand screw. Each screw has a pitch which is equal to pitch P of the grooves 4 on the guide rollers 3 and 3'. Thus, each rotation of the screw shaft 21 causes the movement of the moving blocks 18 and 18' in opposite directions by a distance equal to the pitch of the grooves 4. A timing belt pulley 24 is provided on screw shaft 21 and connected by a timing belt 26 to a timing belt pulley 25 provided on the side plate 7 of the guide roller assembly Y coaxially with the shaft 14, as shown in FIGS. 1 and 4. The two timing belt pulleys have a rotation ratio of 1:1. If the optical fiber drawing machine is in normal operation, optical fiber passes through the first take-up device 2, the distributing guide rollers 17 and 17', the second take-up device 9 and the tensile testing machine 27 without winding about rollers 3 and 3', and is wound on the winder (not shown), as shown by the arrows in FIG. 1. If the optical fiber is broken in the tensile testing machine 27, the second take-up device gradually reduces its speed, and simultaneously, the variable speed motor 13 is driven to rotate the shaft 14 in the direction of an arrow R in FIG. 1. The rotation of the shaft 14 causes the rotation of the arm 15 and the distributing guide rollers 17 and 17' about the accumulating guide roller assemblies in the direction of an arrow Q in FIG. 4 thereby winding and accumulating optical fiber on the accumulating guide roller assemblies. As the timing belt pulley 25 on the side plate 7 and the timing belt pulley 24 on the screw shaft 21 are connected to each other by the timing belt 26, the screw shaft is caused to rotate relative to the blocks 18 and 18' in the direction of an arrow T in FIG. 1 by the same angular distance as that of the rotation of the shaft 14. As a result, screws 22 and 23 cause the right-hand movement of the distributing guide roller 17 and the left-hand movement of the guide roller 17'. As the pitch of the screws is equal to that of the grooves on the accumulating guide rollers, the rotation of the shaft 14 results in the orderly distribution, winding and accumulation of optical fiber in the grooves 4 of the accumulating guide roller assemblies. The second take-up device, which has gradually reduced its speed, reaches stability at a constant speed. Optical fiber is withdrawn at a low speed and guided manually to the winder through the tension testing machine. The rotating speed of the variable speed motor 13 is adjusted so that the difference in take-up speed between the first and second take-up devices may effect accumulation of optical fiber. When the apparatus is brought back to its normal operating condition, the second take-up device is rotated at a higher speed than the first take-up device and motor 13 is rotated in the opposite direction, so that optical fiber may be released from the accumulator. The speed of the optical fiber leaving the second take-up device is, therefore, the sum of the take-up speed of the first take-up device and the speed of the optical fiber released from the accumulator. If all of the accumulated optical fiber has been released, the speed of the second take-up device is lowered to coincide with that of the first take-up device, i.e., of the drawing machine. Thus, any breakage of optical fiber in the tensile testing machine can be rectified without lowering the speed of the drawing machine or stopping it. The apparatus as hereinabove described has, however, a number of disadvantages. As the shafts 6 and 6' for the accumulating guide rollers 3 and 3' are fixed, the bearings 5 are subjected to a high degree of frictional resistance, and as the guide rollers for accumulating optical fiber are caused by the optical fiber to rotate at a speed coinciding with the traveling speed of the optical fiber to be accumulated, the guide rollers impose on the optical fiber an increased tension which may result in breakage, or a worsening of its properties even if it may not be broken. Moreover, the inertia of the guide roller causes a change in the tension of the optical fiber whenever the rotating speed of the guide rollers is varied. FIG. 5 shows an improved accumulator. The accumulating guide rollers are fixed to shafts 6 and 6'. The guide roller assembly Y is rotated by timing belts 35 and 37 via timing belt pulleys in such a way that the peripheral speed of the grooves on the rollers may coincide with the speed of the optical fiber on the first take-up device 2. The shafts 6' for the guide roller assembly Z are driven as a result of operation by a differential gear assembly 42 on the speed of optical fiber on the first take-up device and the speed of accumulation by the rotation of the arm 14. Thus, the peripheral speeds of the guide roller assemblies Y and Z are always maintained equal to the speed of optical fiber traveling past them. As the FIG. 5 arrangement uses a differential gear unit, its backlash creates an instantaneous speed change in the guide roller assembly Z and it causes a change in the tension of a wire or filament on the distributing guide rollers. As the accumulator comprises a plurality of guide rollers equally spaced apart from one another in a circular array, the wire or filament which is accumulated has a polygonal shape, and therefore, the wire or filament on the distributing guide rollers is subjected to the same number of pulsing speed changes as that of the sides of the polygon during each rotation about the accumulator when it is accumulated or released. This causes a change in the tension of the wire or filament on the distributing guide rollers. It is necessary to prevent such tension changes from occurring when the manufacturing process requires the maintenance of a low tension which does not make any appreciable change. The conventional system employs electrical control by the variable speed motor 13 of the speed of the optical fiber to be accumulated or released, and also requires the electrical control of the take-up speed of the second take-up device 9. An error is likely to develop between these two kinds of control. The correction of this error requires a complicated system, as it is necessary to correct the speed of the second take-up device 9 by the speed control dancer rollers 11. SUMMARY OF THE INVENTION The present invention solves this tension change problem. According to this invention, the accumulating guide roller assembly Z is mechanically connected to the second take-up device so that the surface velocity of the assembly Z may coincide with the take-up speed of the second take-up device. Tension and speed control means, such as dancer rollers, are provided between the distributing guide rollers 17 and 17' to maintain the optical fiber at a constant tension and to detect the length (or amount) of optical fiber therebetween. The tension and speed control means transmits a signal to the variable speed motor to correct the speed of optical fiber to be accumulated or released, or to a driving system for the second take-up device to correct its speed. These arrangements make it possible to prevent any tension change that might otherwise arise from the inertia and polygonal arrangement of the accumulating guide rollers, and thereby enable optical fiber to be accumulated or released properly. The accumulator of this invention differs from the above-described apparatus in that the peripheral speeds of the accumulating guide roller assemblies Y and Z are always caused by mutually independent mechanical connections to coincide with the take-up speeds of the first and second take-up devices, respectively, when optical fiber is wound for accumulation on the accumulator by the distributing guide rollers rotating coaxially with the accumulator. Therefore, the speed of the optical fiber being accumulated is always equal to the peripheral speed of the accumulating guide rollers, and there is no instantaneous tension change that might otherwise result from the backlash of the interconnecting gears. The optical fiber is accumulated at a constant tension, since the take-up speed of the second take-up device or the speed of the optical fiber accumulation is finely controlled in accordance with a control signal transmitted by the tension and speed control device provided in the passage for the optical fiber between the distributing guide rollers. The accumulating capacity of the tension and speed control device absorbs any tension change caused by the polygonal arrangement of the accumulating guide rollers. Thus, the accumulator of this invention is very effective for use with a drawing machine for producing a wire or filament having a low tensile strength and which may be easily broken, such as optical fiber. BRIEF DESCRIPTION OF THE DRAWINGS The invention will now be described in detail with reference to the drawings. FIG. 1 is a front elevational view of a first type of accumulator; FIG. 2 is a front elevational view showing the arrangement of accumulating guide rollers; FIG. 3 is a detailed view of a portion designated at B in FIG. 1; FIG. 4 is a sectional view taken along the line A--A of FIG. 1; FIG. 5 is a diagram showing a driving system for another accumulator; and FIG. 6 is a diagram showing a driving system for an accumulator embodying this invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT FIG. 6 is a front elevational view of a preferred embodiment of this invention. Like reference numerals are used to designate parts that are like or corresponding to those of the other FIGURES. Accumulating guide rollers 3 and 3' are fixed to the shafts 6 and 6' supported rotatably by bearings 29 and 29' on the side plates 7, 7', 8 and 8'. Timing belt pulleys 34 of the same size are provided on one end of each shaft 6 in the guide roller assembly Y, and are connected by a single timing belt 35 so that all of the guide rollers are able to rotate at the same speed in the same direction. A timing belt pulley 36 is provided on one of the shafts 6, and driven by a driving timing belt 37. The timing belt 37 is driven from the shaft of a variable speed motor 39 which drives the first take-up device 2 through a speed changer 40 having speed change ratio i 1 . Timing belt pulleys 30 of the same size are provided on the opposite end of each shaft 6' in the guide roller assembly Z, and are connected by a single timing belt 31 so that all of the guide rollers are able to rotate at the same speed in the same direction. A timing belt pulley 32 is provided on one of the shafts 6' and is driven by a driving timing belt 33 which is connected to the shaft of a variable speed motor 44 which drives the second take-up device 9 through a speed changer 50 having a constant speed change ratio i10. The timing belt pulley 32 is designed to provide the timing belts with a transmission ratio of i8 and i9 to enable the peripheral speed of the grooves on the guide rollers 3' to coincide with the take-up speed of the second take-up device 9. Although two timing belt transmissions i8 and i9 are shown, it is, of course, possible to employ only a single transmission if it provides the same transmission ratio. It is also possible to use any connecting means other than the timing belts if it enables transmission at an accurate speed ratio. The arm 15 is secured to the end of the shaft 14 extending through the center of the guide roller assembly Z and is driven by the variable speed motor 13. The distributing guide rollers 17 and 17' are transversely movably provided on the end of the arm 15 to accumulate the wire or filament on the accumulating guide rollers. Tension and speed control means 45, such as dancer rollers, are provided between the distributing guide rollers 17 and 17'. As shown, the tension and speed control means may be mounted on the arm 15 and guide bar indicated at reference numberal 16. A signal representing the displacement of the dancer roller or like means is transmitted through the arm 15 and picked up through a slip ring 46 provided on the shaft 14. The operation of the apparatus will be described with reference to FIG. 6. When the apparatus is in its normal operating condition, the optical fiber leaving the drawing machine passes through the wheel of the first take-up device 2 which is driven by the motor 39 via the speed changer 40, the distributing guide roller 17, the tension and speed control device 45, the distributing guide roller 17' and the wheel of the second take-up device 9. If it has become necessary to accumulate optical fiber, the speed of the second take-up device 9 is changed, and the shaft 14 and the arm 15 are driven by the motor 13 to drive the distributing guide rollers 17 and 17' so that optical fiber may be wound on the accumulating guide roller assemblies Y and Z. The variable speed motors 13 and 44 are controlled to ensure that the winding or unwinding speed V 3 is always equal to the take-up speed V 1 of the first take-up device 2 less the take-up speed V 5 of the second take-up device 9. According to the arrangement hereinabove described, the peripheral speed V 2 of the guide roller assembly Y is always equal to the take-up speed V 1 of the first take-up device 2, as they are mechanically connected to each other, and the peripheral speed V 4 of the guide roller assembly Z is always equal to the take-up speed V 5 of the second take-up device 9, as they are mechanically connected to each other. It follows that the speed of the optical fiber accumulated on the guide rollers is always equal to the peripheral speed of the bottom of the grooves on the guide rollers. Thus, there is no sliding of the optical fiber relative to the guide rollers. There is, therefore, no tension created by the friction between the optical fiber and the guide rollers. A difference is likely to arise between the take-up speed V 5 of the second take-up device 9 and the speed V 3 of accumulation of the variable speed motor 13, as they are controlled from an external source. The difference is, however, detected by way of the displacement of the dancer roller or like control means 45 between the distributing guide rollers 17 and 17', and a signal is picked up through the slip ring 46 on the shaft 14 to correct the external control of the motors 13 and 44. This enables the optical fiber to be accumulated without loosening or being unduly stretched. It is, of course, effective to make such correction for either of the motors 13 and 44. The tension and speed control device 45 maintains the optical fiber at a constant tension and as it has some accumulating capacity, it absorbs any slight changes in the speed of optical fiber that is due to the polygonal arrangement of the accumulating guide rollers. The device 45 is preferably of the construction not creating any tension change by centrifugal force as it is positioned for rotation about the accumulating guide rollers. Other embodiments and modifications of the present invention will be apparent to those of ordinary skill in the art having the benefit of the teaching presented in the foregoing description and drawings. It is, therefore, to be understood that this invention is not to be unduly limited and such modification are intended to be included within the scope of the appended claims.
An accumulator wherein the peripheral speeds of separate, accumulating guide roller assemblies are caused by respective independent mechanical arrangements to coincide with the take-up speeds of first and second take-up devices. Using this arrangement, the speed of the optical fiber being accumulated is always equal to the peripheral speed of the accumulating guide rollers so that there is no instantaneous tension change that would otherwise result from a backlash of interconnecting gears.
1
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus for determining the condition of an air-fuel ratio sensor and, more particularly, an apparatus for determining whether or not the air-fuel ratio sensor, which detects the air-fuel ratio of exhaust gas by detecting a limiting current which flows through a sensor element made of a solid electrolyte when voltage is impressed thereon, is activated. 2. Description of the Related Art An air-fuel ratio sensor for detecting the air-fuel ratio of exhaust gas by detecting a limiting current which flows through a sensor element made of solid electrolyte when voltage is impressed there on and convert the limiting current to signal voltage, is known in the above described type of air-fuel ratio sensor, the limiting current varies in accordance with a change in the sensor element temperature as shown in FIG. 3. As shown in FIG. 3, no limiting current flows until the sensor element temperature increases to some value. Then the limiting current begins to flow. The current increases in accordance with an increase in temperature, i.e. the sensitivity to a change in the air-fuel ratio increases in accordance with an increase in the temperature, and finally the current is stabilized when the temperature becomes higher than some value. Namely, the air-fuel ratio sensor correctly detects an air-fuel ratio only after it is heated up to the activation temperature. To quickly activate the sensor, it is known to provide the air-fuel ratio sensor with an electric heater. The heater will be broken if excessive electric power is supplied thereto. If the supplied electric power is too small, the output voltage of the sensor will drop to deteriorate detecting accuracy. It is necessary, therefore, to supply proper electric power to the heater. For this purpose, it is necessary to determine whether or not the sensor is in a full-activated state. To determine whether or not the air-fuel ratio sensor is activated, Japanese Unexamined Patent Publication Nos. 57-192852 and 58-178248 apply an alternating voltage to the sensor and measure the internal resistance of the sensor. Another prior art applies a negative voltage to the sensor, monitors the output of the sensor, and determines whether or not the sensor is activated. These prior arts involve high cost because they need a circuit for switching the voltages to apply. The prior art that alternately measures a limiting current and resistance cannot detect an air-fuel ratio while it is measuring resistance. Accordingly, while the sensor is in the half-activated state, this prior art is unable to apply feedback-control according to the rich/lean state of the air-fuel ratio, although it is possible to determine the rich/lean state in the half-activated state. An object of the present invention is to provide an apparatus capable of correctly determining whether or not an air-fuel ratio sensor is activated at low cost without interrupting the use of signals. SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide an apparatus which can determine the state of an air-fuel ratio sensor at low cost and with high accuracy. According to the present invention there is provided an apparatus for determining whether or not an air-fuel ratio sensor, which is arranged in an exhaust system of an internal combustion engine to detect the air-fuel ratio of exhaust gas, is activated. The apparatus has a heater for heating the air-fuel ratio sensor, a detector for detecting whether or not the air-fuel ratio sensor has reached a half-activated state to start changing the output thereof after the start of the engine, a unit for integrating power supplied to the heater from the start of the engine until the air-fuel ratio sensor reaches the half-activated state, a unit for estimating, according to the integrated power, the power to be supplied to the heater to bring the air-fuel ratio sensor to a full-activated state, and a unit for determining that the air-fuel ratio sensor is in the full-activated state once the estimated electric power has completely been supplied to the heater. The present invention will be more fully understood from the description of the preferred embodiments of the invention set forth below, together with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS In the drawings: FIG. 1 schematically shows a construction of an embodiment of the present invention. FIG. 2(a)-(d) is a time chart showing the principle of the present invention. FIG. 3 shows changes in a limiting current flowing through an air-fuel ratio sensor. FIG. 4 shows a relationship between cumulative electric power up to a half-activated state and cumulative power up to a full-activated state of the air-fuel ratio sensor. FIG. 5 is a flowchart showing an operation of the embodiment. DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 schematically shows a construction of an embodiment of the present invention. An engine 1 has an exhaust pipe 2 provided with an air-fuel ratio sensor 3. The sensor 3 consists of a sensor element 3a made of a solid electrolyte and a heater 3b for heating the element 3a. An engine control computer (ECU) 10 is a digital computer having a CPU (microprocessor) 11, a RAM (random access memory) 12, a ROM (read only memory) 13, an AD converter 14, and an output interface 15. These parts are connected to one another. The ECU 10 has additional parts mentioned below according to the present invention. A drive circuit 16 has a resistor for detecting a current passing through the element 3a to which a power source 21 applies a voltage. The driver circuit 16 also has an amplifier for amplifying a voltage drop in the resistor according to a given amplification factor. The drive circuit 16 supplies an output voltage to the CPU 11 through the AD converter 14. A heater controller circuit 17 controls power supplied from a heater power source 22 to the heater 3b in response to a control signal from the CPU 11. A heater voltage detector circuit 18 detects a voltage applied to the heater 3b after the heater is energized. A heater current detector circuit 19 detects a current passing through the heater 3b after the heater is energized. The CPU 11 carries out operations mentioned below according to signals from the above-mentioned parts and determines whether or not the element 3a of the air-fuel ratio sensor 3 is active. The CPU 11 also receives signals from other sensors through an input interface and the AD converter 14 and supplies control signals through the output interface 15, to control, for example, fuel injection and ignition timing. The principle of the present invention will be explained. FIG. 2 is a time chart showing the principle of the present invention. Chart (a) of FIG. 2 shows changes in the temperature of the element 3a of the air-fuel ratio sensor 3 after the engine is started. Chart (b) of FIG. 2 shows changes in the output voltage of the sensor 3. For a while after the start of the engine, no limiting current flows because the temperature of the element 3a is low. Accordingly, the output voltage of the sensor 3 corresponds to a stoichiometric air-fuel ratio. The reason of this will be explained. The sensor 3 and drive circuit 16 of the embodiment are the same as those of Japanese Unexamined Patent Publication No. 5-240829. The potential of the element 3a on the exhaust gas side is set to be higher than the ground level of the drive circuit 16. An output voltage Eo of the sensor 3 is expressed as follows: Eo=Vo+Vr+IR (1) where Vo is a potential, Vr is an applied voltage, I is a limiting current passing through the element 3a, and R is resistance for converting the limiting current into a voltage. When the temperature of the element 3a is low, there is no limiting current I, and therefore, Eo=Vo+Vr The formula (1) is written as follows: Eo=Vo+Vr+K(λ-1)R (2) where K is a proportional constant and λ is an excess air ratio. If λ=1, i.e., if it is a theoretical air-fuel ratio, λ-1=0, and therefore, Eo=Vo+Vr. Namely, if there is no limiting current due to a low temperature of the element 3a, the output voltage Eo is equal to that with a stoichiometric air-fuel ratio. When the element 3a reaches a temperature T1, the output voltage of the sensor 3 starts to change at a point A1. The output voltage of the sensor 3 after the start of the engine is integrated as shown in chart (c) of FIG. 2. When the integral exceeds a given threshold, the element 3a becomes half-activated, and a point of the exceeding the threshold is named the half-activated point. At the same time, power supplied to the heater 3b is integrated as shown in chart (d) of FIG. 2. The element 3a is further heated to reach a full-activated state. Then, the limiting current flowing through the element 3a greatly changes in response to an air-fuel ratio as indicated with continuous lines in FIG. 3. Namely, the output voltage of the sensor 3 starts to greatly change from a point A2 where the full-activated state starts. The temperature at which the element 3a enters the half-activated state is about 550° C. in this embodiment, and the temperature at which the element 3a enters the full-activated state is about 650° C. in this embodiment. This means that the element 3a in the half-activated state will reach the full-activated state if a given amount of power is supplied to the heater 3b. Namely, if the half-activated state is determinable, the full-activated state is also determinable. If the engine is started at a high temperature, the element 3a is hot because the temperature ambient air around the sensor 3 is high. If the temperature of the element 3a having a full-activation temperature of 650° C. is, for example, 600° C. when the engine is started, the element 3a quickly reaches the half-activated state and full-activated state because of a high ambient air temperature. If a fixed amount of electric power is supplied to the heater 3b under this situation, the element 3a will overheat and the heater 3b will break. Accordingly, the present invention finds a relationship between cumulative electric power W1 necessary for bringing the element 3a to the half-activated state and cumulative power W2 necessary for bringing the element 3a to the full-activated state as shown in FIG. 4. The relationship is stored as a map in the ROM 13. Then, cumulative electric power for bringing the element 3a to the full-activated state is obtained according to cumulative electric power supplied to bring the element 3a to the half-activated state, as shown in chart (d) of FIG. 2. Once it is detected that the cumulative power for bringing the element 3a to the full-activated state has completely been supplied to the heater 3b, it is determined that the element 3a is in the full-activated state. FIG. 5 is a flowchart showing a routine of determining whether or not the element 3a of the air-fuel ratio sensor 3 is in the full-activated state according to the present invention. The routine is started when the engine is started and is terminated when the element 3a reaches the full-activated state. Step 1 initializes engine controlling parameters stored in the RAM 12, a flag XAFS1 for indicating that the element 3a is in the half-activated state, and a flag XAFS2 for indicating that the element 3a is in the full-activated state. Step 2 reads an output VAF of the air-fuel ratio sensor 3. Step 3 calculates an integral LVAF of the output VAF as follows: LVAFi=LVAFi-1+ABS(VAFi-VAFi-1) where VAFi-1 is a preceding output of the sensor 3, VAFi is the present output thereof, and ABS(VAFi-VAFi-1) is an absolute difference between the present output VAFi and the preceding output VAFi-1. Step 4 calculates power Wi supplied to the heater 3b according to the product of a voltage VHi detected by the heater voltage detector 18 and a current AHi detected by the heater current detector 19. Step 5 calculates cumulative electric power SUMWi from the start of supply of power. Step 6 determines whether or not the integral LVAFi is greater than a threshold L1. If LVAFi≧L1, it is determined that the element 3a is in the half-activated state, and step 7 checks to see if XAFS1=0. If the flag XAFS1 is 0, step 8 sets the flag XAFS1 to 1 and substitutes the cumulative electric power SUMWi for SUMWs. If LVAFi<L1 in step 6, the flow returns to step 2 until LVAF exceeds L1. Step 9 searches, according to SUMWs, the map stored in the ROM 13 for cumulative power SUMWf to bring the element 3a to the full-activated state. Step 10 checks to see if SUMWi≧SUMWf. If SUMWi≧SUMWf, step 11 sets the flag XAF2 to 1 to indicate that the element 3a is in the full-activated state. Step 12 terminates the routine. If SUMWi<SUMWf in step 10, the flow returns to step 2 until SUMWi exceeds SUMWf. In this embodiment, the cumulative power SUMWf used to see whether or not the element 3a is in the full-activated state is an accumulation of electric power supplied to the heater 3b after the activation thereof until the element 3a is put in the full-activated state. The cumulative power SUMWf may be an accumulation of electric power supplied to the heater 3b after the element 3a is put in the half-activated state until the same reaches the full-activated state. In this case, a corresponding actual electric power supplied must be counted after the half-activated state. Namely, cumulative electric power must be cleared as soon as the flag XAFS1 is set to 1 and must again be integrated. As explained above, the present invention determines whether or not the air-fuel ratio sensor is in the half-activated state in which the sensor output starts changing, and calculates cumulative electric power for bringing the sensor to the full-activated state according to cumulative electric power consumed to bring the sensor to the half-activated state. The cumulative electric power for bringing the sensor to the full-activated state reflects the temperature of the sensor at the start of the engine. Consequently, the present invention correctly determines whether or not the sensor is in the half- or full-activated state. The present invention determines whether or not the sensor is in the half- or full-activated state without an alternating voltage or a negative voltage. Namely, the present invention allows the output voltage of the sensor to be used anytime. Even during an intermediate period between the half-activated state and the full-activated state, the output voltage of the sensor is usable to determine whether an air-fuel ratio is rich or lean to allow feedback-control of fuel injection.
An apparatus for determining whether or not an air-fuel ratio sensor, which is arranged in an exhaust system of an internal combustion engine to detect the air-fuel ratio of exhaust gas, is activated. The apparatus has a heater for heating the air-fuel ratio sensor, a detector for detecting whether or not the air-fuel ratio sensor has reached a half-activated state to start changing the output thereof after the start of the engine, a unit for integrating power supplied to the heater from the start of the engine until the air-fuel ratio sensor reaches the half-activated state, a unit for estimating, according to the integrated power, the power to be supplied to the heater to bring the air-fuel ratio sensor to a full-activated state, and a unit for determining that the air-fuel ratio sensor is in the full-activated state once the estimated power has completely been supplied to the heater.
5
BACKGROUND [0001] It is desirable at times to plug tubular systems that are employed to transport fluids. In the downhole industry, for example, operators inject matter referred to as “junk shot” into leaking wellbores to plug the leak. Junk shot is commonly made of ground up tires and metal balls. Although such material often works adequately for its intended purpose, operators are always interested in new devices and methods to improve the art. BRIEF DESCRIPTION [0002] Disclosed herein is plug-inducing matter which includes junk shot comprising members and swellable material substantially covering the members which are configured to swell upon exposure to wellbore fluids. [0003] Also disclosed is a method of plugging a leaking wellbore including injecting junk shot having members covered by swellable material that is swellable in wellbore fluids into a leaking wellbore, exposing the swellable material to wellbore fluids, and swelling the swellable material. BRIEF DESCRIPTION OF THE DRAWINGS [0004] The following descriptions should not be considered limiting in any way. With reference to the accompanying drawings, like elements are numbered alike: [0005] FIG. 1 depicts a cross sectional view of a piece of junk shot disclosed herein; and [0006] FIG. 2 depicts a cross sectional view of an alternate embodiment of a piece of junk shot disclosed herein. DETAILED DESCRIPTION [0007] A detailed description of one or more embodiments of the disclosed apparatus and method are presented herein by way of exemplification and not limitation with reference to the Figures. [0008] Referring to FIG. 1 , plug-inducing matter referred to as junk shot disclosed herein is illustrated at 10 . The junk shot 10 includes, a member 14 that is covered by a swellable material 18 . Although the junk shot 10 illustrated in this embodiment is spherical the invention is not be limited to such a configuration as other shapes are contemplated. Optionally the member 10 may be bonded to the swellable material 18 at an interface 22 therebetween by an adhesive 26 or other means of generating attachment therebetween. [0009] The member 14 , in embodiments disclosed herein is substantially non-swellable, and may be constructed of phenolic, such as is commonly used for tripping balls in the downhole industry, or other materials such as, iron, lead, bismuth, ceramic and glass. It may be desirable to employ a material for the member 14 that has a density comparable to the density of fluid that the junk shot 10 will be injected within to facilitate placement of the junk shot 10 to the desired location. In other applications it may be desirable to employ members 14 having greater density than a target fluid so that the junk shot 10 will tend to sink therewithin. In a hydrocarbon recovery application, for example, where heavy muds and drilling fluids are employed, using a more dense material such as lead or bismuth for the member 14 can make transporting the junk shot 10 to the location of the leak to be sealed an easier task. [0010] The fluid in which the swellable material 18 needs to swell influences material selection for the swellable material 18 . As such, for applications in which the target fluid is well defined the swellable material 18 can be tailored specifically to that target fluid. Generally, for wellbore fluids such as water, brine, hydrocarbons, drilling mud, or combinations of these a material that will swell in either an aqueous or a non-aqueous medium or both is preferred. Materials disclosed in U.S. Patent Application 2010/0147507, the content of which is incorporated by reference herein in its entirety, meet these specific criteria for use as the swellable material 18 . The '507 reference discloses use of a rubber compound based on a base polymer of EPDM (e.g., ethylene propylene diene monomer rubber) or Nitrile with an acrylic copolymer added that can volumetrically swell un bonded as much as 250-300% in refined oil or water respectively. Since swelling materials to these levels can weaken the material significantly, using a compound/material that swells when bonded in the range of 5-35% may be more desirable for the swellable material 18 that covers the member 14 . [0011] In addition to the materials employed for the member 14 and the swellable material 18 , sizes of the junk shot 10 also influence mobility and sealing effectiveness thereof In wellbore applications a maximum radial dimension 30 of between ¾ to about ¼ inches for the junk shot 10 may provide the mobility and sealing effect desired. Accordingly, the foregoing maximum radial dimension 30 of the junk shot 10 can well accommodate a maximum radial dimension 34 of the member 14 of between ½ to ¾ of an inch. [0012] Additionally, the junk shot 10 can include pieces 38 , or chunks, of the swellable material 18 that do not have the member 14 encased therein. The pieces 38 can have well defined shapes, such as spherical, cubic, elliptical, etc, or can have random shapes such as may be generated from grinding or tearing the pieces 38 from a larger portion of the swellable material 18 . Employing a maximum radial dimension 42 of between 1 and 1 1/4 inches for the pieces 38 may maintain a desired distribution of the pieces 38 within the junk shot 10 during transport to assure the pieces 38 aid in plugging a leak. Additionally, since the pieces 38 do not include a member 14 may be configured to swell unbonded in the range of 10-100% volumetrically for best results. [0013] While the invention has been described with reference to an exemplary embodiment or embodiments, it will be understood by those skilled in the art 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 may be made to adapt a particular 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 claims. Also, in the drawings and the description, there have been disclosed exemplary embodiments of the invention and, although specific terms may have been employed, they are unless otherwise stated used in a generic and descriptive sense only and not for purposes of limitation, the scope of the invention therefore not being so limited. Moreover, the use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another. Furthermore, the use of the terms a, an, etc. do not denote a limitation of quantity, but rather denote the presence of at least one of the referenced item.
Plug-inducing matter includes junk shot comprising members and swellable material substantially covering the members which are configured to swell upon exposure to wellbore fluids.
4
This is a divisional of copending application Ser. No. 243,303, filed as PCT US 87/00206 on Jan. 30, 1987, published as WO87/04716 on Aug. 13, 1987 now U.S. Pat. No. 4,891,075. BACKGROUND OF THE INVENTION This invention relates to useful applications of the formation of a dihydropyridine condensation product formed by the reaction of a β-diketone, an aldehyde and an amine. More particularly it relates to a wavelength shifting device which permits a photovoltaic cell to collect energy from the energy-rich portion of the solar spectrum and to sensitive methods of detecting amines and aldehydes. The invention exploits the long-lived fluorescence and large Stoke's shift associated with the lanthanide ion chelate fluorophores that can be made with the condensation products. That part of the solar spectrum below 450 nm is poorly or not at all available for conversion to electricity by photovoltaic cells. Furthermore, this part of the solar spectrum is very rich in energy at the surface of the earth and even more so extraterrestrially. These facts are well documented in "Sunlight to Electricity: Prospects for Solar Conversion by Photovoltaics" Joseph A. Merrigan, MIT Press, Cambridge, Mass. (1975). Attempts have been made to reduce the problem using luminescent solar collectors (LSC) which are dye-doped plastics or glass plates. A type of dye advocated is a weak metal chelate. For example, M.S. Cook and A.J. Thomson in "Chemistry in Britain" (Oct. 1984, p.914-917) advocate the use of ruthenium (II) complexes with 2-2'-bipyridine or 1-10-phenanthroline. They report, however, that these materials do not have long term photostability. This problem stems from the low stability that would be associated with the use of a metal to bidentate chelate even in 1:3 ratio in dilute solution in the plastic or glass. What is required is a fluorophore with a large Stoke's shift which is also able to remain in long term photostability. It is known from U.S. Pat. No. 3,956,341 and International Patent Application PCT/GB85/00337 that an aldehyde (R 1 --CHO), an amine (R 2 --NH 2 ) and a β-diketone (R 3 COCH 2 COR 4 ) (with R 1 , R 2 , R 3 and R 4 being arbitrary organic radicals and R 1 and R 2 optionally being hydrogen) react to form a dihydropyridine condensation product as illustrated in FIG. 1. The reaction is preferrably carried out at a mildly acidic pH (5.5-6.5) and a mildly elevated temperature (30°-80° C). It is dependent only on the basic structure of the aldehyde, amine and β-diketone and not on the nature of the substituents R 1 to R 4 so that it can be used with a wide variety of aldehydes, amines and β-diketones. Examples of β-diketones are trifluoroacetylacetone, thenoyltrifluoroacetone and benzoyl and alpha- and beta-naphthoyl trifluoroacetone as well as the β-diketones mentioned in U.S. Pat. No. 4,374,120. Other β-diketones that might be employed are carboxy-modified versions of the above mentioned β-diketones. The dihydropyridine condensation product, according to Nash (T. Biochem. J. 55, 1953, p.416-421), has the capability to form an enol at the 4 position and probably holds a metal ion by chelation at that site. When the chelated metal is a lanthanide metal ion, especially Eu(III) or Tb(III) but also Sm(III) or Dy(III), the metal ion and the condensation product exist as an acceptor-donor pair, so that the condensation product acts as a chelating chromophore, absorbing excitation radiation at its characteristic absorption peak(s) and by energy transfer inducing the resonance fluorescence of the lanthanide metal ion. These fluorescence properties are recognized in International Patent Application PCT/GB85,/00337 and used to produce lanthanide ion fluorescent labels to be used in fluoroimmunoassays. The valuable properties of the chelating condensation products can be utilized in several ways and the present invention is concerned with the utilization. Any chelates with suitable absorption and donor properties as those described for the condensation product and able to form kinetically stable 1:1 chelates with lanthanide metal ions would serve a similar purpose of wavelength conversion. A class of such chelates and methods for making them are disclosed in European Patent Application No. 0,195,413. Those with good quantum efficiencies for the fluorescence of Eu(III), Sm(III) and Dy(III) are to be preferred as the principal emission bands, as shown in FIG. 3, of these ions are more available to the commonest sort of photovoltaic cells. Except for CdS cells, the absorption edges for most other popular photovoltaic materials lie beyond 800 nm. In addition to the work that has been done on photovoltaic cells and dihydropyridine condensation products, fluorometric methods have been used to detect chemical substances. The sensitivity of these detection systems is inhibited by the high background fluorescence associated with most organic substances. A highly sensitive analytical procedure for the determination of formaldehyde, for example, is useful in the study of biological systems and air pollution. Many biological substances such as sugars, hydroxamino acids, methanol, formic acid etc. are determined by first converting them to formaldehyde by oxidation or reduction. Also, the detection and estimation of amines, especially in amino acids and proteins, are important in biochemical studies. In chromatography it is important to be able to detect small quantities rapidly. The use of chelates of lanthanide ions as fluorescent labels in the determination of aldehydes and amines offers a great improvement in signal to noise ratios over previously used fluorophores. SUMMARY OF THE INVENTION In accordance with the present invention, it has been discovered that photovoltaic cells, when optically coupled to a wavelength-shifting device comprising a polymer containing a lanthanide metal ion chelated to a dihYdropYridine condensation product, can utilize energy from the energy-rich portion of the solar spectrum. This portion of the solar spectrum was previously unavailable to photovoltaic cells. Accordingly, the present invention utilizes a dihydropyridine condensation product which is chelated to a lanthanide ion in a polymer as a wavelength-shifting device which can be coupled to a photovoltaic cell. The condensation product absorbs a significant level of energy and transfers the energy to the lanthanide ion. The lanthanide ion then emits or fluoresces at a longer wavelength. Present photovoltaic cells are only able to collect energy from these longer wavelengths. By coupling this chelated condensation product to a solar cell, energy from the low-wavelength portion of the solar spectrum is finally available for conversion to electricity. The present invention also uses the components of the dihydropyridine condensation product chelated to a lanthanide ion to detect for amines and aldehydes. The dihydropyridine condensation product is composed of a β-diketone, an aldehyde and an amine. It exploits the long-lived fluorescence and large Stoke's shift associated with the lanthanide ion chelate fluorophores that can be made with the condensation products. It is therefore a object of the present invention to provide a photo-converting device which absorbs energy from the energy-rich portion of the solar spectrum (280-460 nm). It is another object of the present invention to provide a coating for present photovoltaic cells which absorbs energy from the energy-rich portion of the solar spectrum (280-460 nm) and emits energy in a form (540 nm and beyond) which is better available to present photovoltaic cells. It is a further object of the present invention to provide a coating for present photovoltaic cells which absorbs energy from the energy-rich portion of the solar spectrum (280-460 nm) and emits energy in a form (540 nm and beyond) which is better available to present photovoltaic cells and the fluorophore has long term photostability. It is another object of the present invention to increase the sensitivity or signal to noise ratio over previously used fluorophores. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an illustration of the dihydropyridine condensation reaction. FIG. 2 is a schematic diagram of the photo-electric device with a coating containing a lanthanide metal ion chelated to a dihydropyridine condensation product. FIG. 3 shows the principal emission lines of some of the lanthanide ions of interest. FIG. 4 illustrates the slightly modified molecule thenoyltrifluoroacetone which provides good solubility and extra coordination ability. FIG. 5 illustrates an example of a chelating aldehyde and a method for producing it. FIG. 6 illustrates the excitation spectrum of the β-diketone shown in FIG. 4 chelating Eu(III) with an emission of 613 nm. FIG. 7 illustrates the excitation spectrum of the dihydropyridine condensation product of the β-diketone of FIG. 4 and the chelating aldehyde of FIG. 5 with a mouse monoclonal antibody against carcinoembryonic antigen (CEA) as an example both of an amine and a polymer. Eu(III) has an emission of 613 nm. FIG. 8 illustrates the excitation spectrum of multiple covalently linked β-diketone of FIG. 4 chelating Eu(III). FIG. 9 illustrates the excitation spectrum of the condensation product of the multiple-covalently linked β-diketone, the chelating aldehyde of FIG. 5 and the monoclonal anti CEA. Eu(III) has an emission of 613 nm. FIG. 10 illustrates the excitation spectrum of the condensation product of the multiple-covalently linked β-diketone, formaldehyde and the monoclonal anti CEA. Eu(III) has an emission of 613 nm. DESCRIPTION OF THE PREFERRED EMBODIMENTS At the outset, the invention is described in its broadest overall aspects with a more detailed description following. The properties of the condensation product are utilized to produce a wavelength-shifting material. Such a material comprises the chelation product of a fluorescing lanthanide metal ion and a solid forming dihydropyridine condensation product of an NH 2 -bearing reagent, a β-diketone-bearing reagent and an aldehyde-bearing reagent, one of which reagents forms part of a polymer. The material absorbs energy at the excitation band absorption maxima of the dihydropyridine condensation product and emits energy at the characteristic wavelength corresponding to the metal ions chelated. Conveniently, the NH 2 -bearing reagent is a polymer. Polyethyleneimine is an example of such a polymer. Alternatively the aldehyde-bearing reagent may be a polymer. If desired, pre-existing polymers used as structural parts of conventional photovoltaic cells may be modified by incorporation of amine or aldehyde or β-diketone groups prior to reaction with the other reagents to form the dihydropyridine condensation product. Such a polymer is the polyimide used with CdS photovoltaic cells as described by S.A. Merrigan in "Sunlight to Electricity: Prospects for Solar Conversion by Photovoltaics." MIT Press, Cambridge, Mass. (1975). The wavelength-shifting material may be dispersed in a transparent material such as glass or a plastic material, for example polystyrene or polypropylene or some co-polymer suitable for use with photovoltaic cells, if it does not itself already form a transparent polymer useful for such purposes. The resulting product may be placed on one face of a silicon or other photovoltaic cell or as a part of a luminescent solar collector device (LSC). Such a device will absorb solar energy at the wavelengths of 280-460 nm, which is the energy-rich region of the solar spectrum. This energy range is generally not available to conventional photovoltaic devices. The device will emit energy in the region of 540-650 nm and beyond, which is a range that is better available to silicon or other photovoltaic cell or device. Further details of the construction and arrangement of an LSC device are given in an article by M.S. Cook and A.J. Thomson. Similar constructions can be used with the characterizing condensation products of this invention. Any chelates with suitable absorption and donor properties as those described for the condensation product and able to form kinetically stable 1:1 chelates with lanthanide metal ions would serve a similar purpose of wavelength conversion. A class of such chelates and methods for making them are disclosed in European Patent Application No. 0,195,413. Those with good quantum efficiencies for the fluorescence of Eu(III), Sm(III), and Dy(III) are to be preferred as the principal emission bands of these ions are more available to the commonest sort of photovoltaic cells. Except for CdS cells, the absorption edges for most other popular photovoltaic materials lie beyond 800 nm. The formation of the condensation product is used to present a metal in a convenient form, possibly having new electronic, electrical or chemical properties. Because it is possible to use a wide variety of amines and aldehydes in the condensation reaction, the choice of these materials can be dictated by a desire to chelate any desired metal. When the metal-bearing condensation product is formed in a polymer or dispersed in a polymer, the metal is present in a kinetically stable state as a result of its strong chelation. Thus it is possible to provide a thin film of one or more metals by this means. The photoelectric device, illustrated in FIG. 2, consists of a photovoltaic cell (1) with a coated polymer (2) on its face. The coated polymer (2) is a material with long term photostability. The coated polymer (2) is a polymer of a dihydropyridine condensation product chelated with a lanthanide metal ion. The coated polymer (2) is composed of the reactants illustrated in FIG. 1 and reacted under the conditions previously mentioned. A suggested β-diketone for this purpose is the modified thenoyltrifluoroacetone illustrated in FIG. 4 which increases solubility and increases the stability constant for chelating lanthanide metal ion in the final dihydropyridine compound. This β-diketone provides extra coordination ability. An example of a chelating aldehyde and a method for producing it is illustrated in FIG. 5. The chelated lanthanide ions which are chelated to the condensation product emit energy within the range most accessible to the photovoltaic cell and are listed in FIG. 3. The coating absorbs energy from the energy-rich portion of the solar spectrum (280-460 nm) as illustrated in FIG. 7. The coated polymer is then absorbed on a transparent material (3) and placed on the face of the photovoltaic cell. The device as shown in FIG. 2 in its entirety is subjected to sunlight and converts energy into electricity. The following reagents were used in the following example which is presented for illustrative purposes only and is not intended to limit the scope of the invention. (1) A commercially available polymer which possesses an amino group, mouse monoclonal antibody against carcinoembryonic antigen (CEA), is in a solution containing approximately 10 mg/ml. (2) A 1:1000 dilution of a aldehyde solution originally 37-40% w/v in the aldehyde of FIG. 5, thus now having a concentration of about 1.4×10 -3 moles/liter. (3) A stock solution of the modified β-diketone illustrated in FIG. 4 in methanol at a concentration of 160 mM. EXAMPLE The coating was manufactured with 400 μl of the mouse monoclonal antibody solution (2.7×10 -8 mole of antibody) were incubated at 37° C. for 1 hour with 200 μl of the diluted aldehyde solution (2.7×10 -7 mole of aldehyde) and 4 μl of the β-diketone solution (5.4×10 -7 mole of β-diketone) in an acetate buffer (0.2 M) at a pH of 5.7. The reaction product was dialysed initially against the acetate buffer to remove unreacted small molecules then against the acetate buffer containing Eu(III) ions at 10 -7 M concentration to form the chelation product (the fluorophore) and finally against the acetate buffer to remove excess Eu(III). The dihydropyridine condensation product chelated to Eu(III) was coated onto a thin, transparent polystyrene sheet by physical adsorption. The coated polystyrene sheet was place on the face of a Radio Shack model photovoltaic cell. The photo-conducting device was exposed to sunlight. The electrical current was measured and compared to the electrical output monitored from the Radio Shack model with only the polystyrene sheet on its face and under the same conditions. According to a second aspect of the invention, the formation of the dihydropyridine condensation product is used as a means of detecting the presence of amines or aldehydes. The detection system is used especially in high performance liquid chromatography (HPLC). Thus, a process for detecting the presence of an amine in a material stream comprises contacting the material stream with a β-diketone and an aldehyde with chelation functionality carrying a lanthanide metal ion by chelation and detecting the presence or absence of fluorescence at the excitation maximum of the dihydropyridine condensation product. Similarly, a process for detecting the presence of an aldehyde in a material stream comprises contacting the material stream with a β-diketone and an amine carrying a lanthanide metal ion by chelation and detecting the presence or absence of the fluorescence at an appropriate excitation maximum of the dihYdropYridine condensation product. The chelate attached to the amine could have a high stability constant for chelating the metal ion as well as being a good donor for example as disclosed in European Patent Application No. 0,195,413. It may be advantageous to include a synergist to stabilize and augment the lanthanide ion fluorescence, for example trioctylphosphine oxide or other known synergist. It may also be desirable for the contacting to be carried out at a suitably elevated temperature to speed up the formation of a detectable quantity of the condensation product, for example, it could be carried out as a post-column treatment of the sample in HPLC. Such a detection method enjoys the sensitivity associated with lanthanide ion fluorescence, especially when time-resolution principles are used to achieve specificity. The absorption maximum of the dihydropyridine condensation product should of course be different from that of the β-diketone starting material, otherwise a separation step might be required. An example of an improved amine detection system would include contacting an unknown solution with a β-diketone and an aldehyde chelated to lanthanide metal ion. The detection of fluorescence at the excitation maximum of the dihydropyridine condensation product as illustrated in FIG. 7 indicates the presence of an amine. An example of an improved aldehyde detection system would operate on the same principles as the amine detection system described above with the exception that the aldehyde reactant is replaced with an amine carrying a lanthanide metal ion by chelation. The invention is further illustrated by the following nonlimiting examples: EXAMPLE 1 Different wavelength-shifting devices were placed in front of a silicon-photovoltaic cell which was then exposed to sunlight. The electrical output from the photovoltaic cell wa measured in volts produced across an electric motor. The results of this experiment are shown below in Table 1. The degree to which the fluorophore enhanced the photovoltaic cell is recorded in terms of percent. The silicon-photovoltaic cell was a Radio Shack model numbered 277-1201. Each wavelength-shifting device included a polystyrene film base. Some of the devices also included coatings of the various fluorophores described in this paper. The dihydropyridine condensation product is denoted as DHP in Table 1. TABLE 1______________________________________Configuration Voltage Across Motor % Increase______________________________________Plain film 0.411 --Film with DHP Tb.sup.3+ 0.422 2.68Film with DHP Eu.sup.3+ 0.445 8.27______________________________________ EXAMPLE 2 This is an example of an amine detection system. Proteins are characterized by their amine tails. The concentration of proteins in a solution was determined by measuring the Eu(III) ion fluorescence associated with the dihydropyridine condensation product. The Eu(III) ion fluoresces at the new excitation wavelength introduced by product formation. The materials used in this example are as follows: ______________________________________TBA-TFA 0.5 × 10.sup.-3 M in a 0.1M acetate buffer at pH 5.5Chelating 0.37 × 10.sup.-3 M in a 0.1M acetate bufferaldehyde at pH 5.5Antibody Serially diluted in a 0.1M acetatesolution buffer at pH 5.5______________________________________ The procedure used in this example is as follows: 0.5 ml each of aldehyde (with Eu) and β-diketone solution were added to 1 ml aliquots of different known concentrations of antibody. The solutions were incubated for one hour at 37° C. and cooled to room temperature. Fluorescence was measured in a Perkin Elmer LS5 spectrofluorometer under a delayed fluorescence mode with the following settings: Delay 0.05 ms Gate 0.5 ms Fixed scale 2.0 Slits Ex 15; Em 20; Ex 277 nm Em 615 nm The results from this example are shown below in Table 2. TABLE 2______________________________________Protein Concentration (mg/ml) M Fluorescence______________________________________0.87 5.7 × 10.sup.-6 680.22 1.4 × 10.sup.-6 180.05 0.36 90 4______________________________________ The same samples were photon counted using a time-gated fluorometer after separation of small molecules. The counts measured are recorded in Table 3. The data in Table 3 was used to construct a calibration curve for determining unknown protein concentrations by interpolation. TABLE 3______________________________________Protein Concentration (mg/ml) Counts______________________________________0.87 2.2 × 10.sup.80.22 5.5 × 10.sup.70.05 1.4 × 10.sup.70.01 3.0 × 10.sup.6 0.003 8.6 × 10.sup.50 2.0 × 10.sup.3______________________________________ EXAMPLE 3 This is an example of an aldehyde detection system. The concentration of formaldehyde, an aldehyde, in a solution was determined by method of the condensation product formation together with delayed-timegated Eu(III) flourescence measurements similar to Example 2. The materials used in this example are as follows: 1. A 1×10 -3 M concentration of β-diketone (TBA-TFA) containing a stoichiometric amount of Eu(III) in a 0.1M acetate buffer at pH 5.5 2. A 2.0M concentration of amine - ammonium acetate in a 0.1M acetate buffer at pH 5.5 3. Formaldehyde solutions diluted in a 0.1M acetate buffer at pH 5.5 The stock solution consisted of a β-diketone solution mixed with ammonium acetate solution in a 1:1 ratio. The procedure used in this example is as follows: 1 ml of the mixed stock solution of β-diketone and ammonium acetate were added to 1 ml aliquots of diluted formaldehyde solutions. The solutions were incubated for 1 hour at 37° C. and cooled to room temperature. The fluorescence of the solution was measured in a Perkin Elmer Spectrofluormometer without separation. The results from this example are as follows: The excitation spectrum did not have two peaks. It had the identical peak corresponding to the β-diketone. The peak at 280 nm in the case of the antibody product is attributed to the antibody. The signal detector was necessary to eliminate noise from the unreacted β-diketone-Eu(III) complex. The readings therefore decreased with increasing concentration as shown below in Table 4. A calibration curve, similar to that constructed in example 2, could be used to determine the formaldehyde concentrations. TABLE 4______________________________________Formaldehyde Reading Ex 350Concentration (M) Em 615 Scale Factor Counts______________________________________10.sup.-3 168 8.6 × 10.sup.610.sup.-4 61 3.2 × 10.sup.810.sup.-5 204 3.8 × 10.sup.910.sup.-6 251 4.4 × 10.sup.910.sup.-7 256 4.5 × 10.sup.9blank 266 4.6 × 10.sup.9______________________________________ The invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and there is no intention to exclude any equivalence thereof. Hence, it is recognized that various modifications are possible when within the scope of the present invention as
Fluorescent lanthanide chelates are formed by reacting a β-diketone, an aldehyde, and an amine to produce a dihydropyridine condensation product which is then chelated with a lanthanide metal ion. These fluorescent chelates are made into wavelength-shifting devices by physically supporting the chelates on a polymer. Such wavelength-shifting devices can be optically coupled to a photoelectric cell to increase the portion of the solar spectrum available to the cell for conversion into electricity. Furthermore, the reaction producing the fluorescent lanthanide chelates is used to detect amines or aldehydes in a sample.
8
BACKGROUND OF THE INVENTION This application is a continuation of Ser. No. 720,146, filed Jun. 24, 1994, now abandoned. This invention relates to improved method and apparatus for removing pile distortions in fabric created by heat-setting and/or dyeing and/or upon treatment by high pressure streams of liquid. In the case of pile fabrics, which have been heat set at a high temperature with the pile erect and then dyed at a lower temperature during which the pile is substantially disturbed, as in jet dyeing, it is then desired to have the pile return to its original erect condition. One attempt in solving this problem is the tensionless dryer. In this machine, the pile fabric is fed onto a mesh belt that is then transported through a long heated tunnel where either mechanical action or perpendicular air blasts directed at the belt cause the fabric to undergo rather gentle undulations. The fabric is statically charged by friction with the air or contact with various parts of the dryer. The required processing time results in a drying unit over one hundred feet long with a low fabric line speed. There are quality problems associated with a lack of control over the fabric for such a long distance and well as marks that occur when the fabric strikes the upper section of the tunnel. Another type of pile conditioning device is the use of a high velocity air jet such as U.S. Pat. No. 4,837,902. In this case, the fabric is heated to the desired temperature and the conditioning is accomplished almost instantaneously by vigorous sawtoothed shaped waves that are small in amplitude, but effective due to high accelerations normal to the fabric surface produced by the wave's small bending radius and high velocity. The disadvantage of this process is direct contact of the heated fabric with the air stream, which tensions the fabric and can set in distortions in sensitive knit fabrics. Also, this process is less effective with highly permeable fabrics, as the air may not be trapped between the fabric and plate. Yet another type of device vibrates and charges the pile fabric in the heated condition by contact with pneumatically excited diaphragms. The contact of the fabric with the diaphragms combined with the rapid vibrations induced by the air stream cause the diaphragm to wear out at a rate in which replacement can be a daily occurrence. Still another type of device vibrates and charges the pile fabric biaxially by means of a rotating cylindrical roll with spaced protrusions or depressions along the exterior surface of the cylinder, followed by optionally vibrating the fabric axially by means of a second rotating cylindrical roll having flat portions continuously extending along the longitudinal axis of the second cylinder. The repeated and rapid front to back and side to side movement of individual pile fibers caused by multiple vibrational waves during biaxial treatment allows the fibers to return to their preferred heat-set orientation. The present invention solves the above problems in a manner not disclosed in the known prior art. SUMMARY OF THE INVENTION A method and apparatus for continuous treatment of webs of fabric having an upright pile comprising spraying the pile fabric with a sheet of liquid and then optionally heat-setting the fabric. The spraying of pile fibers allows the fibers to return to their preferred upright orientation. An advantage of this invention is that heat is not involved in the reorientation process so that the pile fabric is less distressed or deformed than current reorientation methods. It is another advantage of this invention to provide for a uniformity of face finish. The forces involved in the process are aligned with the direction of the desired pile orientation. Yet another advantage of this invention is that a hot tenter frame is not needed, which is a very costly and time consuming operation. Still another advantage of this invention is that it is simple and reliable and provides a distinct improvement in quality. Another advantage of this invention is that the fabric does not undergo shrinking that is the result of a heat-type drying stage and can undergo further wet-type processing downstream. These and other advantages will be in part apparent and in part pointed out below. BRIEF DESCRIPTION OF THE DRAWINGS The above as well as other objects of the invention will become more apparent from the following detailed description of the preferred embodiments of the invention, which when taken together with the accompanying drawings, in which: FIG. 1 is a diagrammatic side elevational view of the apparatus constructed according to the present invention with the fabric being patterned by a liquid stream, then having the pile restored by means of a liquid spray and then heat set; FIG. 2 is a diagrammatic side view of the liquid spray of FIG. 1, showing only the liquid spay means striking a pile fabric; FIG. 3 is a perspective view of an apparatus embodying the instant invention wherein a transverse stream of a control fluid is used to interrupt the fluid streams confined in channels or grooves 166; FIG. 4 is a section view taking along lines II--II of FIG. 3 and depicts the apparatus wherein a fluid stream is directed at a textile substrate; FIG. 5 is an enlarged section view of the inlet and discharge cavity portion of the apparatus of FIG. 4, showing the effects of energizing the control stream; FIG. 6 is a section view taken along lines IV--IV of FIG. 5; and FIG. 7 is a blown-up view of the grooves shown in FIGS. 4 and 5. Corresponding reference characters indicate corresponding parts throughout the several views of the drawings. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT Referring now by reference numerals to the drawings, and first to FIGS. 1-2, an assembly to erect pile fabric is generally indicated by numeral 11. Referring now to FIG. 1, pile fabric 25 is initially removed, with the pile side down, from the underside of supply roll 14. The fabric 25 is then directed vertically upward by a first idler roll 16 then substantially in a horizontal direction by second idler roll 18. The pile fabric 25 then comes in contact with third idler roll 20 that positions the fabric around treatment roll 21. The treatment that occurs at treatment roll 21 is that of patterning and/or napping fabric by means of high velocity liquid stream(s). The apparatus and method of this invention will operate to restore any pile fabric regardless of the cause of disorientation and the high velocity liquid stream(s) treatment is merely included as an illustrative example. The high velocity liquid stream treatment, as shown in FIG. 1, includes a pump 8 connected to a source 2 of the desired working fluid, e.g., water, via conduit 4 and filter assembly 6. Filter assembly 6 is intended to remove undesirable particulate matter from the working liquid that could clog the various orifice assemblies discussed below in more detail. The high pressure output of pump 8 is fed, via high pressure conduit 10 to high velocity fluid orifice assembly 12. Orifice assembly 12 is disclosed in detail by FIGS. 3-6 and will be discussed later below. Conduit 10 may be any suitable conduit capable of safely accommodating the desired fluid pressures and flow rates, and having sufficient flexibility or rigidity to permit orifice assembly 12 to be positioned as desired with respect to the pile fabric to be treated. Situated in close proximity to orifice assembly 12 is treatment roll 21, over which the textile fabric to be treated is placed. Generally, roll 21 has a solid, smooth, inflexible surface (e.g., polished aluminum or stainless steel); a roll having a specially treated or formed surface may be useful in achieving certain special effects on selected substrates. It has been found, for example, that use of a contoured roll surface may result in patterning effects corresponding to the roll surface contours on the substrate. Associated with roll 21 is textile fabric 25, which may be in the form of a continuously moving web that is positioned against a portion of roll 21. In order to generate a pattern on textile fabric 25, contact between the fabric and the high velocity stream of fluid emanating from orifice assembly 12 must be established and interrupted in a way that corresponds to the desired length and lateral spacing of the stripes comprising the pattern. Where a solid area is to be treated, the fluid streams may be made to contact the fabric in closely adjacent or overlapping stripes. In operation, a working fluid, e.g., water, is pumped by pump 8 from fluid source 2, through filter means 6 to the orifice assembly 12. If the portion of fabric 25 directly opposite orifice assembly 12 is to be treated, a valve (not shown) is made to open, e.g., via an electrical or pneumatic command signal, and high pressure water is allowed to pass via conduit 10 to orifice assembly 12, where a thin, high velocity water jet 17 is formed and directed onto the fabric 25. When the desired pattern requires that jet 17 not impact the fabric 25, an appropriate electrically or pneumatically transmitted instruction causes the valve to close. Positioning the desired areas of fabric surface under the jet 17 can be achieved by proper coordination of rotation of roll 21, which preferably may be accomplished by computer control, in conjunction with a rotation sensor mounted in association with roll 21. Assuming that appropriate indicating means are used to specify, via a digital signal, the exact rotational position of roll 21, a computer may be used to generate on/off instructions the valve (not shown) in accordance with pre-programmed pattern data. It is contemplated that roll 21 may be made to rotate continuously, in incremental linear steps, along the axis of the roll with the fabric 25 in the form of a web traveling over roll 21, which better lends itself to commercial production methods. It should be understood that, if desired, an orifice assembly 12 that can generate a multiple jet array is the preferred embodiment in most commercial applications, particularly if computer control is available to control the actuation of the multiple valves necessary in such system. After the optional treatment, the pile fabric 25 is redirected vertically upward for a distance by fourth idler roll 22 that is adjacent the treatment roll 21. The pile fabric 25 is then directed horizontally by fifth idler roll 24. The pile fabric travels horizontally for a distance and then is directed downward by sixth idler roll 26. The pile fabric is then treated, in its downward travel, by the pile reorientation means, generally indicated as the numeral 11, comprising of a flat spray nozzle 100 manufactured by Spraying Systems Company of Wheaton, Ill. (Model- Flat Jet, Part No. 3/8P1530). This nozzle can be of a variety of shapes such as conical, oblong, and so forth, but it is found that a flat nozzle is preferred. This flat spray nozzle creates a sheet of water directed against the back of the pile fabric 25. It is also believed that a spray transverse to the face of the fabric could achieve the same result by lifting the pile back into an upright position. The maximum possible range of values in pounds per square inch gauge is between 10 and 600. A more practical operating range is 30 to 200 p.s.i.g. with the preferred operating range being between 40 and 60 p.s.i.g. Another critical parameter is the minimum cross sectional dimension of the orifice. The maximum possible range of values for this parameter is between 0.000019 and 0.79 square inches. A more practical operating range is between 0.003 to 0.19 square inches with the preferred operating range being between 0.012 and 0.027 square inches. Still another important parameter is that of the distance of the pile fabric 25 to the spray nozzle 100. This distance has an outer range of 0.0625 to 24 inches with a more practical range of 1 to 15 inches and a preferred range of 4 to 10 inches as the optimal operating condition. The only other critical parameter of this invention includes the angle of the spray nozzle 100 from a line normal to the back of the pile fabric 25. This angle has an outer limit of 0 to 70 degrees with a more practical range of 10 to 50 degrees and a preferred range of 20 to 40 degrees as the optimal operating condition. This angle is basically designated as the angle that is in alignment with the optimal orientation of the pile fabric 25. If sprayed from the front of the pile fabric 25, this angle has an outer limit of 90 to 45 degrees with a more practical range of 85 to 55 degrees and a preferred range of 80 to 60 degrees as the optimal operating condition. This angle is basically designated as the angle to lift the pile back into optimal orientation. The flat spray nozzle 100 is supplied liquid, preferably water, from a manifold 102 that can be constructed of a variety of materials such as polyvinyl chloride, stainless steel, and so forth. The manifold 102 is threadedly attached to the flat spray nozzle in the preferred embodiment, which is shown in greater detail in FIG. 2. After receiving the spray treatment, the pile fabric 25 is once again redirected by seventh idler roll 27 into a horizontal plane. The pile fabric 25 is then guided upward vertically by the eighth and ninth dual idler wheels 28 and 29, respectively, while being simultaneously held in position. The pile fabric 25 then passes over tenth idler roll 32 for horizontal entry into the drying chamber 40 comprising of a series of steam cans. An example of a "steam can" heating element is that of a steam heated plate disclosed in commonly assigned U.S. Pat. No. 4,947,528 entitled "Method and Apparatus to Erect Pile Fiber" and issued on Aug. 14, 1990. The disclosure thereof is incorporated herein by reference for full description and clear understanding of the improved features of the present invention. Each steam can is typically held at 280 degrees Fahrenheit. The pile fabric is heat set when the temperature on the face of the pile fabric 25 being lower than that of the back of the fabric 25. This process permanently fixes the pile orientation. The steam can is only one means of heat setting the pile fabric with a host of other possible means including oven and tenter frame, and so forth. The temperature on the face of the fabric has an outer limit of 150 to 320 degrees Fahrenheit a more practical range of 190 to 300 degrees Fahrenheit and a preferred range of 200 to 290 degrees Fahrenheit as the optimal operating condition. The temperature on the back of the fabric has an outer limit of 145 to 310 degrees Fahrenheit a more practical range of 180 to 290 degrees Fahrenheit and a preferred range of 190 to 280 degrees Fahrenheit as the optimal operating condition. The pile fabric 25, once outside of the heat setting chamber 40, is then directed vertically downward by eleventh idler roll 34. The pile fabric is then received by take-up roll 36. FIGS. 3 through 7 depict the high velocity fluid orifice assembly as previously referenced, which may be used for the purpose of forming and interrupting the flow of a fluid stream in an open channel. This apparatus may, if desired, be used to interrupt intermittently the flow of a high pressure liquid stream, but is by no means limited to such application. Low pressure liquid streams, as well as gas streams at various velocities, may be selectively interrupted using the teachings herein. For purposes of the discussion which follows, however, it will be assumed that the fluid stream flowing in the channel is a liquid at relatively high velocity. As seen in the section view of FIG. 4, a conduit 10 supplies, via filter 71 (FIG. 3), a high pressure working fluid to manifold cavity 162 formed within inlet manifold block 160. Flange 164 is formed along one side of manifold block 160; into the base of flange 164 is cut a uniformly spaced series of parallel channels or grooves 166. Each groove 166 extends from cavity 162 to the forward-most edge of flange 164 and has cross-sectional dimensions corresponding to the desired cross-sectional dimensions of the stream. Thus, for example, the groove may have a cross-section resembling the letter "U", or may have a totally arbitrary shape. Control tubes 170, through which streams of relatively low pressure air or other control fluid are passed on command, are arranged in one-to-one relationship with grooves 166, and are, in one embodiment, positioned substantially in alignment with and perpendicular to grooves 166 by means of a series of sockets or wells 172 in flange 164, each of which is placed in direct vertical alignment with a respective groove 166 in flange 164, and into which each tube 170 is securely fastened. The floor of each socket 172 has a small passage 174 which in turn communicates directly with the base of its respective groove 166. Positioned opposite inlet manifold block 160 and securely abutted thereto via bolts 161 are outlet manifold block 180 and optional containment plate 178. Containment plate 178 may be attached to outlet manifold block 180 by means of screws 179 or other suitable means. Within outlet manifold block 180 is machined optional discharge cavity 182 and outlet drain 184. Discharge cavity 182 and outlet drain 184 may extend across several grooves 166 in flange 164, or individual cavities and outlets for each groove 166 may be provided. It is preferred, however, that cavity 182 be positioned so that passage 174 leads directly into cavity 182, and not led into the upper surface of outlet manifold block 180 or containment plate 178. Discharge cavity 182 includes impact cavity 177 which is machined into containment plate 178. Bolts 183 and 185 provide adjustment of the relative alignment between inlet manifold block 160 and the combination of outlet manifold block 180 and containment plate 178. In operation, a working fluid is fed into inlet cavity 162, where it is forced to flow through a first enclosed passage, formed by grooves 166 in flange 164 and the face of outlet manifold block 180 opposite flange 164, thereby forming the fluid into discrete streams having the desired cross-sectional shape and area. The pre-formed streams may be positioned within grooves 166 so that reduced or substantially no contact between the streams and the floor or base of grooves 166 occurs, and that substantially all contact between the streams and the grooves take place at the groove walls, which walls thereby define the lateral boundaries of the streams. It has been discovered that, so long as control tubes 170 remain inactivated, i.e., so long as no control fluid from tubes 170 is allowed to intrude into grooves 166 at any significant pressure, the streams of working fluid may be made to traverse the width of discharge cavity 182 in an open channel formed only by grooves 166 without a significant loss in the coherency or change in the cross-sectional shape or size of the stream, although under certain conditions, some slight spreading of the stream in a direction parallel to the groove walls and normal to the groove floor may occur. After traversing the width of discharge cavity 182, the streams encounter the edge of optional containment plate 178, whereupon the streams are made to flow in a second completely enclosed passage, formed by grooves 166 in flange 164 and the upper end of containment plate 178, just prior to being ejected in the direction of the desired target 25, e.g., a textile substrate. Where precise stream definition is necessary, e.g., in the direction of the open portion of grooves 166, use of containment plate 178 or similar structure is preferred. Such use affords an opportunity to re-define the stream cross-section to exact specification, as defined by the cross-section of this second completely enclosed passage, at extremely close distances to the desired target, thereby virtually eliminating the effects of any significant stream spreading. The ability to define the stream's cross-section at extremely close distances to the target, which occurs even without the use of plate 178 as a consequence of the stream flowing uninterruptedly in grooves 166, serves to minimize any stream placement inaccuracies due to slight non-parallelism in adjacent grooves 166 or problems resulting from the presence of nicks or burrs in the grooves. It is considered an advantageous feature of this invention that passing said stream through a second enclosed passage, and thereby allowing re-definition of the stream cross-section about the entire stream cross-section perimeter, may be achieved without the stream having to leave grooves 166. To interrupt the flow of working fluid which exits from grooves 166 in the direction of the desired target 25, it is necessary only to direct a relatively small quantity of relatively low pressure air or other control fluid, through the individual control tubes 170, into the associated grooves 166 in which flow is to be interrupted and under the working fluid stream. For purposes herein, the term "under" as used in this context shall mean a position between the working fluid stream within the groove and the base of the groove. As depicted in FIG. 5, the control fluid, even though it may be at a vastly lower pressure (e.g., one twentieth or less) than the working fluid, is able to life and divert the working fluid stream defined by the walls of groove 166 and can cause instabilities in the stream which, for example, where the working fluid is a relatively high velocity liquid, may lead to virtual disintegration of the working fluid stream. While, for diagrammatic convenience, FIG. 5 indicates a liquid stream which is merely lifted from the groove and deflected into the curved containment cavity 177 of containment plate 178, in fact, a high velocity liquid stream is observed to be almost completely disintegrated by the intrusion of a relatively low pressure control fluid stream as soon as the liquid stream passes the point where the control fluid stream is introduced into the grooves and the working liquid stream begins to lift from the groove. It is believed containment cavity 177 and containment plate 178 serve principally to contain the energetic mist which results from such disintegration, and are not necessary in all applications. Likewise, if disposing of the interrupted fluid presents no problem, discharge cavity 182 need not be provided and the interrupted fluid may simply be allowed to drain or disperse in place. The following Example is intended to illustrate details of the instant invention and are not intended to be limiting in any way. EXAMPLE A multiple stream nozzle was fabricated as follows: a stainless steel bar six inches long and approximately one inch wide was slotted at 10 slots per inch for the full 6" length. The slots were 0.030" wide by 0.008" deep by 7/16" long, and extended to an edge of the bar. Centered on the slot length of one of the slots, one 0.028" hole is drilled; the depth of the hole was approximately 0.032". Also centered on the same slot, a 0.042" hole was drilled from the back side of the bar so as to communicate with the single 0.028" hole. A lead and gold plated flat clamping plate was used to seal the nozzle and cover approximately 0.125 of 7/16" groove length, and was positioned to be aligned with but not cover the hole. Screws were used to hold the clamping plate to the nozzle. A deflector plate was then placed about 0.065" beyond the 0.028" hole; the edge of the deflector plate rested on the tops of the grooves. To demonstrate the effectiveness of the apparatus, the nozzle was pressurized with water at a pressure of 1600 p.s.i.g. The flow rate from each of the jets was 0.41 gallons per minute. A 0.125" hole associated with a single slot was then connected to a source of pressurized air through a 24 volt Tomita Tom-Boy JC-300 electric air valve (manufactured by Tomita Co., Ltd., No. 18-16. 1 Chome, Ohmorinaka, Ohta-ku, Tokyo, Japan). The air pressure was set at 65 p.s.i.g. By opening the air valve, the water jet could be deflected out of the chosen slot and caused to disintegrate, thereby interrupting the flow of the high pressure water jet from the nozzle. Crisp control of the water stream was observed, with extremely fast response time in switching from "stream on" to "stream off" conditions, as well as vice versa. In the operation of the apparatus described, it has been found that fluid in the grooves 166 tends to go up into passage 174 once it leaves the sharp edge 200 on the downstream side of the passage 174. This is a natural phenomenon since a stream of confined liquid fans out when freed from the constraining force. This fluid in the passage 174 creates numerous problems in the operation of the described apparatus. One problem is that the fluid in the passage 174 must be blown out when the air in the tubes is cut on resulting in a slower reaction time resulting in definition problems on the fabric 25 being treated. Also the fluid in the passage 174 tends to get into the air valves and in time results in defective valve action. Furthermore, the fluid in the passage 174 can cause a back pressure which will cause the air hoses to be blown off when air is supplied. Whenever a fluid expands or fans out it does so at an angle which can be determined so that the impingement point 220 on the downstream side of the passage 174 can be calculated. Since the impingement point 220 is known, the upstream edge 240 of the hole or passage 174 is curved downward to a point tangential to the upper surface of the groove 166 so that the fluid will be guided into and through the position of the passage 166 downstream of the passage 174 rather than backing up into same. By experimentation and testing, it has been found that when the convex or curved edge 240 of the passage approaches a sine curve maximum reflection of the fanned out fluid into the passage 166 occurs. This curve is defined by the equation: ##EQU1## where z=vertical axis y=horizontal axis l=vertical distance from the centerline of the groove to the impingement point 220 m=horizontal distance between the impingement point 220 to tangent point of the curve In the preferred form of the invention l=0.005 and m=0.013. It is not intended that the scope of the invention be limited to the specific embodiment illustrated and described. Rather, it is intended that the scope of the invention be defined by the appended claims and their equivalents.
A method and apparatus for continuous treatment of webs of fabric having an upright pile comprising spraying the pile fabric with a sheet of liquid and then optionally heat-setting the fabric. The spraying of pile fibers allows the fibers to return to their preferred upright orientation.
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CROSS REFERENCE TO RELATED APPLICATION This application is a National Stage of International Application No. PCT/JP2009/070427 filed Dec. 4, 2009, the contents of all of which are incorporated herein by reference in their entirety. FIELD OF THE DISCLOSURE The present invention relates to a control device for a vehicle that includes a thermowax switching valve, which has a heating section for heating thermowax and is selectively opened and closed by melting and solidification of the thermowax. BACKGROUND OF THE DISCLOSURE A thermowax switching valve is often employed as a valve for switching the flow of fluid in a fluid circuit such as a coolant circuit of a water-cooled engine. The thermowax switching valve is selectively opened and closed by expansion and contraction accompanying melting and solidification of the thermowax sealed inside of a case. A heater for heating the thermowax is often provided to force such a thermowax switching valve to open as needed. A control device for a vehicle including such a thermowax switching valve with a heater has been proposed as disclosed in Patent Document 1. The vehicle disclosed in Patent Document 1 includes the above-mentioned thermowax switching valve in a hydraulic circuit of the engine, and a PTC heater for heating the thermowax of the switching valve. The control device for a vehicle disclosed in Patent Document 1 includes an oil temperature sensor that detects the oil temperature in the hydraulic circuit, and estimates the temperature of the thermowax based on the oil temperature detected by the oil temperature sensor. When opening the switching valve, the PTC heater keeps being energized until a sensor value of the oil temperature sensor becomes higher than the melting temperature of the thermowax. PRIOR ART DOCUMENT Patent Document Patent Document 1: Japanese Laid-Open Patent Publication No. 2009-115075 SUMMARY OF THE INVENTION Problems that the Invention is to Solve As described above, the conventional control device for a vehicle includes the temperature sensor that detects the temperature of fluid flowing around the switching valve, and estimates the temperature of the thermowax based on the sensor value of the temperature sensor. However, in particular, in a case where the temperature sensor and the switching valve are arranged apart from each other, the sensor value of the temperature sensor and the temperature of the thermowax might be different. If the temperature of the thermowax is underestimated, the thermowax is undesirably heated more than necessary, and a rubber seal and grease inside the switching valve might deteriorate due to carbonization. Accordingly, it is an objective of the present invention to provide a control device for a vehicle that controls a switching valve, which is operated by heating a thermowax, in a suitable manner. Means for Solving the Problems To achieve the foregoing objective, the present invention provides a control device for a vehicle. The vehicle includes a thermowax switching valve, which includes a heating section for heating thermowax and is selectively opened and closed by melting and solidification of the thermowax. The control device includes a control section that controls the heating state of the heating section while taking into account variation of the thermal capacity accompanying phase transition of the thermowax. In the above-mentioned thermowax switching valve including the heating section, there is correlation between the opening degree and the thermowax temperature. By estimating the thermowax temperature, and controlling the heating state of the heating section based on the estimated temperature, the thermowax is heated without deficiency or excess. The thermowax temperature can be estimated based on a thermal model of the thermowax. In this case, the thermal capacity of the thermowax needs to be obtained accurately. Operation of the thermowax switching valve involves phase transition of the thermowax, and the phase transition involves variation of the thermal capacity of the thermowax. Thus, when estimating the thermowax temperature using the above-mentioned thermal model and controlling the heating state of the heating section based on the estimated result, it is necessary to consider the variation of the thermal capacity accompanying the phase transition of the thermowax. In this respect, according to the above-mentioned configuration, the heating state of the heating section is controlled taking into account the variation of the thermal capacity accompanying the phase transition of the thermowax. Thus, the heating state of the heating section is controlled while accurately grasping the thermowax temperature. According to the above structure, the switching valve operated by heating the thermowax is controlled in a suitable manner. To achieve the foregoing objective, the present invention provides another control device for a vehicle. The vehicle includes a thermowax switching valve, which includes a heating section for heating thermowax and is selectively opened and closed by melting and solidification of the thermowax. The control device includes a target value setting section, a was temperature estimating section, and a control section. The target value setting section sets a target value of the temperature of the thermowax. The wax temperature estimating section computes the amount of heat received by the thermowax based on the amount of heat transferred from the heating section to the thermowax and the amount of heat transferred from the thermowax to a fluid around the switching valve, and which estimates the temperature of the thermowax based on the amount of heat received and the thermal capacity of the thermowax. The control section controls the heating section such that the estimated temperature of the thermowax becomes equal to the target value. The wax temperature estimating section changes the value of the thermal capacity in accordance with variation of the estimate temperature of the thermowax across phase transition points of the thermowax. The amount heat received by the thermowax in the above-mentioned thermowax switching valve is calculated as a value obtained by dividing the amount of heat transferred from the heating section to the thermowax by the amount of heat transferred from the thermowax to the fluid around the switching valve. By dividing the amount of heat received by the thermowax by its thermal capacity, the amount of variation of the thermowax temperature is obtained, and the thermowax temperature can be calculated based on the result. The opening and closing of the thermowax switching valve involves phase transition of the thermowax from the solid phase to the solid-liquid coexisting phase and the liquid phase. The thermal capacity of the thermowax is changed in accordance with the phase transition. In this respect, in the present invention, the value of the thermal capacity is changed in accordance with variation of the estimate temperature of the thermowax across the phase transition points of the thermowax, and the thermowax temperature is estimated using the thermal capacity appropriate for the phase transition of the thermowax. Thus, in the control device for a vehicle according to the present invention, the thermowax temperature is accurately determined, and control of the switching valve operated by heating the thermowax is performed in a suitable manner. In a case where the heating section is controlled based on the estimate temperature of the thermowax as described above, the target value of the thermowax temperature when there is a request for opening the switching valve is preferably set to the temperature less than or equal to the thermowax temperature at which the switching valve is fully opened, that is, to the thermowax temperature at which the switching valve is fully opened or the temperature slightly lower than that to avoid overheating of the thermowax by the heating section. Also, when the switching valve is abruptly opened, the temperature of the fluid flowing around the switching valve is rapidly changed, and might interfere with the control based on the fluid temperature. In such a case also, the switching valve is gradually opened and the rapid temperature change of the fluid is prevented by holding the target value to the thermowax temperature at which the switching valve has a minute opening degree for a certain period of time, and then setting the target value to the thermowax temperature at which the switching valve is fully opened. To further ensure the operation response of the switching valve from the valve closed state to the valve opened state, the thermowax temperature of the switching valve while being closed is preferably preheated. Such preheating is performed by setting the target value when the switching valve is closed to a value at which the amount of heat received by the thermowax becomes greater than “0”, and that is lower than the temperature at which valve opening of the switching valve is started. To further ensure the operation response of the switching valve from the valve closed state to the valve opened state, the thermowax temperature of the switching valve while being closed is preferably kept at the temperature that exists immediately before the switching valve starts to open. Therefore, the response of the switching valve when opening the valve is ensured by setting the target value of the thermowax temperature while the switching valve is closed to a value corresponding to a temperature of the thermowax that exists immediately before the opening of the switching valve is started. Hysteresis that cannot be ignored might exist in the relationship between the thermowax temperature and the switching valve opening degree. That is, there might be a difference that cannot be ignored between the thermowax temperature at which the switching valve opening degree of a predetermined opening degree X is obtained when the opening degree of the switching valve is being changed in a valve opening direction, and the thermowax temperature at which the switching valve opening degree of a predetermined opening degree X is obtained when the opening degree of the switching valve is being changed in a valve closing direction. In such a case also, the target value of the estimate temperature of the thermowax may be set to different values in the case where the switching valve opening degree is changed in the valve opening direction to achieve the target opening degree, and in the case where the switching valve opening degree is changed in the valve closing direction to achieve the target opening degree even if the target opening degree of the switching valve is the same. In this manner, the opening degree of the switching valve is controlled in a suitable manner. The thermal capacity of the thermowax of the switching valve might vary from one unit to another due to change with time and individual differences. In such a case, the thermal capacity used to estimate the thermowax temperature might differ from the actual thermal capacity of the thermowax, and the thermowax temperature cannot be accurately estimated. In this case also, by detecting an opened state of the switching valve, and modifying the thermal capacity in accordance with the difference between the estimate temperature of the thermowax when opening of the valve is detected and the thermowax temperature at which the switching valve is actually opened, the variation of the thermal capacity from one unit to another is learned and modified, and the thermowax temperature is accurately estimated. To easily control the heating section based on the estimate temperature of the thermowax, the thermowax is preferably heated by the heating section when the estimate temperature of the thermowax is lower than the target value, and heating is preferably stopped if such is not the case. In the above-mentioned thermowax switching valve, if the thermal capacity of the case compared to the thermal capacity of the thermowax cannot be ignored, it is necessary to consider the influence of the thermal capacity of the case in the variation of the thermowax temperature with respect to the amount of heat received. In this situation, as the thermal capacity used to compute the amount of variation of the thermowax temperature, the thermal capacity of the case of the switching valve in combination with and the thermowax is used. The present invention may be applied to a vehicle equipped with a switching valve located in a coolant circuit that circulates a coolant for the engine. In particular, the present invention is applied to a vehicle including a switching valve that switches between permitting and stopping circulation of the coolant in the engine. BRIEF DESCRIPTION OF DRAWINGS FIG. 1 A schematic block diagram illustrating the configuration of a coolant circuit of a vehicle according to a first embodiment of the present invention. FIG. 2 A block diagram showing circulation of a coolant at a warm-up initial stage in the coolant circuit. FIG. 3 A block diagram showing circulation of the coolant at a warm-up latter stage in the coolant circuit. FIG. 4 A block diagram showing circulation of the coolant in the coolant circuit after completing warm-up. FIG. 5 A schematic diagram illustrating a thermal model of a thermowax used in the first embodiment. FIG. 6 A graph showing the relationship between the amount of heat received by the thermowax with respect to the wax temperature and the opening degree of the switching valve according to the first embodiment. FIG. 7 A graph showing the setting manner of the target wax temperature according to the first embodiment. FIG. 8 A flowchart showing a wax temperature estimating routine according to the first embodiment. FIG. 9 A flowchart showing a heater energizing routine according to the first embodiment. FIG. 10 A flowchart showing a target wax temperature setting routine according to the first embodiment. FIG. 11 A graph showing the setting manner of a target wax temperature according to a second embodiment of the present invention. FIG. 12 A graph showing the setting manner of the target wax temperature in a case where the target switching valve opening degree is set with a certain margin. FIG. 13 A graph showing changes of a sensor value of the coolant temperature sensor before and after opening the switching valve. FIG. 14 A graph showing the relationship between the amount of heat received by the thermowax with respect to the wax temperatures when there is a difference between the calculated wax temperature and the actual wax temperature. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS First Embodiment A control device for a vehicle according to a first embodiment of the present invention will now be described in detail with reference to FIGS. 1 to 10 . In this embodiment, the invention is applied to a vehicle including a thermowax switching valve provided in a coolant circuit for circulating engine coolant, wherein the circulation is selectively started and stopped. FIG. 1 shows the configuration of the coolant circuit of the vehicle according to this embodiment. The coolant circuit includes an electric water pump 1 for circulating the coolant. As shown in FIG. 1 , in the coolant circuit, the coolant passage is branched at a section downstream of the electric water pump 1 into a first conduit 2 , which passes through an engine 3 , and a second conduit 6 , which passes through an EGR cooler 4 and a heater core 5 . The first conduit 2 is formed to pass through a cylinder block and a cylinder head of the engine 3 in order. The first conduit 2 is connected to a switching valve 8 at a section downstream of the engine 3 . The switching valve 8 is formed as a thermowax-type conduit switching valve, which is selectively opened and closed by melting and solidification of a thermowax. Also, the switching valve 8 includes a heater 9 , which serves as a heating section for heating the thermowax in the switching valve 8 . After passing through a radiator 10 that transfers heat from the engine coolant at a section downstream of the switching valve 8 , the first conduit 2 is connected to a thermostat 7 . The thermostat 7 is selectively opened and closed in accordance with the temperature of the engine coolant that flows around a temperature sensing element inside the thermostat 7 . The engine coolant of the second conduit 6 that has passed through the EGR cooler 4 and the heater core 5 flows into the temperature sensing element. The thermostat 7 closes the valve when the temperature of the engine coolant flowing into the temperature sensing element is low, and inhibits the flow of the coolant through the radiator 10 . The thermostat 7 opens the valve when the temperature of the engine coolant flowing into the temperature sensing element is high, and permits the flow of the coolant through the radiator 10 . Furthermore, the coolant circuit includes a third conduit 11 , which connects part of the second conduit 6 downstream of the EGR cooler 4 to the switching valve 8 in the first conduit 2 . The switching valve 8 permits the flow of the coolant through the third conduit 11 by opening the valve, and inhibits the flow of the coolant through the third conduit 11 by closing the valve. Energization of the heater 9 provided in the switching valve 8 is controlled by an electronic control unit 12 . The electronic control unit 12 is configured as a computer unit including a central processing unit (CPU), a read only memory (ROM), a random access memory (RAM), and an input/output port (I/O). In the electronic control unit 12 , the CPU executes computation processes associated with the energization control of the heater 9 , and the ROM stores programs and data for control. Also, the RAM temporarily stores the computation results of the CPU and the detection results of the sensor. The I/O inputs signals from and outputs signals to external devices. A coolant temperature sensor 13 , which detects the temperature of the engine coolant, is connected to the input port of the electronic control unit 12 . The coolant temperature sensor 13 is located in the vicinity of the coolant outlet of the cylinder head of the engine 3 . In the coolant circuit configured as described above, the flow of the engine coolant is controlled in the following manner after the engine 3 is started. FIG. 2 shows the state of the coolant circuit in a warm-up initial stage. As shown in FIG. 2 , the switching valve 8 at this time is closed so that the flow of the engine coolant through the third conduit 11 is stopped. Also, the thermostat 7 at this time is closed and stops the flow of the coolant through the radiator 10 since the temperature of the engine coolant that flows into the temperature sensing element is low. Therefore, the engine coolant is circulated through only the second conduit 6 in the coolant circuit at this time. Circulation of the engine coolant in the engine 3 is stopped, and the engine coolant inside the engine 3 is kept heated by the heat generated by the engine 3 . This promotes a temperature increase of the engine coolant inside the engine 3 , and thus promotes warming of the engine 3 . FIG. 3 shows the state of the coolant circuit in a warm-up latter stage. As shown in FIG. 3 , the switching valve 8 is open at this time, and permits the flow of the engine coolant through the third conduit 11 . The thermostat 7 at this time is still closed, and stops the flow of the coolant through the radiator 10 . Thus, in the coolant circuit at this time, the engine coolant that has passed through the engine 3 flows through the third conduit 11 , and circulation of the coolant inside the engine 3 is started. FIG. 4 shows the state of the coolant circuit after completion of warm-up. As shown in FIG. 4 , the switching valve 8 at this time is closed, and the flow of the engine coolant through the third conduit 11 is stopped. Since the temperature of the engine coolant that passes through the temperature sensing element is sufficiently increased, the thermostat 7 at this time is opened. Thus, in the coolant circuit at this time, the engine coolant that has passed through the engine 3 flows to the radiator 10 , and the heat that the engine coolant absorbed from the engine 3 is transferred by the radiator 10 . In this embodiment, the electronic control unit 12 estimates the thermowax temperature of the switching valve 8 using a thermal model when controlling the opening degree of the switching valve 8 . The electronic control unit 12 then controls the opening degree of the switching valve 8 by controlling the heating state of the heater 9 such that the estimated thermowax temperature becomes equal to a target wax temperature. FIG. 5 shows the thermal model used to estimate the thermowax temperature. In the thermal model, the amount of heat received by the thermowax per unit time (P−P_xw) is calculated using the input heat amount P of the heater 9 and the amount of heat P_xw that is transferred from the thermowax to the engine coolant. Further, the amount of temperature variation of the thermowax per unit time is calculated by dividing the amount of heat received by the thermal capacity of the thermowax. The amount of heat P_xw is calculated as a value obtained by multiplying the difference value (T_x−T_w) between the estimate temperature T_x of the thermowax and the coolant temperature T_w of the engine coolant by the coefficient of heat transfer K_xw from the thermowax to the engine coolant. Also, in this embodiment, a sensor value of the coolant temperature sensor 13 is used as the coolant temperature T_w of the engine coolant used for computing the amount of heat P_xw. In this physical model, the temperature of the thermowax when starting the engine 3 (initial wax temperature T_x 0 ) is assumed to be equal to the coolant temperature of the engine coolant (initial coolant temperature T_w 0 ). The estimate temperature T_x is obtained by integrating the temperature variation amount per unit time computed based on the amount of heat received (P−P_xw) to the initial wax temperature T_x 0 . Selectively opening and closing the thermowax switching valve 8 involves phase transition of the thermowax from a solid phase to a solid-liquid coexisting phase and a liquid phase. The thermal capacity of the thermowax is changed in accordance with the phase transition. In this embodiment, three values including the solid thermal capacity M_xs, the solid-liquid coexisting thermal capacity M_xsL, and the liquid thermal capacity M_XL are prepared as the thermal capacity of the thermowax used to compute the amount of temperature change, and the values are switched in accordance with the state of the thermowax. That is, in this embodiment, the value of the thermal capacity is changed in accordance with the variation of the estimate temperature T_x of the thermowax across the phase transition points of the thermowax. In this embodiment, the thermal capacities (M_xs, M_xsl, M_xl) are calculated as the thermal capacity of the thermowax of the switching valve 8 in combination with the case for accommodating the switching valve 8 . That is, the thermal capacities specifically represent the thermal capacity of the case and the thermowax of the switching valve 8 . Conventionally, it is unnecessary to estimate the temperature using such a model since the thermostat is used in a region with a relative margin. However, the temperature increase of the coolant becomes rapid by stopping water, and it is necessary to estimate the temperature using the above-mentioned model to prevent boiling of the coolant. FIG. 6 shows the relationship between the amount of heat received by the thermowax with respect to the opening degree of the switching valve 8 and the temperature of the thermowax. As shown in FIG. 6 , there is correlation between the opening degree of the switching valve 8 and the temperature of the thermowax. Thus, the switching valve 8 can be opened by a necessary opening degree by calculating the temperature of the thermowax necessary to open the switching valve 8 by a necessary opening degree (target switching valve opening degree), setting the calculated temperature as the target wax temperature, and controlling the heating state of the heater 9 such that the temperature of the thermowax estimated in accordance with the thermal model becomes equal to the target wax temperature. As shown in FIG. 6 , the switching valve 8 starts to open at the thermowax temperature slightly higher than the temperature at the boundary between the solid phase and the solid-liquid coexisting phase of the thermowax, and is fully opened at the thermowax temperature slightly higher than the temperature at the boundary between the solid-liquid coexisting phase and the liquid phase of the thermowax. The opening and closing control of the switching valve 8 based on the thermostat temperature according to this embodiment is performed in the following manner. In this embodiment, setting of the target wax temperature under the following conditions is performed in the manner shown in FIG. 7 . (a) When Switching Valve 8 is Fully Opened When performing heating control of the heater 9 based on the estimate temperature of the thermowax as described above, in this embodiment, the target wax temperature when there is a request for fully opening the switching valve 8 is set to or slightly lower than the temperature of the thermowax when the switching valve 8 is fully opened to avoid overheating of the thermowax by the heater 9 in a suitable manner. (b) When the Switching Valve 8 is Fully Closed If the heater 9 is not energized, the switching valve 8 is kept fully closed. However, even when the switching valve 8 is fully closed, if the engine coolant in the cylinder head is boiling, it is necessary to urgently open the switching valve 8 so that circulation of the engine coolant in the engine is started and boiling of the engine coolant is avoided. In this embodiment, to ensure the valve opening response of the switching valve 8 in the case as described above, the electronic control unit 12 sets the target wax temperature at the time when the switching valve 8 is fully closed to a value corresponding to a temperature of the thermowax that exists immediately before the opening of the switching valve 8 is started. That is, by preheating the thermowax, the switching valve 8 is held in a standby state where the switching valve 8 can promptly open. If the thermowax is preheated to any level, the operation response of the switching valve 8 from a valve closed state to a valve opened state is improved as compared to a case where the thermowax is not preheated. Thus, the amount of heat received becomes greater than 0, and the operation response of the switching valve 8 from the valve closed state to the valve opened state is improved only by setting the target value of the switching valve while being closed to a value lower than the temperature at which opening of the switching valve is started. (c) When Switching Valve 8 is Shifted from Valve Closed State to Valve Opened State If the switching valve 8 is abruptly opened, the temperature of the engine coolant around the coolant temperature sensor 13 is rapidly changed, and might hinder various types of engine controls based on the detection result of the engine coolant temperature. In such a case also, by holding the target wax temperature to the temperature of the thermowax at which the switching valve 8 has a minute opening degree for a certain period of time, and then setting the target wax temperature to the thermowax temperature at which the switching valve 8 is fully opened, the switching valve 8 is gradually opened, and the value of the engine coolant temperature sensor is prevented from being abruptly changed. The switching valve 8 needs to be promptly opened to prevent boiling of the engine coolant in the cylinder head. In such a case, the switching valve 8 is not held at the minute opening degree for the certain period of time, but is immediately set to the target wax temperature when there is a request for fully opening the switching valve 8 . FIG. 8 shows a flowchart of a wax temperature estimating routine according to this embodiment. The process of this routine is started by the electronic control unit 12 at the starting of the engine 3 . When this routine is started, the electronic control unit 12 first reads the coolant temperature T_w 0 at the starting of the engine 3 in step S 100 . The electronic control unit 12 then sets the coolant temperature T_w 0 at the starting of the engine 3 as an initial wax temperature T_x 0 in step S 101 . In the subsequent step S 102 , the electronic control unit 12 determines whether the thermowax is in the solid phase. The determination is made based on whether the estimate temperature T_x of the thermowax is less than or equal to a boundary temperature T_x 1 between the solid phase and the solid-liquid coexisting phase of the thermowax. If the thermowax is solid (if the decision outcome of S 102 is positive), the electronic control unit 12 updates the value of the estimate temperature T_x of the thermowax according to the following equation (1) in step S 103 . T — x=T — x (previous value)+( P−P — xw )/ M — xs   (1) where P in the equation (1) is the input heat amount of the heater 9 , P_xw is the amount of heat transfer from the thermowax to the engine coolant, and M_xs is the solid thermal capacity of the thermowax. In the subsequent step S 104 , the electronic control unit 12 determines whether the thermowax at that time is in the solid-liquid coexisting phase. The determination is made based on whether the estimate temperature T_x of the thermowax is greater than the boundary temperature T_x 1 between the solid phase and the solid-liquid coexisting phase of the thermowax, and is less than or equal to a boundary temperature T_x 2 between the solid-liquid coexisting phase and the liquid phase. If the thermowax is in the solid-liquid coexisting phase (if the decision outcome of S 104 is positive), the electronic control unit 12 updates the value of the estimate temperature T_x of the thermowax according to the following equation (2) in step S 105 . T — x=T — x (previous value)+( P−P — xw )/ M — xsl   (2) Where M_xsl in the equation (2) is the solid-liquid coexisting thermal capacity of the thermowax. In the subsequent step S 106 , the electronic control unit 12 determines whether the current thermowax is in the liquid phase. The determination is made based on whether the estimate temperature T_x of the thermowax is greater than the boundary temperature T_x 2 between the solid-liquid coexisting phase and the liquid phase. If the thermowax is in the liquid phase (if the decision outcome of S 106 is positive), the electronic control unit 12 updates the value of the estimate temperature T_x of the thermowax in accordance with the following equation (3) in step S 107 . T — X=T — X (previous value)+( P−P — xw )/ M — xl   (3) Where M_xl in the equation (3) is the liquid thermal capacity of the thermowax. As described above, after updating the estimate temperature T_x of the thermowax, the electronic control unit 12 returns to step S 102 in the next control cycle, and repeatedly updates the estimate temperature T_x. FIG. 9 shows a flowchart of a heater energizing routine according to this embodiment. The process of this routine is repeatedly performed per predetermined number of control cycles by the electronic control unit 12 . When this routine is started, the electronic control unit 12 determines whether the estimate temperature T_x of the thermowax is lower than the target wax temperature set in a target wax temperature setting routine in step S 200 as described below. Then, if the estimate temperature T_x is lower than the target wax temperature (if the decision outcome of S 201 is positive), the electronic control unit 12 turns on energization of the heater 9 in step S 201 . If such is not the case (if the decision outcome of S 201 is negative), the electronic control unit 12 turns off energization of the heater 9 in step S 202 , and terminates the process of the current routine. In this embodiment, when the estimate temperature T_x of the thermowax is lower than the target wax temperature, the heater 9 heats the thermowax, and if such is not the case, heating is stopped. FIG. 10 shows a flowchart of the target wax temperature setting routine according to this embodiment. The process of this routine is started immediately after starting the engine 3 by the electronic control unit 12 . When this routine is started, the electronic control unit 12 first checks whether there is a request for opening the switching valve 8 in step S 300 . If there is no opening request (if the decision outcome of S 300 is negative), the electronic control unit 12 proceeds to step S 301 , and sets the target wax temperature to a wax temperature for preheating in step S 301 , and returns to the process of step S 300 after the predetermined control cycles. If there is the opening request (if the decision outcome of S 300 is positive), the electronic control unit 12 checks whether there is a request for avoiding abrupt change in the value of the coolant temperature sensor. That is, the electronic control unit 12 determines whether the switching valve 8 needs to be urgently opened to avoid boiling. If there is a request for avoiding abrupt change in the value of the coolant temperature sensor (if the decision outcome of S 302 is positive), the electronic control unit 12 sets the target wax temperature to the wax temperature at which the switching valve 8 has the minute opening degree for a certain period of time in step S 303 and then sets the target wax temperature to the wax temperature at which the switching valve 8 is fully opened in step S 304 . The electronic control unit 12 then returns to the process of step S 300 after the predetermined control cycles. If there is no request for avoiding abrupt change in the coolant temperature sensor value (if the decision outcome of S 302 is negative), the electronic control unit 12 immediately proceeds to step S 304 , and sets the target wax temperature to the wax temperature at which the switching valve 8 is fully opened. Subsequently, the electronic control unit 12 returns to the process of step S 300 after the predetermined control cycles. In this embodiment described above, the heater 9 corresponds to the heating section. Also, in this embodiment, the electronic control unit 12 executes processes performed by a target value setting section, a wax temperature estimating section, and a control section. This embodiment has the following advantages. (1) According to this embodiment, in the vehicle equipped with the thermowax switching valve 8 , which includes the heater 9 for heating the thermowax and is selectively opened and closed by melting and solidification of the thermowax, the electronic control unit 12 controls the heating state of the heater 9 taking into account the variation of the thermal capacity accompanying phase transition of the thermowax. More specifically, the electronic control unit 12 executes the following: setting of the target wax temperature, which is the target value of the temperature of the thermowax; computing the amount of heat received by the thermowax based on the amount of heat transferred from the heater 9 to the thermowax (input heat amount P) and the amount of heat P_xw transferred from the thermowax to the engine coolant around the switching valve 8 , and estimating the temperature of the thermowax (estimate temperature T_x) based on the amount of heat received and the thermal capacity of the thermowax; controlling the heater 9 such that the estimate temperature T_x of the thermowax becomes equal to the target wax temperature; and changing the value of the thermal capacity used for computing the estimate temperature T_x in accordance with the variation of the estimate temperature T_x of the thermowax across the phase transition points of the thermowax. The amount of heat received by the thermowax of the above-mentioned thermowax switching valve 8 is calculated as a value (P−P_xw) obtained by dividing the amount of heat (P_xw) transferred to the fluid around the switching valve from the thermowax from the amount of heat (input heat amount P) transferred from the heater 9 to the thermowax. By dividing the amount of heat received by the thermowax by the thermal capacity, the amount of temperature variation of the thermowax is calculated, and the thermowax temperature can be calculated from the result. The opening and closing of the thermowax switching valve 8 involves phase transition of the thermowax from the solid phase to the solid-liquid coexisting phase and the liquid phase, and the thermal capacity of the thermowax is changed in accordance with the phase transition. In this respect, according to this embodiment, the value of the thermal capacity is changed in accordance with the variation of the estimate temperature T_x of the thermowax across the phase transition points of the thermowax, and the thermowax temperature is estimated using the thermal capacity appropriate for the phase transition of the thermowax. Thus, in the control device for a vehicle according to this embodiment, the thermowax temperature is accurately grasped, and the switching valve operated by heating the thermowax is controlled in a suitable manner. (2) In this embodiment, the target wax temperature when there is a request for fully opening the switching valve 8 is set to the temperature slightly lower than the thermowax temperature at which the switching valve 8 is fully opened. Thus, overheating of the thermowax by the heater 9 is avoided in a suitable manner. (3) In this embodiment, when opening the switching valve 8 when there is a request for reducing the valve opening speed, the target wax temperature is held to the thermowax temperature at which the switching valve 8 has the minute opening degree for the certain period of time. Thereafter, the target value is set to the thermowax temperature at which the switching valve 8 is fully opened. Thus, the switching valve 8 is gradually opened, and abrupt temperature change of the fluid is prevented. (4) In this embodiment, the target wax temperature when the switching valve 8 is fully closed is set to the value corresponding to a temperature of the thermowax that exists immediately before the switching valve 8 starts to open. This ensures the valve opening response of the switching valve 8 . (5) In this embodiment, when the estimate temperature T_x of the thermowax is lower than the target wax temperature, the thermowax is heated by the heater 9 , and if such is not the case, heating is stopped. Thus, the heater 9 is easily controlled based on the estimate temperature of the thermowax. (6) In this embodiment, the thermal capacity of the case of the switching valve 8 in combination with the thermowax is used as the thermal capacity used to compute the amount of temperature variation of the thermowax. Thus, even if the thermal capacity of the case with respect to the thermal capacity of the thermowax is as great as it cannot be ignored, the thermowax temperature is accurately estimated. (7) In this embodiment, since the switching valve 8 is controlled in a suitable manner by accurately grasping the thermowax temperature, deterioration due to carbonization and of the rubber seal and the grease inside the switching valve 8 due to overheating are prevented in a suitable manner. Second Embodiment Subsequently, a control device for a vehicle according to a second embodiment of the present invention will now be described with reference to FIGS. 11 and 12 . In this embodiment, the setting manner of the target wax temperature is changed, but other parts are common to the first embodiment. Hysteresis that cannot be ignored exists in the relationship between the thermowax temperature and the switching valve opening degree. That is, there might be a great difference between the thermowax temperature at which the switching valve opening degree of a predetermined opening degree X is obtained when the opening degree of the switching valve 8 is being changed in the valve opening direction, and the thermowax temperature at which the switching valve opening degree of a predetermined opening degree X is obtained when the opening degree of the switching valve 8 is being changed in the valve closing direction. In such a case also, even if the target opening degree of the switching valve 8 is the same, the target wax temperature may be set to different values in the case where the switching valve opening degree is changed in the valve opening direction to achieve the target opening degree, and in the case where the switching valve opening degree is changed in the valve closing direction to achieve the target opening degree. In this manner, the opening degree of the switching valve 8 is controlled in a suitable manner. More specifically, in this embodiment, even if the target switching valve opening degree is the same, different target wax temperatures are used in the case where the switching valve 8 is activated in the valve opening direction by turning on energization, and in the case where the switching valve 8 is activated in the valve closing direction by turning off energization as shown in FIG. 11 . That is, when activating the switching valve 8 in the valve opening direction by turning on energization, the thermowax temperature at an intersection P 1 of the target switching valve opening degree and an operation line Lon of the switching valve 8 when energization is on is set as the target wax temperature, and the thermowax temperature at an intersection P 2 of the target switching valve opening degree and an operation line Loff of the switching valve 8 when energization is off is set as the target wax temperature. Thus, even when there is hysteresis in the relationship between the thermowax temperature and the switching valve opening degree, the switching valve opening degree is controlled in a suitable manner based on the thermowax temperature. In a case where the target switching valve opening degree is set with a certain margin as shown in FIG. 12 , when energization is turned on so that the switching valve 8 is activated in the valve opening direction, the thermowax temperature at an intersection P 3 of the upper limit value of the target switching valve opening degree and the operation line Lon of the switching valve 8 when energization is on is set as the target wax temperature. Also, when the switching valve 8 is activated in the valve opening direction by turning on energization, the thermowax temperature at an intersection P 4 of the lower limit value of the target switching valve opening degree and the operation line Loff of the switching valve 8 when energization is off is set as the target wax temperature. Third Embodiment Subsequently, a control device for a vehicle according to a second embodiment of the present invention will now be described with reference to FIGS. 13 and 14 . This embodiment is common to the above-mentioned embodiments except that a modification and learning process of the thermal capacity of the thermowax is performed. The thermal capacity of the thermowax of the switching valve 8 might vary from one unit to another due to change with time and individual differences. In such a case, the thermal capacity used to estimate the thermowax temperature differs from the actual thermal capacity of the thermowax, and the thermowax temperature cannot be accurately estimated. In this embodiment, an opened state of the switching valve 8 is detected, and the thermal capacity is modified in accordance with the difference between the estimate temperature of the thermowax at the time when opening of the switching valve 8 is detected and the thermowax temperature at which the switching valve actually opens. Accordingly, the variation of the thermal capacity from one unit to another is modified and learned, and the thermowax temperature is accurately estimated. The an opened state of the switching valve 8 is detected in the following manner. As described above, the first conduit 2 of the coolant circuit of the vehicle according to this embodiment is formed to pass through the cylinder block of the engine 3 , and then through the cylinder head. Also, the coolant temperature sensor 13 is arranged in the vicinity of the coolant outlet of the cylinder head. In this case, when the switching valve 8 in the fully closed state is opened and circulation of the engine coolant in the engine 3 is started, first, the engine coolant located in the cylinder head passes through the mounting position of the coolant temperature sensor 13 . Subsequently, the engine coolant located in the cylinder block passes through the mounting position of the coolant temperature sensor 13 . When circulation of the engine coolant is stopped, the temperature of the engine coolant in the cylinder head becomes higher than that of the engine coolant in the cylinder block. Therefore, the sensor value of the coolant temperature sensor 13 before and after the switching valve 8 is opened reaches a peak immediately after the switching valve 8 is opened as shown in FIG. 13 . Since the peak does not appear at times other than when the switching valve 8 is opened, the opened state of the switching valve 8 can be detected. That is, in this embodiment, the electronic control unit 12 determines that the switching valve 8 is opened in accordance with the appearance of the peak of the sensor value of the coolant temperature sensor 13 . FIG. 14 shows the relationship between the amount of heat received by the thermowax with respect to the calculated wax temperature, that is, the estimate temperature T_x and the actual wax temperature when there is a difference between them. Such a difference is generated when the thermal capacities (M_xs, M_xsl, M_xl) used to calculate the estimate temperature T_x separate from the actual values. If the thermowax is solid before starting to open the valve, the thermowax temperature (estimate temperature T_x) is represented by the following equation (4). T — x=T — x 0 +f ( P−P — xw ) dt/M — xs   (4) where T_x 0 is the initial temperature of the thermowax, P is the input heat amount of the heater 9 , P_xw is the amount of heat transferred from the thermowax to the engine coolant, and M_xs is the solid thermal capacity of the thermowax. The amount of heat received by the thermowax until an opening state of the switching valve 8 is detected is represented by ∫(P−P_xw)dt/M_xs. Thus, the actual solid thermal capacity M_xs′ of the thermowax has a value that satisfies the following equation (5). Valve opening starting temperature of switching valve= T — x 0+∫( P−P — xw ) dT/M — xs′   (5) Therefore, an appropriate thermowax temperature can be estimated by modifying the solid thermal capacity of the thermowax to a value M_xs′ that satisfies the above equation (5). While the solid thermal capacity M_xs of the thermowax is very important for determining an opened state of the switching valve 8 , the error in the solid-liquid coexisting thermal capacity M_xsl and the liquid thermal capacity M_xl influence the opening degree of the switching valve 8 by a relatively small degree. Therefore, in the third embodiment, only the modification and learning of the solid thermal capacity M_xs is performed to reduce calculation load. If necessary, of course, M_xsl and M_xl may be modified by multiplying by M_xs′/M_xs. According to this embodiment, the thermowax temperature is accurately estimated regardless of the variation of the thermal capacity of the thermowax. In this embodiment, the electronic control unit 12 is configured to perform processes as a detection section for detecting an opened state of the switching valve 8 , and a modification section for modifying the thermal capacity in accordance with the difference between the estimate temperature T_x of the thermowax when valve opening of the switching valve 8 is detected and the thermowax temperature at which the switching valve 8 is actually opened. Each of the above embodiments may be modified as follows. In the above embodiments, the sensor value of the coolant temperature sensor 13 is used as the coolant temperature T_w of the engine coolant used for computing the amount of heat P_xw transferred from the thermowax to the engine coolant. However, if the switching valve 8 and the coolant temperature sensor 13 are arranged apart from each other and circulation of the engine coolant in the engine 3 is stopped, the sensor value of the coolant temperature sensor 13 and the temperature of the engine coolant around the switching valve 8 might be different. In this case, a value obtained by multiplying the total fuel amount ga of the engine 3 by a certain coefficient K 1 represents the temperature increase of the engine coolant around the switching valve 8 by the heat of the engine 3 , and the coolant temperature around the switching valve 8 can be computed by the following equation (6). T — w=T — w 0 +K 1 ×∫ga dt   (6) where T_w 0 in the equation (6) is the initial coolant temperature, that is, the coolant temperature sensor value at the beginning of the engine start-up. Also, the value obtained by multiplying the total fuel amount ga by a certain coefficient K 2 may be used as a value corresponding to the difference between the coolant temperature sensor value and the engine coolant temperature around the switching valve 8 , and the coolant temperature around the switching valve 8 may be computed by the following equation (7). T — w=Thw+K 2×∫ ga dt   (7) where Thw in the equation (7) is the coolant temperature sensor value. In the third embodiment, the valve opening of the switching valve 8 is detected by the appearance of the peak of the coolant temperature sensor value, but the valve opening of the switching valve 8 may be detected by another method. For example, an opening degree sensor may be provided in the switching valve 8 , and the valve opening of the switching valve 8 may be directly detected based on the detection result of the sensor. Alternatively, a sensor for detecting the water flow in the third conduit 11 may be provided, and the valve opening of the switching valve 8 may be indirectly detected by the presence and absence of the water flow in the third conduit 11 . In the above embodiments, the thermal capacity of the case of the switching valve 8 in combination with the thermowax is used as the thermal capacities (M_xs, M_xsl, M_xl), but if the thermal capacity of the case is small and its influence can be ignored, the thermal capacity of only the thermowax may be used. In the above embodiments, after holding the target wax temperature to the thermowax temperature at which the switching valve 8 has the minute opening degree for the certain period of time, the target wax temperature is set to the thermowax temperature at which the switching valve 8 is fully opened to avoid rapid change of the coolant temperature sensor value. Of course, in a case where rapid change of the coolant temperature sensor value does not cause a problem, or in a case where quick response of an opening state of the switching valve is required, the target wax temperature may be set to the thermowax temperature at which the switching valve 8 is fully opened from the beginning. In the above embodiments, the heater 9 is preheated to ensure the opening response of the switching valve 8 . However, preheating may not be performed if high valve opening response is not required, and electric consumption during standby may be reduced. In the above embodiments, the target wax temperature is set based on three cases including when the switching valve 8 is fully opened, when fully closed, and when transferring from the closed state to the opened state. However, if more precise switching valve opening degree control is required, a finer target wax temperature setting may be performed. In the above embodiments, the heating state of the heater 9 is controlled only by turning on and off energization. However, if more precise switching valve opening degree control is required, the amount of energization of the heater 9 may be finely controlled. A different model from the above embodiments may be employed as the thermal model associated with computation of the estimate temperature of the thermowax. As the heating section for heating the thermowax of the switching valve 8 , any heating device such as a hot wire heater, a PTC heater, and a heat pump may be used. In the above embodiments, the present invention is embodied in the control of the switching valve 8 , which switches the presence and absence of the water flow in the engine 3 . However the present invention may be embodied in the control of a switching valve other than that in the coolant circuit of the vehicle, such as a valve that switches the presence and absence of water flow in the radiator. Also, the present invention may be embodied in the control of a switching valve located in places other than the coolant circuit, such as a valve provided in a hydraulic circuit of the engine and that switches the oil flow in the hydraulic circuit. DESCRIPTION OF THE REFERENCE NUMERALS 1 . . . Electric Water Pump, 2 . . . First Conduit, 3 . . . Engine, 4 . . . EGR Cooler, 5 . . . Heater Core, 6 . . . Second Conduit, 7 . . . Thermostat, 8 . . . Thermowax Switching Valve, 9 . . . Heater (Heating Section), 10 . . . Radiator, 11 . . . Third Conduit, 12 . . . Electronic Control Unit (Target Value Setting Section, Wax Temperature Estimating Section, Control Section), 13 . . . Coolant Temperature Sensor.
An electronic control unit ( 12 ) calculates the heat receiving quantity of a thermo wax to estimate the temperature of the thermo wax on the basis of the calculated heat receiving quantity and the heat capacity of the thermo wax, and controls a heater so that the temperature of the thermo wax reaches a predetermined target value. Further, the electronic control unit ( 12 ) changes the value of the heat capacity used to estimate the temperature of the thermo wax depending on the variation of the estimated temperature of the thermo wax across the phase transition point of the thermo wax so as to preferably control a switching valve which is operated by heating the thermo wax.
6
This application is the U.S. National Phase of International Application Number PCT/NL02/00026 filed on 15 Jan. 2002, which is incorporated herein by reference. BACKGROUND OF THE INVENTION The invention relates to a method to modulate plant growth or development. Apart from short-term environmental factors, such as the daily rhythm of night and day and the immediate availability of water and nutrients, long-term environmental factors, such as periods with low temperature, (lack of) humidity, or little day length, have an important role in the life cycle of many plants. Where a short-term environmental factor such as ambient light has an immediate effect on day-to-day morphogenesis (e.g. seedlings grown in the light are characterised by short hypocotyls and expanded green cotyledons and seedlings grown in darkness are etiolated, with elongated hypocotyls and closed cotyledons) long-term environmental factors often determine or have effect on the transition of a plant from one phase to another phase in its development, and in particular effect plants that are in a developmental pause in their development. For example, periods with low temperatures occurring in the temperate climate zone during winters effect many transitional aspects of plants. Typical transitional events are stem elongation (bolting) and the onset of flowering and the formation of fruit (fruiting), another is the event that is seen as the break-through event of dormant seed, germination. Some plant species need a developmental pause comprising a prolonged period of low temperature and/or little light or day length to induce flowering, and, in a process called vernalisation, for many plants traditionally artificial methods (such as forcing) are in widespread use to provide for the premature bolting, flowering and/or fruiting, or germination of a plant, seed, seedling or bulb to obtain commercially attractive plants or plant parts (seedlings, flowers or flowering plants, fruit) in a season in which otherwise such a product would nor or not natively be available. In some species flowering and stem elongation may be induced at the same time. Other species need a period of low temperature to induce the elongation of the stem, a process that we will further refer to as bolting. In these species the process of flower induction and formation precedes the required period of low temperature, so the two processes are temporally separated. Yet other processes influenced by long-term environmental factors (e.g. low temperatures or dryness) are quiescence, dormancy and germination of seeds. These long-term environmental factors or processes often synchronise a plant's development to the seasons and/or climatic conditions of the place of growth, and reflect evolutionary adaptations to various conditions under which a particular plant or species grows. Tulip is an example of a species used as a model to study these various aspects of long-term environmentally induced changes in plant growth, via the study of the process of bolting [4]. Another process where low temperature is often involved is seed dormancy. Low temperature induced stem elongation can be viewed as a form of dormancy breaking, and stratification, vernalisation and dormancy breaking in tree buds are similar processes driven by low temperature. In germination of dormant seed in Arabidopsis, besides the chilling requirement to overcome dormancy, other similarities between bolting of tulips and the germination of the dormant seed are the fact that all organs are formed within a protective structure to enable rapid growth after dormancy has been removed, reserve substances are stored in specialised leaf like organs (for example in the form of starch in the cotyledons of Arabidopsis, and also in the form of starch in the bulb scales of tulip), and during dormancy there is a low water potential [5]. SUMMARY OF THE INVENTION The invention provides a method to modulate a developmental transition of a plant, thereby for example providing a break-through in a developmental pause, said method essentially independent of a long-term environmental factor as discussed above, thereby providing a method to modulate transition of a plant from one developmental phase to another. In particular, a method for modulating developmental transitions in plants is provided wherein said transition comprises germination, bolting, the onset of flowering or fruiting. Herein we present the isolation of a low temperature induced expression product of a plant RING finger, subclass RING-H2 protein from Tulip with homology to other plant (such as Arabidopsis) proteins that interacts with developmental regulators. The implications of this are expression of said plant RING finger or RING-H2 protein, as shown herein for the low temperature induced TGRING1 expression, targets a plant's homologue of ABI3 for proteolysis, and thereby ends a developmental pause, e.g. the state of dormancy or quiescence, allowing the plant to break-through (for example transcend) from one developmental phase to another and grow towards its subsequent developmental state. Although the fact that RING or RING-H2 proteins have been recognized as involved in ubiquitination or proteolysis before, the involvement of these proteins in developmental changes in plants has not been demonstrated ear er This is especially true for the developmental changes such as those relating to germination, stratification, bolting, the onset of flowering or fruiting, low temperature induced stem elongation, dormancy breaking, bulb induction, timing of flowering. For example, Stoop-Myer et al [17] show that an N-terminal fragment of COP1 retains part of it's functionality. They indicate this fragment to have at least two functional domains, the RING and coiled-coil domains. But, importantly they don't assign the retained functionality to the RING domain, and neither do they propose a function for this domain alone. Also, McNellis et al [18] show that an N-terminal fragment of COP1 retains part of it's functionality. Again they indicate this fragment to have at least two functional domains, the RING and coiled-coil domains. Again, they don't assign the retained functionality to the RING domain. McNellis et al [19] show by overexpression of COP1 it's role in photomorphogenesis. They indicate COP1 to have at least three functional domains, the RING domain, the coiled-coil domain, and the WD-40 repeat domain. But, importantly they don't assign the functionality of COP1 to the RING domain, and neither do they propose a function for this domain alone. Kurup et al [16] show in their article that AIP2 has an interaction with the arabidopsis developmental regulator ABI3. They fail to recognize the role of AIP2 and other RING-H2 proteins in developmental transitions, on the contrary, they propose a role for AIP2 as a transcriptional activator. The article by Freemont [20] is the first published article that proposes a general role for RING and RING-H2 domains in ubiquitination and proteolytic targeting. His article focuses mainly on RING proteins found in animal systems with one exception: PRT1 [21]. The arabidopsis PRT1 protein is apparently involved in a particular kind of pathway, the ‘N-end rule’ ubiquitination pathway. However, neither in this article nor in the article by Potuschak et al, [21] is there any mention of using RING finger or RING-H2 proteins for manipulating the protein level of developmental regulators in order to obtain a developmental change in plants. Although the fact that RING or RING-H2 proteins have been recognized as involved in ubiquitination or proteolysis before, the involvement of these proteins in developmental changes in plants has not been demonstrated earlier This is especially true for the developmental changes such as those relating to germination, stratification, bolting, the onset of flowering or fruiting, low temperature induced stem elongation, dormancy breaking, bulb induction, timing of flowering. Tamminen [22] illustrates that ectopic expression of ABI3 results in changes in freezing tolerance. The present invention provides the use of RING or RING-H2 proteins for developmental transitions of plants by manipulating the protein level of ABI3 or other developmental regulators by targeting them for proteolysis by ubiquitination. The article by Torii et al [23] shows that the arabidopsis protein CIP8 interacts with the arabidopsis photomorphogenic regulator COP1. The interaction is ascribed to the RING domain of COP1 and the RING-H2 domain of CIP8. However, the article does not indicate or propose a functional role for the RING or RING-H2 domain in ubiquitination or proteolysis. It only proposes a role as a protein-protein interaction domain. Typical plant proteins having the desired RING finger or RING-H2 motif can be found in FIG. 1A and B, and others may be found by simple alignment as shown herein. In a preferred embodiment the invention provides a method for modulating a developmental transition of a plant comprising modulating expression of a RING finger or RING-H2 protein or functional fragment thereof in said plant or parts thereof, in particular wherein said transition comprises germination, stratification, bolting, the onset of flowering or fruiting. Such a RING finger or RING-H2 protein, as herein is disclosed, provides ubiquination and/or proteolysis of a target protein (e.g. developmental regulatory protein) related to the transition from one developmental phase to another, thereby for example providing for proteasome-mediated degradation and removal of the target protein (e.g. regulatory protein) involved. A target protein as used herein is a protein capable of modulating a developmental transition of a plant. Particular regulatory proteins to be mentioned here comprise for example COP1, HY5, FLC, FRIGIDA and LD. Preferred herein is modulation of a regulatory protein that in Arabidopsis is known as abscisic acid-insensitive3 (ABI3) or a homologue thereof. The invention provides a method wherein said RING finger or RING-H2 protein or functional fragment thereof is at least functionally equivalent or homologous to a plant RING finger or RING-H2 protein as shown in FIGS. 1A and 1B . A functional fragment of a RING finger protein contains for example the RING finger (C3HC4) motif: Cx(2)Cx(9,39)Cx(1,3)Hx(2,3)Cx(2)Cx(4,48)Cx(2)C (SEQ ID. No: 16) and a functional fragment of a RING-H2 proteins contains for example the RING-H2 (C3H2C3) motif: Cx(2)Cx(9,39)Cx(1,3)Hx(2,3)Cx(2)Cx(4,48)Cx(2)C (SEQ. ID. NO: 17) or a motif functionally equivalent thereto. The above used coding is according to the IUPAC-rules: C stands for cysteine, H stands for histidine and x codes for any amino acid. The numbers between the brackets show the number of repetitions, so for example, x(9,39) means a stretch of 9 to 39 amino acids residues, where each residue can be any amino acid. In TGRING1 this motif comprises amino acids 248-288 of SEQ. ID. NO: 15. The invention also provides an isolated and/or recombinant nucleic acid encoding a plant RING finger or RING-H2 protein or functional fragment thereof comprising an amino acid sequence that is preferably at least 50%-60% homologous, more preferred 70% homologous and even more preferred 95% homologous to the sequence in FIG. 3 , and retains a similar function [i.e. is “essentially equivalent” to the sequence in FIG. 3 ]. “Essentially equivalent” as used herein means a functional equivalent, e.g. deliberate amino acid substitution may be made on the basis of similarity in polarity, charge, solubility, hydrophobicity, and/or the amphipathetic nature of the residues as long as the biological activity of the polypeptide is retained. Homology is generally over the full-length of the relevant sequence shown herein. As is well-understood, homology at the amino acid level is generally in terms of amino acid similarity or identity. Similarity allows for “conservative variations”, i.e. substitution of one hydrophobic residue such as isoleucine, valine, leucine or methionine for another, or the substitution of one polar residue for another, such as arginine for lysine, glutamic for aspartic acid, or glutamine for asparagine. Deliberate amino acid substitution maybe made on the basis of similarity in polarity, charge, solubility, hydrophobicity, and/or the amphipathetic nature of the residues as long as the biological activity of the polypeptide is retained. In a preferred embodiment, all percentage homologies referred to herein refer to percentage sequence identity, e.g. percent (%) amino acid sequence identity with respect to a particular reference sequence can be the percentage of amino acid residues in a candidate sequence that are identical with the amino acid residues in the reference sequence, after aligning the sequences and introducing gaps, if necessary, to achieve the maximum percent sequence identity, without considering any conservative substitutions as part of the sequence identity. Amino acid similarity or identity can be determined by genetic programs known in the art. The invention provides a method wherein said RING finger or RING-H2 protein act as a ubiquitin-protein ligase (E3) or subunit of such an enzyme. Modification with chains of ubiquitin (Ub) constitutes a primary mechanism by which proteins are targeted for proteasomal degradation. Protein ubiquitination is accomplished through a complex process involving ubiquitin-activating enzymes (E1s), ubiquitin-conjugatingenzymes (E2s) and, in some cases, specificity-conferring ubiquitinligases (E3). The E1 enzyme acts first and passes Ub to an E2 enzyme ready for targeting to a protein substrate (target protein). RING finger or RING-H2 protein, which may act as nucleic acid or protein binding domains may also act as ubiquitin protein ligase (E3) or subunits of such enzymes. Ubiquitin ligases E3 are loosely defined as proteins or protein complexes are responsible for substrate recognition and promoting polyubiquitin ligation to the substrate marking it for degradation by the 26S proteosome. E3 enzymes assemble multiubiquitin chains on a variety of regulatory proteins and thus targets them for proteolysis by the 26S proteosome. The invention provides a method according to the invention wherein said RING finger or RING-H2 protein may interact at least with a target protein and/or a ubiquitin conjugating enzyme (E2) allowing transfer of ubiquitin residues from said ubiquitin conjugating enzyme to said target protein. E3s may interact with E2s to form thioester linkages with ubiquitin before modifying target proteins. Some E3s do not act as ubiquitin carriers that form thioester intermediates, but instead act as bridges between E2s and target proteins that provide a favorable environment for the transfer of ubiquitin. The RING finger or RING-H2 protein may provide a site of interaction with E2 that allows for the direct transfer of Ub from E2 to target lysines. This reaction results in the formation of an isopeptide bond between the C terminus of ubiquitin and the epsilon amino group of a lysine residue in the protein substrate. Lysine residues within the attached ubiquitin residues can serve as acceptor sites, resulting in the assembly of a multiubiquitin chain, which can to function as a recognition signal for the 26S proteasome. The RING finger or RING-H2 protein may have other roles in ubiquitination reactions than providing binding sites for E2s. RING finger or RING-H2 protein can instead function as allosteric activators of E2s. The invention further provides a method according to the invention wherein said RING finger or RING-H2 protein act as an allosteric activator of a ubiquitin conjugating enzyme (E2). It is understood that said RING finger or RING-H2 protein acts in pathways other than ubiquitin or in ubiquitin-like pathways, to modulate a developmental transition of a plant. In particular, the invention provides such a nucleic acid derived from a bulb. A bulb as used herein is a modified underground stem which has one or more buds enclosed in fleshy modified leaves or scales which supply energy to the bud(s) when they start to grow, for example onions and tulips have bulbs. Also, the invention provides a vector comprising a nucleic acid according to the invention, and host cell comprising a nucleic acid or vector according to the invention. An example of such a vector is the plant transformation vector pBIN19, which is often used to deliver a piece of DNA, for example a piece of DNA encoding the TGRING1 protein or functional fragment thereof, to the genome of a plant. The procedure or method for preparing a transformant can be performed according to the conventional technique used in the fields of molecular biology, biotechnology and genetic engineering. Preferably, such a host cell comprises a plant cell, allowing the generation of a plant or part thereof comprising a nucleic acid according to the invention. ‘Plant cell’, as used herein, amongst others comprises seeds, suspension cultures, embryos, meristematic regions, callous tissues, protoplasts, leaves, roots, shoots, bulbs, gametophytes, sporophytes, pollen and microspores. The target plant may be selected from any monocotyledonous or dicotyledonous plant species, such as for example ornamental plants, vegetables, arable crops etc. ‘Dicotyledons’ (and all scientific equivalents referring to the same group of plants) form one of the two divisions of the flowering plants or angiospermae in which the embryo has two or more free or fused cotyledons. ‘Monocotyledons’ (and all scientific equivalents referring to the same group of plants) form one of the two divisions of the flowering plants or angiospermae in which the embryo has one cotyledon. ‘Angiospermae’ or flowering plants are seed plants characterized by flowers as specialized organs of plant reproduction and by carpels covering the ovaries. Also included are gymnospermae. Gymnospermae are seed plants characterized by strobili as specialized organs for plant reproduction and by naked sporophylls bearing the male or female reproductive organs, for example woody plants. ‘Ornamental’ plants are plants that are primarily in cultivation for their habitus, special shape, (flower, foliage or otherwise) colour or other characteristics which contribute to human well being indoor as cut flowers or pot plants or outdoors in the man made landscape, for example bulbous plant species like Tulipa, Freesia, Narcissus, Hyacinthus etc. ‘Vegetables’ are plants that are purposely selected or bred for human consumption of foliage, tubers, stems, fruits, flowers of parts of them and that may need an intensive cultivation regime. ‘Arable crops’ are generally purposely bred or selected for human objectivity's (ranging from direct or indirect consumption, feed or industrial applications such as fibers) for example soybean, sunflower, corn, peanut, maize, wheat, cotton, safflower and rapeseed. In particular, the invention provides use of a nucleic acid or a vector according to the invention in a method for modulating a plant. Preferably, said method comprises modulating a developmental transition of said plant. Preferably, said modulation is achieved by providing said plant with a nucleic acid encoding a RING finger or RING-H2 protein or functional fragment thereof. The invention is for example considered useful to replace forcing of plants with the purpose to accelerate a transition, for example to obtain early flowering bulbs for sale, but can equally well be applied to delay transition in plants where that may be required. In a particular embodiment, the invention provides a method, for example useful in in-vitro propagation of bulbs, such as tulip bulbs, comprising transient expression of said nucleic acid encoding a RING finger of RING-H2 protein. Other examples of transitions which can be influenced or modulated (accelerated or delayed) with the described invention comprise germination, stratification, bolting, the onset of flowering, fruiting, flowering timing, low temperature induced stem elongation, dormancy breaking or bulb induction, whereby said nucleic acid can also be transiently expressed. The invention additionally provides a plant (if desired only transiently) provided with a nucleic acid encoding a RING finger or RING-H2 protein or functional fragment thereof. The invention also provides a method for a determining a stage in a or leading up to a developmental transition of a plant comprising determining expression of a RING finger or RING-H2 gene product (mRNA or protein or functional fragment thereof in said plant or parts thereof, and/or comprising determining ubiquination and/or proteolysis of a target protein which interacts or is affiliated with said RING finger or RING-H2 gene product (mRNA or protein or functional fragment thereof). Such a method is useful in a method for selecting a plant for being at a transition phase of its development comprising determining expression of a RING finger or RING-H2 gene product functional fragment thereof in said plant or parts thereof, for example to determine whether said plant is in or close to a distinct developmental phase such as for example germination, stratification, bolting, the onset of flowering or fruiting. The invention further provides a method for selecting a plant for being at a transition phase of its development comprising determining expression of a RING finger or RING-H2 gene product or functional fragment thereof and/or comprising determining ubiquination and/or proteolysis of a target protein which interacts or is affiliated with said RING finger or RING-H2 gene product (mRNA or protein or functional fragment thereof. Plants with the desired characteristics are now easily selectable and herein also provided. The invention also provides a method for obtaining a plant or progeny thereof having a desired quality trait related to developmental transitions comprising determining expression of a RING finger or RING-H2 gene product or functional fragment thereof in said plant or parts thereof, and/or comprising determining ubiquination and/or proteolysis of a target protein which interacts or is affiliated with said RING finger or RING-H2 gene product (mRNA or protein or functional fragment thereof. It is for example now possible to more easily select or breed plants with a desired developmental transition pattern. For example to obtain tulips or other plants with a reduced cold requirement for flowering, or a plant of which the germination of the seeds is either delayed or accelerated, it is now possible to check the progeny of different crosses for expression levels of a RING finger or RING-H2 mRNA or protein or functional fragment thereof regulating said quality (cold requirement or time of seed germination). The invention is further explained in the detailed description without limiting the invention thereto. DETAILED DESCRIPTION Plant Material and RNA Isolation Tulip bulbs were harvested in the summer (July) and stored at 20° C. until at least two weeks after stage G (September). All storage treatments were performed in dark ventilated rooms. Bulbs were then either transferred to 5° C. for low temperature treatment, or to 17° C. For the differential display analysis, after transfer to 5° C. or 17° C., samples were taken after 4, 8 and 12 weeks. The same was done in another year for the Northern blot analysis of differential expression during temperature treatment. For the Northern blot analysis of the different organs after planting, bulbs were transferred to 17° C. in September until the end of December and then transferred to 5° C. for 12 weeks. After planting and growing at 23° C. (12 hr light/12 hr dark), organ samples were taken at the indicated days after planting. All samples were frozen in liquid nitrogen and stored at −80° C. or freeze dried. RNA was isolated using CTAB as described [3]. Northern blots were performed using formaldehyde/agarose gels as described [1]. Hybridization was performed at 68° C. using 50% formamide buffer, and an α 32 P-CTP labeled RNA probe. Cloning Procedure Differential display PCR (DDRT-PCR) was performed as described [2]. The differential band was excised, and reamplified using the same conditions as during the DDRT-PCR, except that dNTP concentration was 100 μM. The PCR product was cloned. All cloning of PCR products was in the pGEM-T vector (Promega, Madison USA). After sequencing, two nested 5′ RACE (Rapid Amplification of cDNA Ends) reactions were performed using the Marathon kit (ClonTech, Palo Alto USA) with fragment specific primers. The resulting fragment was cloned and sequenced. The total fragment was now reamplified and cloned using new primers from the 5′-end (5′-GTCGTCGGCTTCCCCTCCGCCAAG-3′ SEQ. ID. NO: 1) and 3′-end (5′-TTTAACCACAATAGCTCATTGCAAGGCTTC-3′ SEQ. ID. NO: 2) and proofreading enzyme (KlenTaq, ClonTech). Two clones were sequenced on both strands and found to be identical. Requested EST clones were also sequenced on both strands. Sequencing was performed on an automated sequencer (ALFexpress, Amersham Pharmacia Biotech, Uppsala, Sweden), using kits recommended by manufacturer. Sequence Analysis Sequences were analyzed using DNASIS (Hitachi Software, Olivet, France) and GeneRunner (Hastings Software Inc, Hastings on Hudson, USA) software packages. Database searches were performed using the NCBI Blast server Multiple alignments were performed at EBI ClustalW server, using standard settings. Alignments were shaded using Boxshade 3.2 (ISREC, Epalinges s/Lausanne, Switzerland). Results Cloning and Sequence of TGRING-H2 and Similar EST Sequences Using differential display a screening was performed for mRNA's expressed at a higher level in the bottom internode of dry stored tulip bulbs at 5° C. compared to those stored at 17° C. A 218 bp fragment was found to be differential and was cloned. Because DDRT-PCR fragments often derive from the non-coding 3′-end, a 5′-RACE reaction was performed. The resulting fragment was sequenced and new 5′- and 3′-primers were designed to reamplify the full-length cDNA using proofreading enzyme. The resulting 1222 bp clone contains an open reading frame of 327 amino acids with a predicted molecular mass of 36.7 kD. The cDNA is either full length or close to full length because there is an in frame stop codon preceding the predicted start codon. The transcript size was also confirmed on a Northern blot (not shown). The encoded acidic protein (isoelectric point 5.02) has as most significant feature a C-terminal RING-H2 domain, a variant RING-finger domain. It is predicted to be targeted to the cytoplasm. The protein will be further referred to as TGRING1. Database searches revealed two partially sequenced EST-sequences and one published Arabidopsis sequence, CIP8 [COP-1 Interacting Protein 8; [13]] with significant homology beyond the RING-H2 domain. The EST-clones, rice EST C10402 and arabidopsis EST TAI386, were requested and full length sequenced. Recently, the sequence of the Arabidopsis EST TAI386 sequence has been published as AIP2, an ABI3 interacting protein [8], and will be further referred to as such. The rice EST will be further referred to as OSRING1. A multiple alignment shows that the two EST sequences are highly homologous to the tulip sequence over the whole length of the protein. OSRING1 shows 58% identity and 72% similarity over 300 amino acids, and AIP2 51% and 64% respectively over 301 amino acids. The homology of CIP8 to TGRING1 is highest in the C-terminal part, but extends beyond the RING-H2 domain ( FIG. 1A ). Further database research revealed that, although many sequences from every eukaryotic phylum contain the RING-H2 domain, some contain a RING-H2 domain with a conserved motif consisting of 25-40 amino acids directly N-terminal to the RING-H2 domain. These extended RING-H2 domains are found in sequences from plant, animal and viral origin ( FIG. 1B ). TGRING1 Expression The expression level of TGRING1 in bottom internodes is higher during the low temperature treatment compared to the control treatment ( FIG. 2A ). It is higher in the earlier part of the treatment than in later stages of the treatment. TGRING1 expression was examined in different tissues after planting of the bulbs. Expression in the internodes is examined at the moment when they just start to elongate rapidly and expression in the flower when it shows the first colouring. Roots and leaves show no rapid growth phase, so expression is examined at an arbitrary moment ( FIG. 2B ). The highest expression is detected in flower tissue and the lowest in the leaves. We showed that one of the underlying mechanisms of low temperature induced stem elongation in tulips is a gradual change in the sensitivity for auxin in the bottom internodes over the course a low temperature treatment of a few months. This was shown by an increase in auxin induced internodal elongation and auxin induced gene expression of primary auxin response genes, after longer periods of low temperature treatment. By using differential display we have isolated a cDNA clone that is expressed at higher levels during the low temperature treatment, as compared to a control treatment. It codes for a protein with a C-terminal RING-H2 domain. Although this is a feature shared by a lot of proteins, both in arabidopsis and other species, only two arabidopsis sequences showed homology over the whole length of TGRING1. One of these, AIP2, has a sufficiently high homology to be a true homologue. This is also true for rice OSRING1, which has slightly higher identity and similarity because it is of monocotyledonous origin, as TGRING1. The Arabidopsis CIP8 is a more distantly related protein. The extended RING-H2 domain shared by these four proteins is conserved beyond the plant kingdom, which indicates a special function for this domain. The Arabidopsis proteins AIP2 and CIP8 are isolated as proteins interacting with developmental regulators. CIP8 interacts with COP1 through specific interaction of the RING-H2 domain of CIP8 and the RING-finger domain of COP1 [13]. The interaction of AIP2 with ABI3 is mediated by the C-terminal half of AIP2, containing the RING-H2 domain [8]. But surprisingly, it interacts with the B2 and B3 domains of ABI3, which do not contain a RING-finger domain. So either the C-terminal part of AIP2 that does not contain the RING-H2 domain interacts with ABI3, or the RING-H2 domains can interact with different domains with no apparent sequence homology, despite the fact that the RING-H2 domains are highly similar in sequence (43% identity and 71% similarity between the RING-H2 domains of AIP2 and CIP8). Low temperature induced stem elongation can be viewed as a form of dormancy breaking. Stratification, vernalisation and dormancy breaking in tree buds are similar processes driven by low temperature. Interesting now is that the TGRING1 arabidopsis homologue AIP2 is an ABI3 interacting factor. The Arabidopsis abscisic acid-insensitive3 (abi3) mutant was originally isolated for its ability to germinate in the presence of inhibiting concentrations of abscisic acid (ABA; [7]) and has a role in embryo maturation and dormancy maintenance [9]. Recent publications have shown that ABI3 also has a role in vegetative quiescence processes. The abi3-4 mutant shows a rapid induction of flowering and ABI3 is expressed in the apex of dark grown seedlings [8;11;12]. Another recent publication proposes a function for the RING finger domain in targeted ubiquitin-mediated proteolysis. RING finger proteins act therein as E3 ubiquitin protein ligases [6]. Taken all these things together we show here that the low temperature induced TGRING1 expression has a role in targeting the tulip homologue of ABI3 for proteolysis, and thereby removing the state of dormancy, allowing the plant to grow under favourable conditions. Analysis of AIP2 in Arabidopsis during processes as stratification and vernalization and its influence on ABI3 protein levels are ways to further show this phenomenon, considering that the fact remains that two totally different approaches to analyze similar phenomena as seed dormancy and low temperature induced flowering in tulip result in the cloning of homologous proteins having the above described RING-H2 motif. The expression of AIP2 during cold stratification. Purpose of the Experiment Determine the expression pattern of the arabidopsis homologue AIP2 of the cloned tulip TGRING1 during seed stratification by low temperature. Experimental Setup Dry Arabidopsis thaliana seeds of the Cape Verdian ecotype (Cvi, planting date 21 june, harvested november 1, start experiment november 11, all in 2001) were sown on wet filter paper and either put in the dark at 20° C. or at 4° C. for 1, 3, 5 or 7 days. Per treatment, a part of the seeds was after treatment transferred to 20° C. in the light (16 hrs light/8 hrs dark) to determine germination percentage; the rest of the seeds were frozen in liquid nitrogen and stored at −80° C. for RNA isolation. Germination percentage was determined 7 days after seeds were placed at 20° in the light. RNA extraction and Northernblotting was performed as described for the experiments on tulip. Results FIGS. 4 a and b show the expression level of AIP2 after the indicated amount of days of treatment. The AIP2 probe hybridized with a single band of approximately 1200 bp. The expression level is strongly increased 1 day after incubation at 4° C., both compared to dry seeds (twelvefold higher) and seeds incubated at 20° C. (fivefold higher). The expression stays higher during the low temperature treatment, compared to the 20° C. treatment. FIG. 3 c shows the germination percentage of the seeds after the different treatments. The seeds were not very dormant, yet the low temperature treatment increased the germination percentage, compared to seeds kept at 20° C. Germination was 100% after three or more days at 4° C. The results show that the arabidopsis AIP2 mRNA is strongly upregulated during cold stratification. This shows that the AIP2 protein is not only conserved in sequence but also in function, moreover it is even functionally conserved in different developmental processes requiring low temperature induction, namely low temperature induced stem elongation in tulip and seed stratification in arabidopsis. The increased expression during cold stratification correlates with an increased germination percentage after the treatment. Because AIP2 interacts with ABI3 and has a RING-H2 domain it is likely that the dormancy breaking occurs by proteolytic targeting of the ABI3 protein via ubiquitination, thus removing the state of dormancy. AIP2 would then act as a monomeric E3 ubiquitin ligase. By analogy the tulip TGRING1 protein would have the same function in the process of low temperature induction of stem elongation, which can be seen as a form of dormancy breaking. This experiment shows that AIP2 and homologous proteins are clear markers for dormancy breaking. It also shows the involvement of a RING domain protein in dormancy breaking in another process as low temperature induced stem elongation in tulips, namely cold seed stratification. FIGURE LEGENDS FIG. 1A Multiple alignment of TGRING1 and homologous proteins from Arabidopsis and rice. Residues are shaded black when more than 50% of the residues is identical and gray when more than 50% of the residues is similar. Fully conserved residues are indicated by an asterisk, conserved substitutions by a colon, and semi conserved substitutions by a dot. The RING-H2 domain is underlined, and the N-terminal extension of the RING-H2 domain is underlined by a dashed line. FIG. 1B Multiple alignment of the extended RING-H2 domains of proteins from animal, plant and viral origin. Shading is as indicated for A. Species are indicated as follows: Mm is Mus Musculus (mouse), Rr is Rattus rattus (rat), At is Arabidopsis thaliana , Os is Oryza sativa (rice), Hs is Homo sapiens (human), Tg is Tulipa gesneriana and Hh is human Herpesvirus. Database accession numbers are: PRAJA1 NP — 032879, NDAP1 BAA06979, RHC2a AAC69860, os329 BAA88184, hs311 BAA91254 and ICPO P28284. FIG. 2A Expression of TGRING-1 in the bottom internode of tulip during low temperature treatment (5° C.) compared to a control treatment (17° C.). FIG. 2B Expression of TGRING-1 in different tissues after planting. As a reference, the expression level in the bottom internode at day 0 after planting is shown. This expression level is the same as that at week 12 of the 5° C. treatment in FIG. 2A (different exposure times are used for FIG. 2A and FIG. 2B ). The other internode samples were taken at the moment that they started to grow rapidly: leaves and roots show no exponential growth phase and samples were taken at an arbitrary moment; flower tissue was sampled when colouring started. 25 micrograms of total RNA was used per lane. Equal loading was checked by ethidium bromide staining (not shown). FIG. 3 Nucleic acid of TGRING1 (SEQ. ID. NO: 14) The predicted 327 amino acid (SEQ. ID. NO: 15)open reading frame is coded for by bases 104-1182 and is indicated above the nucleic acid sequence. The bases coding for the RING-H2 domain are underlined. FIG. 4A Expression of AIP2 during treatment of imbibed seeds at either 4° C. or 20° C. An RNA probe was used complementary to bp 665-1120 of the AIP2 mRNA sequence (GenBank accesion ATH251087). The band corresponds to a size of approximately 1200 bp. 8 μg of total RNA was loaded per lane; the bottom panel shows a methylene blue staining of the blot to confirm equal loading. ds indicates dry seeds. FIG. 4B Quantification of the intensities of the bands in FIG. 4 a. FIG. 4C Percentage germination of the seeds after the indicated treatments. INCORPORATION OF SEQUENCE LISTING Incorporated herein by reference in its entirety is the Sequence Listing for the application. The Sequence Listing is disclosed on a computer-readable ASCII text file titled, “sequence.txt”, created on Dec. 15, 2008. The sequence.txt file is 25 kb in size. Literature REFERENCE LIST 1. Ausubel, F, Brent, R, Kingston, R E, Moore, D D, Seidman, J G, Smith, J A, Struhl, K: Short protocols in molecular biology. John Wiley & Sons, New York (1995). 2. Bauer, D, Muller, H, Reich, J, Riedel, H, Ahrenkiel, V, Warthoe, P, Strauss, M: Identification of differentially expressed mRNA species by an improved display technique (DDRT-PCR). Nucleic Acids Res. 21: 4272-4280 (1993) 3. Chang, S, Puryear, J, Cairney, J: A simple and efficient method for isolating RNA from pine trees. Plant Molecular Biology Reporter 11: 114-117 (1993). 4. De Hertogh, A A, Le Nard, M: Tulipa. In: De Hertogh, A. A and Le Nard, M. (eds), The Physiology of Flower Bulbs, pp. 617-682. Elsevier Science Publishers; Amsterdam (1993). 5. Dennis, F G Jr: A physiological comparison of seed and bud dormancy. In: Lang, G, A. (ed), Plant Dormancy: Phsysiology, Biochemistry and Molecular Biology, pp. 47-56. CAB International, Wallingford UK (1996). 6. Freemont, P S: RING for destruction? [In Process Citation]. Curr. Biol. 10: R84-R87 (2000). 7. Koornneef, M, Reuling, G, Karssen, C M: The isolation and characterization of abscisic acid-insensitive mutants of Arabidopsis thaliana . Physiologia Plantarum 61: 377-383 (1984). 8. Kurup, S, Jones, H D, Holdsworth, M J: Interactions of the developmental regulator ABI3 with proteins identified from developing Arabidopsis seeds. Plant J 21: 143-155 (2000). 9. Ooms, J J J, Lèon-Kloosterziel, K M, Bartels, D, Koornneef, M, Karssen, C M: Acquisition of desiccation tolerance and longevity in seeds of Arabodopsis thaliana . A comparative study using abscicic acid-insensitive abi3 mutants. Plant Physiol 102: 1185-1191 (1993). 10. Rietveld, P L, Wilkinson, C, Fransen, H M, Balk, P A, Van der Plas, L H W, Weisbeek, P J, De Boer, A D: Low temperature sensing in tulip is mediated through an increased response to auxin. J Exp Bot 51: (2000). 11. Rohde, A, De Rycke, R, Beeckman, T, Engler, G, Van Montagu, M, Boerjan, W: ABI3 affects plastid differentiation in dark-grown arabidopsis seedlings [In Process Citation]. Plant Cell 12: 35-52 (2000). 12. Rohde, A, Montagu, Mv, Boerjan, W: The ABSCICIC ACID-INSENSITIVE3 (ABI3) gene is expressed during vegetative quiescence processes in Arabidopsis. Plant, Cell and Environment 216-270 (1999). 13. Torii, K U, Stoop-Myer, C D, Okamoto, H, Coleman, J E, Matsui, M, Deng, X W: The RING finger motif of photomorphogenic repressor COP1 specifically interacts with the RING-H2 motif of a novel Arabidopsis protein. J Biol Chem 274: 27674-27681 (1999). 14. pBIN19 Nucleic Acids Research 12(22), 8711-8721 (1984). 15. Bachmair, A, Novatchkova, M, Potuschak, T, Eisenhaber, F: Ubiquitylation in plants: a post-genomic look at a post-translational modification. Trends Plant Sci 2001, 6:463-70. 16. Kurup, S. Jones, H D, Holdsworth, M J: Interactions of the developmental regulator ABI3 with proteins identified from developing Arabidopsis seeds. Plant J 2000, 21:143-55. 17. Stoop-Myer, C, Torii, K U, McNellis, T W, Coleman, J E, Deng, X W: Short communication: the N-terminal fragment of Arabidopsis photomorphogenic repressor COP1 maintains partial function and acts in a concentration-dependent manner. Plant J 1999, 20:713-7. 18. McNellis, T W, Torii, K U, Deng, X W: Expression of an N-terminal fragment of COP1 confers a dominant-negative effect on light-regulated seedling development in Arabidopsis. Plant Cell 1996, 8:1491-503. 19. McNellis, T W, Von Arnim, A G, Deng, X W: Overexpression of Arabidopsis COP1 results in partial suppression of light-mediated development: evidence for a light-inactivable repressor of photomorphogenesis. Plant Cell 1994, 6:1391-400. 20. Freemont, P S: RING for destruction? Curr Biol 2000, 10: R84-7. 21. Potuschak, T. Stary, S, Schlogelhofer, P, Becker, F, Nejinskaia, V, Bachmair, A: PRT1 of Arabidopsis thaliana encodes a component of the plant N-end rule pathway. Proc Natl Acad Sci USA 1998, 95:7904-8. 22. Tamminen, I, Makela, P, Heino, P, Palva, ET: Ectopic expression of ABI3 gene enhances freezing tolerance in response to abscisic acid and low temperature in Arabidopsis thaliana . Plant J 2001, 25:1-8. 23. Torii, K U, Stoop-Myer, C D, Okamoto, H, Coleman, J E, Matsui, M, Deng, X W: The RING finger motif of photomorphogenic repressor COP1 specifically interacts with the RING-H2 motif of a novel Arabidopsis protein. J Biol Chem 1999, 274:27674-81.
The invention relates to a method to modulate plant growth or development. The invention provides a method for modulating a developmental transition of a plant comprising modulating expression of a RING-H2 protein or functional fragment thereof in said plant or parts thereof.
2
FIELD OF THE INVENTION [0001] The present invention relates to a torsion adjustment structure, member, and method for hinge device and in particular to a torsion adjustment structure, member, and method of torsion adjustment suitable for an enclosed hinge device. BACKGROUND OF THE INVENTION [0002] “Rotating Shaft Structure with Automatic Locking Mechanism,” developed by the present inventor, is disclosed in the ROC Patent No. M296586 on Aug. 21, 2006 (corresponding to the PRC Patent No. 200620001995.4), as shown in FIG. 17 . The invention mainly involves inserting the shaft 101 of an axial member 10 into, in the order of, a friction disc 30 , a plate connecting part 40 , a cam member 50 , an elastic body 60 , and securingly fixed onto the main frame 20 , wherein the cam member 50 comprises a fastening part 501 and a sliding part 502 , and when the axial member 10 rotates, the wedge slot 502 a of the sliding part 502 is driven to slide and engage into the wedge block 501 a of the fastening part 501 , achieving the auto-locking function. [0003] However, the recent design of hinge device has varied greatly to meet different demands in torque. Therefore, to expand the product's applicability and resolve the issue of materials preparation, there is still room for improvement in the design of hinge devices. SUMMARY OF THE INVENTION [0004] The main object of the present invention is to provide a torsion adjustment structure, member, and method for hinge device, employing the hole diameters of a plurality of enclosing ends of an enclosing part as the torsion adjustment means, in which the interferences between the external pivoting diameter of the pivotal axle and the hole diameters of the plurality of the enclosing ends are different to achieve the purpose of torsion adjustment. [0005] The major improvement of the present invention lies in the fact that the plurality of the enclosing part has the function of additive torsion adjustment and the easy adjustment of total torsion so as to enhance the product's applicability and resolve the issue of material preparation; furthermore, the enclosing end can also strengthen the structural stability and thus reduce the rotational shaking of the pivotal axle. [0006] A torsion adjustment method for hinge device according to one preferred embodiment of the present invention comprises at least the following steps: [0007] an enclosing part is formed to have a plurality of enclosing ends; [0008] the plurality of the enclosing ends are formed to have openings of the same direction and point to the inner side, and the hole diameters of the plurality of the enclosing ends are formed to be different; [0009] the pivotal axle is pivoted onto the plurality of the enclosing ends so as to enable the external pivoting diameter of the pivotal axle having different interferences with the hole diameters; [0010] with the aforementioned steps, the pivotal axle may generate different frictional torsions with the plurality of the enclosing ends. [0011] A torsion adjustment method for hinge device according to another preferred embodiment of the present invention comprises at least the following steps: [0012] an enclosing part is formed to have a plurality of enclosing ends; [0013] the plurality of the enclosing ends are formed to have openings of the opposite directions and the hole diameters of the plurality of the enclosing ends are formed to be different; [0014] the pivotal axle is pivoted onto the plurality of the enclosing ends so as to enable the external pivoting diameter of the pivotal axle having different interferences with the hole diameters; [0015] with the aforementioned steps, the pivotal axle may generate different frictional torsions with the plurality of the enclosing ends. [0016] A torsion adjustment structure for hinge device according to a further preferred embodiment of the present invention comprises: [0017] an enclosing part having a first enclosing end and a second enclosing end; [0018] an arresting part securingly fixed onto one side of the enclosing part; [0019] a pivotal axle having a first axle segment pivoted onto the first and second enclosing ends to have two frictional torsions, between which a difference can be found, and a second axle segment is pivoted onto the arresting part and inserted through, in the order of, the locking retainer, a locking rotator, and elastic parts with the end of the second axle segment being securingly retained with a nut. BRIEF DESCRIPTION OF THE DRAWINGS [0020] The present invention can be more fully understood by reference to the following description and accompanying drawings, in which: [0021] FIG. 1 is the perspective view of a torsion adjustment member of the present invention; [0022] FIG. 2 is the cross-sectional view taken through the A-A line of the enclosing part in FIG. 1 ; [0023] FIG. 3 is schematic view of the preferred embodiment of a torsion adjustment member of the present invention; [0024] FIG. 4 is an alternative of the preferred embodiment of FIG. 1 ; [0025] FIG. 5 is a further alternative of the preferred embodiment of FIG. 1 ; [0026] FIG. 6 is the perspective view of the second embodiment of the torsion adjustment member; [0027] FIG. 7 is the cross-sectional view taken through the B-B line of the enclosing part in FIG. 6 ; [0028] FIG. 8 is a schematic view of the preferred embodiment of the torsion adjustment structure in FIG. 6 ; [0029] FIG. 9 is an alternative of the preferred embodiment of the enclosing part of the present invention; [0030] FIG. 10 is the schematic view of the exploded perspective view of FIG. 3 ; [0031] FIG. 11 is an exploded perspective view of FIG. 10 from another view angle; [0032] FIG. 12 is the cross-sectional view taken through the C-C line in FIG. 3 ; [0033] FIG. 13 is the cross-sectional view taken through the D-D line in FIG. 3 ; [0034] FIGS. 14 and 15 are the schemation of preferred embodiments of the pivotal axle connected with a fixed seat of the present invention; [0035] FIG. 16 is a schematic view for the exploded perspective view of FIG. 8 ; and [0036] FIG. 17 is an exploded perspective view of a prior art. DETAILED DESCRIPTION OF THE INVENTION [0037] With reference to FIGS. 1 to 3 , one preferred embodiment of the torque adjustment method for hinge device according to the present invention comprises the following steps: [0038] an enclosing part 1 is formed to have a first enclosing end 11 and a second enclosing end 12 ; [0039] the first and second enclosing ends 11 , 12 are formed to have openings 15 of the same direction and point to an inner face 14 , and the hole diameters, d 1 and d 2 , of the first and second enclosing ends 11 , 12 are formed to be different; [0040] a pivotal axle 3 is pivoted onto the first and second enclosing ends 11 , 12 so as to enable the external pivoting diameter of the pivotal axle 3 having different interferences with the hole diameters d 1 and d 2 ; [0041] in other words, the pivotal axle 3 may generate different frictional torsions with the first and second enclosing ends 11 , 12 , respectively; consequently, there is a difference in the frictional torsion generated between the pivotal axle 3 with the first and second enclosing ends 11 , 12 such that the aim of torsion adjustment can be achieved and the enclosing part 1 can also enhance the structural stability and thus reduce the rotational shaking of the pivotal axle 3 . [0042] For example, when the pivotal axle 3 rotates toward the inner face 14 and the frictional torsions generated between the pivotal axle 3 pivoted with the first enclosing end 11 and the second enclosing end 12 are 5 kg/cm and 4 kg/cm, respectively, the additive frictional torsion is 9 kg/cm; when the pivotal axle 3 rotates toward the external side, and the frictional torsion generated between the pivotal axle 3 pivoted with the first enclosing end 11 is 3 kg/cm due to the effect of the opening 15 and that with the second enclosing end 12 is 2 kg/cm, the additive frictional torsion is 5 kg/cm. Consequently, the “positive difference” of the total frictional torsion may reach about 4 kg/cm (9 kg/cm−5 kg/cm=4 kg/cm). However, before the addition is made, the “positive difference” of the frictional torsion generated at the first enclosing end 11 is about 2 kg/cm (5 kg/cm−3 kg/cm=2 kg/cm) and the “positive difference” of the frictional torsion generated at the second enclosing end 12 is about 2 kg/cm (4 kg/cm−2 kg/cm=2 kg/cm). The preferred embodiment of the present invention, however, may effectively adjust the “positive difference” of the frictional torsion, reaching as high as 4 kg/cm (9 kg/cm−5 kg/cm=4 kg/cm), which is an advantage of the torsion adjustment of the accumulating frictional torsion. [0043] With reference to FIG. 4 , the enclosing part 1 may also comprise a first enclosing end 11 , a second enclosing end 12 , and a third enclosing end 13 , whose openings 15 have the same direction and point to the inner side, the hole diameters of the first and third enclosing ends 11 , 13 are smaller than that of the second enclosing end 12 ; in other words, after the pivotal axle 3 is being pivoted, it generates a first frictional torsion, a second frictional torsion, and a third frictional torsion, wherein the first and third frictional torsions are larger than the second frictional torsion. [0044] With reference to FIG. 5 , the enclosing part 1 may also comprise a first enclosing end 11 , a second enclosing end 12 , and a third enclosing end 13 , whose openings 15 have the same direction and point to the inner side, and the hole diameters of the first and third enclosing ends 11 , 13 are larger than that of the second enclosing end 12 ; in other words, after the pivotal axle 3 is being pivoted, it generates a first frictional torsion, a second frictional torsion, and a third frictional torsion, wherein the first and third frictional torsions are smaller than the second frictional torsion. [0045] With reference to FIGS. 6 to 8 , the second embodiment of the torque adjustment method for hinge device according to the present invention comprises the following steps: [0046] an enclosing part 1 is formed to have a first enclosing end 11 a and a second enclosing end 12 a; [0047] the first and second enclosing ends 11 a , 12 a are formed to have openings 15 of the opposite direction, and the hole diameters, d 1 and d 2 , of the first and second enclosing ends 11 a , 12 a are formed to be different; a pivotal axle 3 is pivoted onto the first and second enclosing ends 11 a , 12 a so as to enable the external pivoting diameter of the pivotal axle 3 having different interferences with the hole diameters d 1 and d 2 ; [0048] in other words, the pivotal axle 3 may generate different frictional torsions with the first and second enclosing ends 11 a , 12 a , respectively; consequently, there is a difference in the frictional torsion generated between the pivotal axle 3 with the first and second enclosing ends 11 a , 12 a such that the aim of torsion adjustment can be achieved and the enclosing part 1 can enhance the structural stability and thus reduce the rotational shaking of the pivotal axle 3 . [0049] For example, when the pivotal axle 3 rotates toward the inner face 14 and the frictional torsion generated between the pivotal axle 3 pivoted with the first enclosing end 11 a is 3 kg/cm and that with the second enclosing end 12 a is 6 kg/cm, the additive frictional torsion is 9 kg/cm; when the pivotal axle 3 rotates toward the external side, and the frictional torsion generated between the pivotal axle 3 pivoted with the first enclosing end 11 a is 5 kg/cm due to the effect of the opening 15 and that with the second enclosing end 12 a is 2 kg/cm, the additive frictional torsion is 7 kg/cm. Consequently, the “positive difference” of the total frictional torsion may maintain at 2 kg/cm (9 kg/cm−7 kg/cm=2 kg/cm) even if the first enclosing end 11 and the second enclosing end 12 have opposite openings 15 without being completely cancelled out to be zero. [0050] With reference to FIG. 9 , the enclosing part 1 may also comprise a first enclosing end 11 , a second enclosing end 12 , and a third enclosing end 13 with the first and third openings 15 having the same direction and pointing to the inner side, and the opening 15 of the second enclosing end 12 pointing to the opposite direction, and the hole diameters of the first and third enclosing ends 11 , 13 are larger than that of the second enclosing end 12 ; in other words, after the pivotal axle 3 is being pivoted, it generates a first frictional torsion, a second frictional torsion, and a third frictional torsion, wherein the first and third frictional torsions are smaller than the second frictional torsion. Furthermore, if the hole diameters of the first and third enclosing ends 11 , 13 are smaller than that of the second enclosing end 12 , the first and third frictional torsions are larger than the second frictional torsion, which may also be another embodiment. [0051] With reference to FIGS. 10 to 15 , the torsion adjustment structure for hinge device comprises: [0052] an enclosing part 1 having a first enclosing end 11 and a second enclosing end 12 ; [0053] an arresting part 2 securingly fixed onto one side of the enclosing part 1 (for example, the enclosing part 1 is on its one side disposed with a protruded block 16 and a notch 26 is disposed on the arresting part 2 , wherein the protruded block 16 may be embeddingly fixed onto the notch 26 to join together the enclosing part 1 and the arresting part 2 ); [0054] a pivotal axle 3 having a first axle segment 31 pivoted onto the first and second enclosing ends 11 , 12 , to have two frictional torsions, between which a difference can be found, and a second axle segment 32 pivoted onto the arresting part 2 and inserted through, in the order of, the locking retainer 4 , a locking rotator 5 , and an elastic part 7 with the end of the second axle segment 32 being securingly retained with a nut 6 . [0055] The openings 15 of the first enclosing end 11 and the second enclosing end 12 are in the same direction and point to the inner face 14 . The locking retainer 4 has a positioning slot 41 and is securingly fixed onto the arresting part 2 . The locking rotator 5 has a positioning block 51 and is jointly rotatable with the second axle segment 32 of the pivotal axle 3 . When the locking rotator 5 is in the locking position, the positioning block 51 is positioned into the positioning slot 41 . The locking retainer 4 is disposed with a pin 42 and the arresting part 2 is correspondingly formed to have a pin hole 24 to securingly fix the locking retainer 4 onto the arresting part 2 . [0056] The other side of the enclosing part 1 is disposed with a stopping portion 17 and the first axle segment 31 of the pivotal axle 3 is disposed with a positioning portion 37 . When the pivotal axle 3 is being rotated, the positioning portion 37 of the pivotal axle 3 may be abutted against the stopping portion 17 so as to limit the rotation angle of the pivotal axle 3 . The elastic part 7 is a plurality of spring discs 71 or springs (not shown), and the plurality of the spring discs 71 are formed to have arc faces 72 and alternately inserted in opposite faces onto the end of the second axle segment 32 . The second axle segment 32 of the pivotal axle 3 is formed to have at least a flat face 321 , and the locking rotator 5 and the plurality of the spring discs 71 are correspondingly formed to have fastening holes 53 and 73 , respectively, so as to be inserted onto the second axle segment 32 . A gasket 8 is disposed between the nut 6 and the elastic part 7 . The first axle segment 31 of the pivotal axle 3 may be formed to have oil grooves 311 . [0057] With reference to FIGS. 14 and 15 , the extending end 18 of the enclosing part 1 is formed to have a positioning hole 19 and the pivotal axle 3 may be connected with a fixed seat 9 . With reference to FIG. 16 , the torsion adjustment structure according to the present invention may be further re-designed such that the openings 15 of the first enclosing end 11 and the second enclosing end 12 point to opposite direction and the opening 15 of the first enclosing end 11 points to the inner face 14 . [0058] While the invention has been described with reference to the a preferred embodiment thereof, it is to be understood that modifications or variations may be easily made without departing from the spirit of this invention, which is defined by the appended claims.
A torsion adjustment structure, member, and method for hinge device uses the hole diameters of a plurality of enclosing ends of an enclosing part as the torsion adjustment means, in which the interferences between the external pivoting diameter of the pivotal axle and the hole diameters of the plurality of the enclosing ends are different, such that the total torsion can be easily adjusted and the product's applicability can be expanded.
4
CROSS REFERENCE TO RELATED APPLICATIONS This patent application claims benefit of U.S. provisional Serial No. 60/188,958, filed Mar. 13, 2000. BACKGROUND OF THE INVENTION This invention concerns ultraviolet (UV or black) lights of a type used by technicians in carrying out leak detection inspections by illuminating potential leak sites to detect the presence fluorescent tracer dyes. This is commonly done in servicing air conditioning refrigeration systems, automobile air conditioning systems components, hydraulic machinery, etc. The dyes are typically mixed with a compatible oil and injected into the system. If leaks are present, a trace of the dye and oil mixture flow onto external surfaces. This leakage fluoresces when illuminated with UV and sometimes blue light, emitting visible light which can be seen by the technician. Such UV lights particularly adapted for leak detection service applications have been developed in recent years, utilizing selective reflection filters, sometimes referred to as “dichroic” filters which transmit ultraviolet wavelengths and reflect back visible light to maximize the user's ability to see any fluorescence that occurs. Such lights require high wattage lamps as a UV source as compared with most other application of UV lights, which therefore emit considerable heat energy. The use of reflecting or “dichroic” filters is a significant improvement over absorbent filters used in the past selectively which absorbed visible light from the high intensity light emitted by the lamps, since the filters themselves overheated if the light was used for long periods and sometimes cracked during such use. For this reason, the dichroic filters have been designed to transmit infrared radiation as well as UV to prevent overheating of the dichroic filter and other components. This is described in copending U.S. application Ser. No. 08/964,839, filed on Nov. 5, 1997 and U.S. Pat. No. 5,905,268. In those lights, visible light is reflected back into the housing such that some heating of the interior of the light occurs. In another types of testing, dyed smoke is used to initially locate leak, requiring a flashlight to detect the smoke. Also, it is often useful to have a flashlight available in darkened locations in buildings where equipment is being serviced. The previously UV lights have not been able to be used as an ordinary flashlight. Accordingly, it is the object of the present invention to provide a UV light which while utilizing a high intensity lamp as a powerful source of UV light does not result in overheating of the light nor specifically the optical components eliminating visible light, and which emits a very high proportion of the UV light generated by the lamp. It is another object to provide such a UV light which is also conveniently useable as a flashlight. SUMMARY OF THE INVENTION The above objects as well as others which will become apparent upon a reading of the following specification and claims are achieved by using a reflector rather than a dichroic filter to selectively act to produce a beam of UV light while also directing the visible and IR radiation out from the light. The reflector selectively reflects only emitted UV light by the lamp, while transmitting visible and IR radiation. Such dichroic reflector is commonly known in the art as a “cold mirror”. The cold mirror reflector is angled with respect to the high wattage lamp so that the UV light beam is directed out of a light housing through a first window formed on one side of the light. On the other hand, visible and infrared light is transmitted through the cold mirror reflector and out from a second window in the front end of the light housing. A detachable cap may be secured over the second housing wind to optionally block the visible-infrared light beam from exiting the light housing. Heating of the cold mirror reflector is minimized as none of the wavelengths are absorbed by that optical element, nor is retained elsewhere within the light housing when the cap is removed. At the same time, the light is capable of a dual use, i.e., as a pure UV light source and also as a flashlight increasing its utility to the user, particularly where tracer smoke testing is to be practiced. The light according to the invention is also compact and may be manufactured at low cost. DESCRIPTION OF THE DRAWINGS FIG. 1 is a perspective exterior view of an embodiment of a light according to the invention. FIG. 2 is a partially sectional view taken through the light shown in FIG. 1 . FIG. 3 is a top view of the partial section of FIG. 2 . FIG. 4 is a partially sectional view taken through the center of the light showing the reflector mounting. FIG. 5 is an enlarged partially sectional view of the head portion of an alternate embodiment of the invention. DETAILED DESCRIPTION In the following detailed description, certain specific terminology will be employed for the sake of clarity and a particular embodiment described in accordance with the requirements of 35 USC 112, but it is to be understood that the same is not intended to be limiting and should not be so construed inasmuch as the invention is capable of taking many forms and variations within the scope of the appended claims. Referring to the drawings, and in particular FIG. 1, the UV light 10 according to the present invention includes a housing 11 comprised of an elongated handle 12 and head portion 14 both made of a suitable molded plastic. A UV light beam window 16 faces to one side of the light 10 , while a visible-infrared window facing the end of light 10 is shown covered with a plastic cap 18 . FIG. 2 shows the inner details of the UV light 10 . A 12 volt 100 watt lamp 20 which is a powerful source of UV and visible radiation of a much greater power than the type used with a standard flashlight. The lamp 20 may be of the Xenon type of high color temperature (3500K) which produces substantial long wave ultraviolet emissions. The envelop is made of quartz which is itself highly transmittive to long wavelength ultraviolet, i.e., 340-380 nm. Such a lamp is available from Osram Sylvania under part number FCR 64625 HLX. The lamp 20 is located at the approximate focal point of a parabolic reflector 30 , electroformed of nickel on an accurately shaped stainless steel mandrel. A focal length of 0.187 inches allows the lamp 20 to be approximately located at the focal point to maximize beam concentration. As described in copending U.S. application Ser. No. 09/491,413, filed on Jan. 26, 2000 and U.S. application Ser. No. 08/964,839, filed on Nov. 5, 1997, the parabolic reflector 30 is preferably coated to eliminate destructive interference which would reduce the intensity of the reflected UV light The surface of the parabolic reflector 30 has a plurality of coatings applied thereto, one of aluminum and one of silicon dioxide. The interface of silicon dioxide and air, and silicon dioxide and aluminum produces a double refraction in an opposite sense, which offset each other to eliminate the potential destructive interference which otherwise could occur. The first coating is of aluminum, while the second coating is of silicon dioxide. The thickness of the silicon dioxide should be uniform and accurately held to achieve this effect, the thicknesses determined by the “quarter wave stack” principle. The refractive index of each interface, i.e., the silicon dioxide and air, silicon dioxide and aluminum determines the effective phase shift of the reflected light. A thickness of aluminum of 0.057 microns and of silicon dioxide of 0.066 microns has been successfully used for this purpose. The silicon dioxide-air interface causes an approximate 13 degree forward phase shift, the silicon dioxide-aluminum interface a 13 degree lagging phase shift, thereby offsetting each other. Silicon dioxide coatings have heretofore been employed simply to protect the substrate from scratches and oxidation but have not been sufficiently uniform nor of the proper thickness to achieve enhanced reflection of ultraviolet wavelengths. A coated parabolic reflector 30 suitable for this use is available from American Galvano, 312 N. Cota St., Unit I, Corona, Calif. 91720. The lamp 20 can be powered from a 12 volt power source such as a vehicle cigarette lighter socket by use of a plug connector 24 connected by cables 26 , a strain fitting 28 at the entrance to the handle 12 . An on-off switch 33 connects one lead to the lamp 20 , a connector 32 connecting the other lead. Batteries or an AC power source can also be used. A selective dicbroic reflector 36 is mounted within the head portion 14 opposite the reflector 30 and lamp 20 , inclined at 45° such as to redirect UV light emitted from the lamp 20 and parabolic reflector 30 out through the window 16 in one side of the housing 11 . The selective reflector 36 acts as a beam splitter, transmitting visible and infrared light while reflecting UV light such as to direct a pure UV beam out through the lens window 16 . The window 16 may be covered with a window lens constructed of borosilicate glass which is believed to block shorter wavelengths of UV light which might be hazardous to the eyes, i.e., around 320 nm and lower. The cold mirror reflector 36 preferably is of dichroic design utilizing a series of coatings of a predetermined thickness to create selective reflection. This invention contemplates a design of such coatings to produce selective reflection of UV light rather than transmission of UV light as described in U.S. Pat. No. 5,905,268, so that a UV light beam is directed out through the side facing window 16 . At the same time, the coatings are designed so that visible light is transmitted through the reflector 36 rather than reflected, so that a beam of visible light is directed out through the window 38 covered by cap 18 . Window 38 is also preferably covered with a clear lens covering constructed of borosilicate glass to block any deep UV light. As disclosed in U.S. Ser. No. 09/491,413, filed on Jan. 26, 2000, dichroic optical elements from ZC & R Coatings for Optics, Inc. of Torrance, Calif. are preferred as having coatings of tantalum pentoxide which do not absorb UV. A suitable cold mirror having a part number CM-UV-350 is commercially available from ZC & R. That particular cold mirror has a high percentage of reflectance and low percentage of transmittance of wavelength in the range of 350 nm to 450 and a high percentage of transmittance of wavelength from 600 nm to 1200 nm and higher. Deep UV, i.e., below 340 nm is largely transmitted. Thus, both visible and infrared are caused to be transmitted out of the light 10 to minimize heating and to create a visible beam for use in other tests and as a flashlight. The coatings of the cold mirror reflector 36 can also be applied by ZC & R to minimize blue visible light at wavelengths over 400 nm where the tracer dyes do not fluorescence in response to such blue light in order to eliminate the need for “blue blocker” eyeglasses which are necessary when the UV light beam also contains blue light. Elimination of blue light in the UV beam is advantageous for some leak testing applications as described in the above referenced copending application. The cold mirror reflector 36 can comprise a rectangular piece of coated borosilicate glass as seen in FIGS. 3 and 4. A molded-in groove 40 holds the reflector 36 in position in the head 14 at a 45° angle. The cap 18 also of a molded plastic such as silicone can be opaque to block the visible light, or the cap 18 can be removed to use the light 10 as a flashlight. If the visible light does not interfere with observation of the fluorescence, since being directed at 90° to the UV beam, the cap can be removed, tab 42 assisting in its removal, to maximize cooling of the housing interior. Alternatively, as shown in FIG. 5, the head 14 A can be formed with forward facing louvers 44 which shield vent openings 46 to improve cooling with the cap 18 in place.
A UV light utilizing an angled dichroic cold mirror reflector to selectively direct UV light out of a window on the side of the light housing while transmitting visible and infrared light out a window in the end of the housing to eliminate heat. The light may be used both as a flashlight and a black light for UV inspection. A removable cap can be placed over the end window to block visible light.
5
This application is a divisional of application Ser. No. 08/693,615, filed Aug. 7, 1996, U.S. Pat. No. 5,849,829, which claims benefit of Provisional Patent Application Ser. No. 60/002,046, filed on Aug. 8, 1995, in the name of Anne Buegman and entitled “Permeation-Resistant ETFE Composition and Coatings”; the disclosure of which is hereby incorporated by reference. FIELD OF THE INVENTION The instant invention relates to a composition of ethylene-tetrafluoroethylene copolymer (ETFE) which can be used as a coating or a surface-protecting laminate on a substrate to retard permeation by water to the substrate. BACKGROUND OF THE INVENTION ETFE copolymers are known in the art. U.S. Pat. No. 4,123,602—Ukihashi et al. (1978) discloses such polymers with about 40 to 60 mole % of each comonomer, using modifiers such as 1% perfluoro butylethylene. Such modifiers and other adjuvants are common in the art and are considered to be part of the copolymer. Films of various fluoropolymers including ETFE, which can have various fillers including mica, are used for cladding metal substrates in Japanese Kokai 4-229246—Sahara et al. (1992). There is no focus in this kokai on minimizing permeation or on using mica in ETFE, or on what proportions would be needed. Mica coated with oxides to produce sparkling optical effects is the subject of U.S. Pat. No. 3,087,829—Linton (1963). Mica is used in fluoropolymer coatings for cookware to minimize stain formation, as in U.S. Pat. No. 4,353,950—Vassiliou (1982). The disclosure of the previously identified patents and patent publications is hereby incorporated, by reference. SUMMARY OF THE INVENTION The instant invention solves permeation and corrosion problems associated with conventional ETFE containing coatings by providing an additive such as mica. A mixture comprising or consisting essentially of ETFE and mica can be used effectively as a powder. The powder of ETFE and mica and be applied upon a substrate in order to provide a permeation and corrosion resistant coating. The instant invention provides a permeation-resistant composition of matter comprising or consisting essentially of at least one fluoropolymer such as a copolymer of ethylene and tetrafluoroethylene (ETFE) and at least one additive such as mica which is either uncoated or coated with oxide, wherein the ETFE is a copolymer of about 40 to about 60 mole % of ethylene and about 60 to about 40 mole % tetrafluoroethylene, based on the copolymer, and wherein the additive is present in amounts of about 3 to about 25% by weight based on the ETFE plus mica, e.g., normally about 7.5 to about 15% by weight mica. In one aspect, the instant invention provides coating compositions, processes and coatings that can be laminated onto a suitable substrate. In another aspect, the instant invention relates to a dry powder coating that can be adhered to a substrate by one or more primer coatings or layers. The dry powder can be heated in order to form a substantially continuous coating or layer upon the substrate, e.g, a substrate coated with a primer. DETAILED DESCRIPTION While any suitable fluoropolymer can be employed in connection with the instant invention, it has been found that an ETFE based fluoropolymer and typically about 10% by weight mica in a coating gives maximum resistance to water permeation. Any suitable process can be employed for applying the fluoropolymer containing composition onto a substrate, e.g., an electrostatic-spray process for applying a powder mixture comprising ETFE and mica. Depending upon the conditions of the spraying process, some of the mica of the composition can be lost; but, under normal process conditions the resultant coating contains at least about 4 to 5% by weight mica in the coating on the coated substrate. The coating of the instant invention can be employed in a virtually unlimited array of environments for improving the corrosion and permeation resistance of the underlying substrate, e.g., water vapor permeation resistance. Examples of such substrates include molds, tubes, chemical containers and reactors, among others. For example, for coating the inside of chemical containers or equipment vessels by rotolining, or for coating by film lamination a minimum of about 5% mica is satisfactory. More mica is generally better than less, but over a certain level such as over 25%, excess mica can degrade the mechanical integrity and properties of the coating. Normally, a mica having a platelet thickness of about 1-2 microns and an average diameter of about 10 to 130 microns is employed. If desired, one or more water or corrosion resistant additives can be employed along with mica. Additionally other additives may be used such as those that alter the properties of the coating composition or the coated substrate. For instance, various flow agents such as silica may be added to the ETFE /mica blend to improve ease of application. The use of a coating consisting essentially of mica in ETFE in accordance with the invention retarded water penetration drastically in standard Atlas Cell tests using ASTM method C868, from 2 days with no mica, to over 2 weeks with about 10% mica. While the previous description has focused upon a coating consisting essentially of ETFE and mica, a skilled person in this art understands that one or more fluoropolymers can be employed instead of and in conjunction with ETFE. For best results, however, the composition will contain ETFE as the predominant fluoropolymer. Suitable ETFE is available commercially and typically has an average particle size of less than about 50 microns. The instant invention can be employed as a coating on a variety of substrates which may include a plurality of films, coatings or layers in order to obtain a composite or laminate structure. For example, one or more primer coatings or layers can be located between the substrate and ETFE/mica composition. While any suitable primer can be employed, examples of particularly useful primers include a mixture of ETFE with adhesion promoting polymers such as amide-imide polymers, polyphenylene sulfide (PPS), mixtures thereof, among others. One or more primer coatings can be prepared and applied by using any suitable conventional method. When a primer is employed, the ETFE/mica composition becomes a so-called topcoat. That is, the ETFE/mica composition is exposed to the environment containing the corrosive or permeating species thereby protecting the underlying substrate. The topcoat composition can be obtained by using any suitable method. One such method comprises dry blending ETFE and mica powders by using about 90% by weight TEFZEL*R* ETFE sold commercially by DuPont Company (as product code 532-6018) and about 10% platelet shaped Iriodine*R* oxide coated mica additive from Merck, Germany. While any suitable substrate can be coated, examples of suitable substrates include steel, high carbon steel, aluminum, among others. Depending upon the characteristics desired in the coated substrate, at least one member from the group of pigments, flow agents, stablizers, among others, can be added to the ETFE/mica or primer coatings. An example of a suitable stabilizer comprises copper iodide, e.g., cuprous iodide (CuI). The surface characteristics or substrate profile are not critical parameters for the final performance of the coating; but, surface roughening by any conventional means such grit blasting, etching, among others, can aid adhesion of the coating to the substrate. If desired, a primer coating or layer can be located between the instant coating and the substrate. While the primer does not play a critical role for the permeation resistance of the coating, the primer can enhance adhesion of the coating to the substrate thereby improving the useful life of the coating. One suitable primer is sold by the DuPont Company as product code 699-123. An example of a suitable primer composition, which was obtained from commercially available materials, is given in Table I (in weight percent). TABLE I Primer Composition Carbon black 0.990 Acrylic emulsion copolymer 0.283 Colloidal silica, Ludox*R* AM from DuPont 0.876 Amide imide polymer 3.015 Polyphenylene sulfide 3.003 50:50 Ethylene-tetrafluoroethylene 19.340 copolymer 4,4′-Methyene dianiline 0.033 Hydroxypropyl cellulose 0.091 Cuprous iodide 0.014 Sodium polynaphthalene sulphonate 0.073 Octyl phenol polyether alcohol 1.382 Deionized water 64.721 Triethanol amine 0.039 N,N-Dimethylethanolamine 0.116 Heavy naphtha 0.406 N,N-Diethyl-2-amino ethanol 0.425 Triethyl amine 0.850 Furfuryl alcohol 2.367 N-Methyl-2-pyrolidone 1.976 The following example is provided to illustrate not limit the scope of the invention as defined in the appended claims. In the following example, parts, percentages and proportions are by weight except where indicated otherwise. EXAMPLE A substrate comprising carbon steel was roughened by conventional gritblasting methods under conditions sufficient to obtain a surface roughness (Ra) of about 10 to about 15 um. The primer described above in Table 1 was applied by using conventional methods to the roughened substrate until a dry film thickness (DFT) of about 10 to about 15 microns was achieved. The primer was air-dried. ETFE was passed through a 250 micron filter. A first corrosion resistant coating consisting essentially of preblended ETFE/mica was prepared. The preblended ETFE/mica mixture was coated upon the carbon steel substrate at ambient temperature with a flat jet nozzle dry powder spray gun made by Gema Company of Switzerland (product code GEMA PG1 or PGC1 normally with a corona ring), that was operated at a spraying voltage of about 10 kv to about 30 kv. The first coating was applied with a relatively smooth flow and the coating was air dried. A thermocouple was attached to the coated substrate, which was then heated in an oven at maximum oven temperatures of about 310° C. While heating, the temperature of the substrate was measured with the thermocouple. The substrate was heated for about 20 minutes at a temperature of about 295 to about 300° C. The substrate was removed from the oven and coated while still hot using the so-called hot flocking process. This heating step causes the particles of ETFE within the coating to coalesce thereby forming a substantially continuous coating upon the substrate. The application of the ETFE/mica composition was stopped when the thermocouple temperature dropped below about 260° C. (melting temperature of ETFE). The coated substrate was then baked for 20 minutes at 295-300° C. before a subsequent coating was applied. The substrate was coated repeatedly with the ETFE/mica composition. For best results and in order to obtain a smooth bubble-free coating of all ETFE powder-mica coating, the ETFE/mica composition is applied at about 100 to about 150 micron DFT per coat. Such a coating is visually glossy and smooth, and free of bubbles substantially throughout the thickness of the coating. The DFT of the coatings can be tailored for a wide range of applications. To achieve a relatively high DFT, ETFE/mica coatings should be applied successively as described above to the desired total DFT, typically in the range of 500 to 2,500 microns in thickness. Normally, the last or final coating (also known as the top-coat) is heated for a period of about 30 to 45 minutes at a temperature of about 295 to 300° C. The water vapor resistance of the previously described coated substrate was tested in a conventional Atlas Cell. Coated substrates were exposed to the liquid-gas interface of a solution media of pure deionized water and/or acid at a low concentration, hydrochloric acid specifically 0.05M HCl in deionized water, at the boiling temperature until the coating shows blistering failure. When the water permeates through the coating and contacts the substrate, blisters can form. Tests were conducted using DFTs of 400-500 microns. Under these conditions the blistering resistance was more than 4 weeks for both liquids. Other experiments were conducted and showed that if the coating is applied at a minimum DFT of 150 microns the same water vapor resistances are obtained. These results are also useful for molds and chemical processing industry equipment. The system without mica addition shows very poor water vapor resistance. The following Table 2, illustrates the blister formation time as a function of weight percent mica and DFT. TABLE 2 % Mica Time(hours) DFT(microns) 0 72 398 5 <336 398 7.5 <336 356 10 >720 439 Table 2 illustrates that the presence of mica provides improved water vapor resistance to permeation, e.g., without mica blistering occurs after 3 days exposure. Table 2 also illustrates that a substrate coated with a first layer comprising a primer and a second layer of ETFE/mica achieves desirable water vapor resistance properties. While the ETFE/nica coating can be tailored for a variety of environments, for best results the coating is applied at a minimum DFT of 150 microns.
A coated substrate comprising: (a) a substrate; (b) a primer layer containing adhesion-promoting polymer on said substrate; and (c) at least one topcoat of a permeation resistant composition of ethylene-tetrafluoroethylene (ETFE) copolymer and mica, therein the ETFE is a copolymer of about 40 to 60 mole % ethylene and about 60 to 40 mole % tetrafluoroethylene, wherein the mica is present in amounts of about 3 to about 25 wt % based on the ETFE and mica, and wherein the topcoat having a thickness of at least 150 μm. The coated substrate is formed by applying the primer to the substrate and drying, followed by dry powder coating at least one layer of ETFE and mica composition, followed by heating said layer.
8
This is a continuation of application Ser. No. 08/636,755 filed Apr. 19, 1996, now U.S. Pat. No. 5,888,856, which is a divisional of application Ser. No. 08/561,334, filed Nov. 21, 1995, now U.S. Pat. No. 5,693,961, the disclosure of which is incorporated herein by reference. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a top-gate type polycrystalline silicon thin film transistor (TFT). 2. Description of the Related Art Polycrystalline silicon TFT's are used in integrated circuits, particularly, load elements of a static random access memory (SRAM) and liquid crystal devices (LCD's). In a prior art method for manufacturing a top-gate type TFT, a polycrystalline silicon layer, a gate insulating layer, a gate electrode layer, a non-doped insulating layer, and a metal connection layer are formed on a substrate, and then, a hydrogen passivation using hydrogenation by plasma discharge is carried out, to thereby reduce trap state densities of the polycrystalline silicon layer and improve the performance of the TFT, That is, a hydrogen passivation time is so long that saturated trap reduction characteristics and saturated threshold voltage characteristics can be obtained (see: I-WEI WU et al. "Effect of Trap-State Density Reduction by Plasma Hydrogeneration in Low-Temperature Polysilicon TFT", IEEE ELECTRON DEVICE LETTERS, VOL. 10, No. 3, pp. 123-125, March 1989 and "Performance of Polysilicon TFT Digital Circuits Fabricated with Various Processing Techniques and Device Architechtures", SID 90 Digest, pp. 307-310, 1990). This will be explained later in detail. In the above-described prior art method, when a gate length of the TFT is too small, for example, less than 10 μm, a parasitic bipolar phenomenon may occur, so that the electric property is fluctuated. For example, the breakdown voltage of the TFT is reduced, and the threshold voltage of the TFT is fluctuated. SUMMARY OF THE INVENTION It is an object of the present invention to provide a top-gate type TFT capable of suppressing the reduction of the breakdown voltage and the fluctuation of the threshold voltage. Another object is to provide a method for manufacturing such a top-gate type TFT. According to the present invention, in a top-gate type thin film transistor including a polycrystalline silicon pattern having a channel region, a source region and a drain region on a substrate, a gate electrode via a gate insulating layer on the polycrystalline silicon layer, an insulating layer thereon, and metal electrodes coupled to the source region and the drain region, dangling bonds of silicon of the channel region at an interface with the gate insulating layer and dangling bonds of silicon of a part of the drain region are combined with hydrogen. Thus, in the channel region, since only dangling bonds of silicon at the interface of the channel region and the gate insulating layer are combined with hydrogen, no parasitic bipolar phenomenon occurs. BRIEF DESCRIPTION OF THE DRAWINGS The present invention will be more clearly understood from the description as set forth below, in comparison with the prior art, with reference to the accompanying drawings, wherein: FIG. 1 is a cross-sectional diagram illustrating a prior art top-gate type TFT; FIG. 2 is a graph showing I DS -V G characteristics of the TFT of FIG. 1; FIG. 3 is a graph showing trap state reduction characteristics and threshold voltage characteristics of the TFT of FIG. 1 dependent upon a hydrogen passivation time period; FIGS. 4A through 4J are cross-sectional views illustrating a first embodiment of the method for manufacturing a top-gate type TFT according to the present invention; FIG. 5 is a plan view of the TFT of FIG. 4J; FIG. 6 is a graph showing hydrogen passivation time in relation to drain voltage characteristics of the TFT of FIG. 4J and 5; FIG. 7 is a graph showing hydrogen passivation time in relation to threshold voltage characteristics of the TFT of FIG. 4J and 5; FIG. 8 is a graph showing hydrogen peak intensity characteristics for estimating the amount of hydrogen trapped in the polycrystalline silicon pattern of FIGS. 4J and 5; FIGS. 9A and 9B are cross-sectional views illustrating devices used for obtaining the characteristics of FIG. 8; FIG. 10 is a graph showing degassed heavy hydrogen characteristics of the device of FIG. 4B; FIGS. 11A through 11B are cross-sectional views illustrating a second embodiment of the method for manufacturing a top-gate type TFT according to the present invention; FIG. 12 is a plan view of the TFT of FIG. 11B; FIG. 13 is a graph showing current to voltage characteristics of the TFT of FIG. 11B and 12; FIGS. 14A through 14E are cross-sectional views illustrating a third embodiment of the method for manufacturing a top-gate type TFT according to the present invention; FIGS. 15 is a plan view of the TFT of FIG. 14E; and FIGS. 16A through 16F are cross-sectional views illustrating a fourth embodiment of the method for manufacturing a top-gate type TFT according to the present invention. DESCRIPTION OF THE PREFERRED EMBODIMENTS Before the description of the preferred embodiments, a prior art method for manufacturing a TFT will now be explained with reference to FIG. 1 (see: the above-mentioned documents by I-WEI WU et al.). In FIG. 1, a prior art top-gate type TFT is illustrated. That is, a 100 nm thick amorphous silicon is deposited on a fused quartz substrate 101 by a low pressure chemical vapor deposition (LPCVD) process, and a heating operation is performed thereupon at a temperature of 600° C. for four hours in a nitrogen atmosphere, to thereby from a polycrystalline silicon layer 102. The polycrystalline silicon layer 102 is patterned into an island. Then, a 100 nm thick gate silicon oxide layer 103 is formed, and also, a 350 nm thick polycrystalline silicon gate electrode layer 104 is formed. After the gate electrode layer 104 is patterned, 2×10 15 phosphorous ions/cm 2 are doped in self-alignment with the patterned gate electrode layer 104, to form N + -type source and drain regions in the polycrystalline silicon layer 102. Then, a 700 nm thick non-doped low temperature silicon oxide (LTO) layer 105 is deposited by a LPCVD process, and a heating operation at 600° C. is carried out to anneal the doped impurity ions within the source and drain regions of the polycrystalline silicon layer 102. Thereafter, contact holes are perforated within the LTO layer 105 and the gate silicon oxide layer 103, and a 1 μm thick AlSiCu layer 106 is deposited. Then, the device of FIG. 1 is sintered at a temperature of 450° C. for 30 minutes within a H 2 --N 2 forming gas. Finally, a hydrogen passivation is carried out for 16 hours in a parallel-plate plasma reactor at a substrate temperature of 350° C. with an H 2 and Ar gas mixture at a power density of 0.21 W/cm 2 and a frequency of 30 kHz. As a result, dangling bonds of silicon of the polycrystalline silicon layer 102 are completely combined with hydrogen. Thus, the TFT is completed. In the TFT of FIG. 1, hydrogen atoms can diffuse in the 700 nm thick non-doped LTO layer 105 to reach the active channel region of the polycrystalline silicon layer 102. Therefore, as shown in FIG. 2, when a gate length L is 50 μm, a gate width W is 20 μm, and a drain voltage V DS is 5V, the drain current (I DS )-to-gate voltage (V G ) characteristics are improved. That is, a leakage current is decreased some hundred times (≈10 -2 ), an ON current is increased some thousand times (≈10 3 ) at the gate voltage V G =20V and some hundreds of thousands of times (≈10 5 ) at the gate voltage V G =5V. Also a subthreshold voltage characteristic is improved. Also, as shown in FIG. 3, which shows the trap state reduction and threshold voltage characteristics of the polycrystalline silicon layer 102, when the hydrogen passivation time is longer than 16 hours, saturated trap state reduction characteristics and saturated threshold voltage characteristics are obtained. The TFT of FIG. 1 can be applied to a case where the gate length L is relatively large, such as, L=50 μm. However, when the gate length L becomes small, for example, when L=10 μm, the electric property of the TFT is fluctuated. That is, the P - -type channel region of the polycrystalline silicon layer 102 is in a floating state, and accordingly, the voltage V BODY at the channel region is dependent upon the drain voltage V DS . Also, when the voltage V BODY at the channel region reaches 0.6V, a parasitic bipolar phenomenon may occur to thereby fluctuate the electrical property of the TFT. Therefore, the drain voltage V DS is required to be sufficiently high, by which the voltage V BODY at the channel region reaches 0.6V. However, the insulating layer 105 is made of a double structure of non-doped silicon oxide and flattened boron-including phospho-silicated glass (BPSG) and the gate length L is smaller than 10 μm. Therefore, when a hydrogen passivation is carried out for 16 hours, the drain voltage is smaller than 6V when the voltage V BODY at the channel region reaches 0.6V. As a result, the breakdown voltage is reduced, and the threshold voltage is fluctuated. In view of the requirement for a ±20 percent fluctuation of the power supply voltage, the prior art TFT of FIG. 1 cannot be applied to 5V system devices. FIGS. 4A through 4J are cross-sectional views illustrating a first embodiment of the method for manufacturing a top-gate TFT according to the present invention. First, referring to FIG. 4A, a non-doped silicon oxide layer 2 is deposited on a fused quartz substrate 1 by a CVD process. In this case, other insulating layers made of silicon nitride or a stacked configuration of non-doped silicon oxide and BPSG can be used instead of the non-doped oxide layer 2. Also, if a monocrystalline silicon substrate is used instead of the fused quartz substrate 1, the non-doped silicon oxide layer 2 is grown by thermally oxidizing the monocrystalline silicon substrate. Then, an about 80 nm thick amorphous silicon layer is deposited by an LPCVD process at a substrate temperature of about 500° C. with a source gas of Si 2 H 6 . Then, the amorphous silicon is heated for about 12 hours at a temperature of about 600° C. in a nitrogen atmosphere to change the amorphous silicon into a polycrystalline silicon layer 3. In this case, before or after the conversion of the amorphous silicon into the polycrystalline silicon layer 3, about 2×10 17 boron ions per cm 2 are implanted thereinto, so that the polycrystalline silicon layer 3 is of a P - -type. Next, referring to FIG. 4B, the polycrystalline silicon layer 3 is patterned into an island-shaped polycrystalline silicon pattern 3a. Next, referring to FIG. 4C, an about 100 nm thick non-doped gate silicon oxide layer 4 is formed by an LPCVD process. Then, an about 200 nm thick polycrystalline silicon layer 5 is formed by an LPCVD process. Next, referring to FIG. 4D, the polycrystalline silicon layer 5 is patterned into a gate electrode layer 5a. Note that the gate electrode layer 5a can be made of polycide, silicide or metal. Next, referring to FIG. 4E, about 1×10 15 phosphorous ions/cm 2 are implanted at an energy of about 50 keV into the polycrystalline silicon pattern 3a in self-alignment with the gate electrode layer 5a. As a result, an N + -type source 31 and an N 30 -type drain region 32 are formed in self-alignment with the gate electrode layer within the polycrystalline silicon pattern 3a. Also, simultaneously, a P - -type channel region 33 is formed within the polycrystalline silicon pattern 3a between the N + -type source region 31 and the N + -type drain region 32. Next, referring to FIG. 4F, an about 50 nm thick non-doped silicon oxide layer is formed by an LPCVD process, and then, an about 350 nm thick BPSG layer is formed by an atmospheric pressure CVD (APCVD) process. Thus, an insulating layer 6 made of silicon oxide and BPSG is formed. Then, a heating operation is carried out at about 900° C. for about 30 minutes to anneal the source region 31 and the drain region 32 and flatten the insulating layer 6. In this case, the non-doped silicon oxide of the insulating layer 6 protects the active region of the TFT, i.e., the polycrystalline silicon pattern 3a. Also, since the BPSG of the insulating layer 6 includes impurities such as boron and phosphorous, the non-doped silicon oxide of the insulating layer 6 prevents such impurities from being diffused into the polycrystalline silicon pattern 3a. Note that phospho-silicated glass (PSG) layer, boron-silicated glass (BSG) or a stacked configuration thereof can be used instead of the BPSG of the insulating layer 6. However, silicon nitride is never used for the insulating layer 6, since the silicon nitride prevents hydrogen from being diffused into the polycrystalline silicon pattern 3a. Also, if the source region 31 and the drain region 32 are of a lightly-doped drain (LDD) structure or the source region 31 and the drain region 32 are shifted slightly from the gate electrode 5a, the gate silicon oxide layer 4 is removed from the source region 31 and the drain region 32. Therefore, in this case, the non-doped silicon oxide of the insulating layer 6 is required to cover the source region 31 and the drain region 32 again. Next, referring to FIG. 4G, contact holes CONT1 and CONT2 are perforated in the insulating layer 6 and the gate silicon oxide layer 4, so that the source region 31 and the drain region 32 are partly exposed. Next, referring to FIG. 4H, an about 1 μm thick Al--Si--Cu alloy layer 7 is deposited by sputtering. Then, the device is sintered at a temperature of about 400° C. for about 20 minutes in a H 2 /N 2 forming gas. As a result, an ohmic contact is realized between the regions 31 and 32 and the Al--Si--Cu alloy layer 7. Note that a barrier layer made of TiW, Ti, TiSi 2 or TiN can be provided between the regions 31 and 32 and the Al--Si--Cu alloy layer 7. Also, other metal such as AlSi can be used for the layer 7. Next, referring to FIG. 4I, the Al--Si--Cu alloy layer 7 is patterned, so that electrode layers 7a and 7b are formed on the source region 31 and the drain region 32, respectively. Finally, referring to FIG. 4J, a hydrogen passivation is carried out for about 30 minutes in a parallel-plate plasma reactor at a substrate temperature of about 350° C. with H 2 --Ar gas at a power density of 0.21 W/cm 2 and a frequency of 30 kHz. Note that FIG. 5 is a plan view of the device of FIG. 4J, which is taken along the line IV--IV of FIG. 5. In FIG. 4J, in the channel region 33, only dangling bonds of silicon at an interface with the gate silicon oxide layer 4 are combined with hydrogen. On the other hand, in the source region 31 and the drain region 32, most of the dangling bonds of silicon therein are combined with hydrogen. After that as occasion demands, a step for forming a passivation layer is carried out; however, in this case, such a step is carried out at a temperature lower than about 500° C. This will be explained later in detail. In FIG. 6, which shows hydrogen passivation time in relation to drain voltage characteristics where the gate length L is 6.0 μm and the gate width W is 2.0 μm, the hydrogen passivation time is changed in the first embodiment. As explained above, a parasitic bipolar phenomenon may occur when the voltage V BODY of the channel region 33 is 0.6V. As shown in FIG. 6, when the hydrogen passivation time is zero, the drain voltage V DS is 6.5V at V BODY =0.6V. Also, when the hydrogen passivation time is 30, 60 and 150 minutes, the drain voltage V DS is 6.4V, 6.0V and 5.9V, respectively, at V BODY =0.6V. That is, when the hydrogen passivation time is 60 minutes, the reduction of the drain voltage V DS at V BODY =0.6V is saturated. Therefore, when the hydrogen passivation time is larger than 60 minutes, a parasitic bipolar phenomenon may occur, so that the device cannot be applied to a 5V system. In FIG. 7, which shows hydrogen passivation time in relation to threshold voltage characteristics where the gate length L is 6.0 μm, the gate width 2 is 2.0 μm, and the drain voltage V DS is 5.0V, when the hydrogen passivation time is from 0 to 30 minutes, the threshold voltage V th is remarkably reduced, and when the hydrogen passivation time is from 30 to 120 minutes, the threshold voltage V th is gradually reduced. That is, when the hydrogen passivation time is 120 minutes, the reduction of the threshold voltage V th is saturated. Also, as is not shown, when the hydrogen passivation time is 30 minutes under the above-described condition, a leakage current is reduced several times (≈10 -1 .5) (see 10 -2 in the prior art) as compared with a case where no hydrogen passivation is carried out. Also, an ON current is increased some tens of hundreds of times (≈10 4 ) (see 10 5 in the prior art) as compared with a case where no hydrogen passivation is carried out. Thus, in the first embodiment, when the hydrogen passivation time is 30 minutes, the breakdown voltage is remarkably improved, although the improvement of the leakage current and the ON current are deteriorated slightly. In FIG. 8, which shows hydrogen peak intensity characteristics for estimating the amount of hydrogen trapped in the polycrystalline silicon pattern 3a of FIGS. 4J and 5, devices as illustrated in FIGS. 9A and 9B are heated by a thermal desorption spectroscopy (TDS) apparatus to about 1150° C., and as a result, hydrogen degassed from the TDS apparatus is analyd by a quadrupole mass spectrometer. Note that the device as illustrated in FIG. 9A is comprised of a fused quartz substrate 901, a non-doped silicon oxide layer 902, an about 80 μm thick P - -type polycrystalline silicon layer 903, an about 150 nm thick non-doped silicon oxide layer 904 formed by an LPCVD process, and an about 350 nm thick BPSG layer 905. On the other hand, the device as illustrated in FIG. 9B is the same as the device as illustrated in FIG. 9A excluding the non-doped silicon oxide layer 904 and the BPSG layer 905. First, after a plasma hydrogen passivation is performed upon the device as illustrated in FIG. 9A for 30, 60 and 150 minutes, the amount of hydrogen degassed from the TDS apparatus is measured as indicated by a solid line in FIG. 8. In this case, the amount of hydrogen is remarkably increased for the hydrogen passivation time of 0 to 60 minutes, and the amount of hydrogen is gradually increased for the hydrogen passivation time larger than 60 minutes. Next, after a plasma hydrogen passivation is performed upon the device as illustrated in FIG. 9A for 30, 60 and 150 minutes, the BPSG layer 905 is removed, and thereafter, the non-doped silicon oxide layer 904 is removed by heavy hydrogen dilute fluorine acid to obtain the device of FIG. 9B. At this time, hydrogen combined with dangling bonds of silicon at the interface with the non-doped silicon oxide layer 904 is replaced by heavy hydrogen. Then, the amount of hydrogen gassed from the TDS apparatus is measured as indicated by a dot line in FIG. 8. In this case, the amount of hydrogen trapped in the polycrystalline silicon layer 903 is measured. That is, the amount of hydrogen trapped in the polycrystalline silicon layer 903 is gradually increased for the hydrogen passivation time of 0 to 30 minutes and longer than 60 minutes. On the other hand, the amount of hydrogen trapped in the polycrystalline silicon layer 903 is remarkably increased for the hydrogen passivation time between 0 to 30 minutes. The graph as shown in FIG. 8 reveals the following phenomenon. That is, dangling bonds of most silicon of the non-doped silicon oxide layer 904 and dangling bonds of silicon of the polycrystalline silicon layer 903 at the interface with the non-doped silicon oxide layer 904 are combined with hydrogen for the first 30 minutes of the hydrogen passivation. Thereafter, dangling bonds of silicon of the polycrystalline silicon layer 903 are combined with hydrogen. In other words, hydrogen rapidly propagates in the interface of the polycrystalline silicon layer 903 with the non-doped silicon oxide layer 904, while hydrogen gradually propagates in the interior of the polycrystalline silicon layer 903. Also, generally, the hydrogen diffusion preventing power of BPSG is low, while the hydrogen diffusion preventing power of non-doped silicon oxide and polycrystalline silicon is high. Returning to FIG. 4J, in view of the foregoing, hydrogen at the interface of the channel region 33 with the gate silicon oxide layer 4 is diffused from the interfaces of the source region 31 and the drain region 32 with the gate silicon oxide layer 4. Thus, in the first embodiment, the hydrogen passivation time is preferably 30 minutes; however, it depends on the thickness of the gate silicon oxide layer 4 and whether or not a BPSG layer is in direct contact with the regions 31 and 32. Also, referring to FIGS. 6 and 8, when the hydrogen passivation time is very long, for example, longer than 60 minutes, dangling bonds of silicon of the bulk of the channel region 33 of FIG. 4J are also combined with hydrogen. As a result, minority carriers (which are in this case holes) generated in the channel region 33 are hardly recombined with electrons, so as to lengthen the life time of the minority carriers in the channel region 33, which may cause a parasitic bipolar phenomenon. As a result, the voltage V BODY at the channel region 33 easily rises. As explained above, in the device of FIG. 9B, after the non-doped silicon oxide layer 904 (FIG. 9A) is removed by heavy hydrogen dilute fluoride acid, the hydrogen at the interface of the polycrystalline silicon layer 903 and the non-doped silicon oxide layer 904 is replaced by heavy hydrogen. Therefore, when the device of FIG. 4B is heated by the TDS apparatus, and heavy hydrogen degassed from the TDS apparatus is analyzed by the quadrupole mass spectrometer, the amount of degassed heavy hydrogen is changed as shown in FIG. 10. That is, the amount of degassed heavy hydrogen is at peak when the temperature of the device of FIG. 4B heated by the TDS apparatus is about 600° C. Also, most of the heavy hydrogen in the polycrystalline silicon layer 903 is degassed when the temperature of the device of FIG. 4B heated by the TDS apparatus is about 700° C. Thus, as stated above, an operation for forming a passivation layer or the like on the device of FIG. 4J is carried out preferably at a lower temperature than 500° C. FIGS. 11A and 11B are cross-sectional views illustrating a second embodiment of the method for manufacturing a top-gate type TFT according to the present invention, and FIG. 12 is a plan view of the TFT of FIG. 11B, which is a cross-sectional view taken along the line IX--IX of FIG. 12. Note that FIGS. 11A, 11B and 12 correspond to FIGS. 4I, 4J and 5, respectively. That is, the manufacturing steps as illustrated in FIGS. 4A through 4H are applied to the second embodiment. Referring to FIG. 11A, an electrode layer 7a covers not only the source region 31 entirely but also a part of the channel region 33 (also see FIG. 12). Finally, referring to FIG. 11B, a hydrogen passivation is carried in the same way as in FIG. 4J. In this case, since the electrode layer 7a' covers the source region 31 and a part of the channel region 33, dangling bonds of silicon in the source region 31 are hardly combined with hydrogen. As a result, as shown in FIG. 13, the second embodiment is advantageous over the first embodiment in respect to the breakdown voltage. FIGS. 14A through 14E are cross-sectional views illustrating a third embodiment of the method for manufacturing a top-gate type TFT according to the present invention, and FIG. 15 is a plan view of the TFT of FIG. 14F, which is a cross-sectional view taken along the line IV--IV of FIG. 15. Note that FIGS. 14A through 14E and 15 correspond to FIGS. 4G through 4J and 5, respectively. Also, the manufacturing steps as illustrated in FIGS. 4A through 4F are applied to the third embodiment. Referring to FIG. 14A, an about 100 nm thick polycrystalline silicon layer is deposited on the insulating layer 6 by a CVD process, and is patterned. As a result, a polycrystalline silicon pattern 8 is formed to cover the source region 31 and a part of the channel region 33. Note that a silicon nitride layer can be used instead of the polycrystalline silicon layer 8. Next, referring to FIG. 14B, an about 300 nm thick BPSG layer 9 is deposited by an APCVD process, and a heating operation is performed upon the BPSG layer 9 to reflow it. Further, in a similar way as that in FIG. 4G, contact holes CONT1 and CONT2 are perforated in the BPSG layer 9, the polycrystalline silicon layer 8, and the insulating layer 6 and the gate silicon oxide layer 4, so that the source region 31 and the drain region 32 are partly exposed. Next, referring to FIG. 14C, in the same way as in FIG. 4H, an about 1 μm thick Al--Si--Cu alloy layer 7 is deposited by sputtering. Then, the device is sintered at a temperature of about 400° C. for about 20 minutes in a H 2 /N 2 forming gas. As a result, an ohmic contact is realized between the regions 31 and 32 and the Al--Si--Cu alloy layer 7. Next, referring to FIG. 14D, in the same way as in FIG. 4I, the Al--Si--Cu alloy layer 7 is patterned, so that electrode layers 7a and 7b are formed on the source region 31 and the drain region 32, respectively. Finally, referring to FIG. 14E, in the same way as in FIG. 4J, a hydrogen passivation is carried out for about 30 minutes in a parallel-plate plasma reactor at a substrate temperature of about 350° C. with H 2 --Ar gas at a power density of 0.21 W/cm 2 and a frequency of 30 kHz. In FIG. 4J, since the polycrystalline silicon pattern 8 covers the source region 31 and a part of the channel region 33, dangling bonds of silicon in the source region 31 are hardly combined with hydrogen. As a result, the third embodiment is advantageous over the first embodiment in respect to the breakdown voltage. FIGS. 16A through 16D are cross-sectional views illustrating a fourth embodiment of the method for manufacturing a top-gate type TFT according to the present invention. Also, the manufacturing steps as illustrated in FIGS. 4A through 4E are applied to the fourth embodiment. Referring to FIG. 16A, an about 50 nm thick non-doped silicon oxide layer 10 is deposited on the entire surface by an LPCVD process. Then, an about 350 nm thick BPSG layer is deposited by an LPCVD process and a heating operation is performed thereupon to reflow it. Then, the BPSG layer is patterned, so that a BPSG pattern 11, which covers the drain region 32 and does not cover the source region 31, is obtained. Then, an about 500 nm thick non-doped silicon oxide layer 12 is deposited by an LPCVD process. Further, a photoresist layer 13 is coated on the silicon oxide layer 12. Next, referring to FIG. 16B, the photoresist layer 13 and the silicon oxide layer 12 are etched back. As a result, a silicon oxide layer 12' is left, and the height of the silicon oxide layer 12' is approximately the same as that of the BPSG layer 11. Next, referring to FIG. 16C, in a similar way as shown in FIG. 4G, a contact hole CONT1 is perforated in the silicon oxide layers 12' and 10 and the gate silicon oxide layer 4, so that the source region 31 is partly exposed. Simultaneously, a contact hole CONT2 is perforated in the BPSG layer 11, the silicon oxide layer 10 and the gate silicon oxide layer 4. Next, referring to FIG. 16D, in the same way as in FIG. 4H, an about 1 μm thick Al--Si--Cu alloy layer 7 is deposited by sputtering. Then, the device is sintered at a temperature of about 400° C. for about 20 minutes in a H 2 /N 2 forming gas. As a result, an ohmic contact is realized between the regions 31 and 32 and the Al--Si--Cu alloy layer 7. Next, referring to FIG. 16E, in the same way as in FIG. 4I, the Al--Si--Cu alloy layer 7 is patterned, so that electrode layers 7a and 7b are formed on the source region 31 and the frain region 32, respectively. Finally, referring to FIG. 16F, in the same way as in FIG. 4J, hydrogen passivation is carried out for about 30 minutes in a parallel-plate plasma reactor at a substrate temperature of about 350° C. with H 2 --Ar gas at a power density of 0.21 W/cm 2 and a frequency of 30 kHz. In FIG. 16F. Since the source region 31 is covered by only non-doped silicon oxide, dangling bonds of silicon in the source region 31 are hardly combined with hydrogen. As a result, the fourth embodiment is advantageous over the first embodiment in respect to the breakdown voltage. Although the above-described embodiments relate to an N-channel type top-gate type TFT, the present invention can be also applied to a P-channel type top-gate type TFT. Also, in the above-described embodiments, an insulating substrate made of non-doped monocrystalline silicon can be used instead of the fused quartz substrate 1 and the silicon oxide layer 2. As explained hereinbefore, according to the present invention, in a channel region of a top-gate type TFT, since only dangling bonds of silicon of a channel region at an interface with a gate insulating layer are combined with hydrogen, a bipolar parasitic phenomenon hardly occurs therein. As a result, the reduction of the breakdown voltage and the fluctuation of the threshold voltage can be suppressed.
In a top-gate type thin film transistor including a polycrystalline silicon pattern having a channel region, a source region and a drain region on a substrate, a gate electrode via a gate insulating layer on the polycrystalline silicon layer, an insulating layer thereon, and metal electrodes coupled to the source region and the drain region, dangling bonds of silicon of the channel region at an interface with the gate insulating layer and dangling bonds of silicon of a part of the drain region are combined with hydrogen.
7
BACKGROUND OF THE PRESENT INVENTION Field of Invention The present invention relates to a field of permanent magnetic device, and more particularly to a method for producing a neodymium-iron-boron rare earth permanent magnetic device having a high performance. Description of Related Arts Neodymium-iron-boron rare earth permanent magnetic materials are widely applied in the nuclear magnetic resonance imaging of medical industry, hard disk drivers of computers, loudspeaker boxes, mobiles, etc., because of its excellent magnetic property. To meet the requirements of energy-saving and the low carbon economy, the neodymium-iron-boron rare earth permanent magnetic materials are applied in fields of auto parts, household appliances, energy-saving and controlling motors, hybrid electric vehicles, wind power generation, etc. In 1982, Japan Sumitomo Special Metals Co. firstly published Japanese patents about the neodymium-iron-boron rare earth permanent magnetic materials, i.e., JP1,622,492 and JP2,137,496, and then Japan Sumitomo Special Metals Co. applied for United States patents and European patents. The characteristic, ingredients, and producing method of the neodymium-iron-boron rare earth permanent magnetic materials were disclosed. The main phase is Nd2Fe14B phase, and the grain boundary phases are Nd-rich phase, B-rich phase, and impurities comprising rare earth oxides. On Apr. 1, 2007, Japan Hitachi Metals Co. was merged with Japan Sumitomo Special Metals Co., and took up the rights and obligations of the patent licenses of the neodymium-iron-boron rare earth permanent magnetic materials of Japan Sumitomo Special Metals Co. On Aug. 17, 2012, Japan Hitachi Metals Co. submitted a case to United States International Trade Commission (ITC), based on the fact that Japan Hitachi Metals Co. owns the U.S. Pat. No. 6,461,565, U.S. Pat. No. 6,491,765, U.S. Pat. No. 6,537,385, and U.S. Pat. No. 6,527,874 applied in United States. SUMMARY OF THE PRESENT INVENTION With expanding of application market of neodymium-iron-boron rare earth permanent magnetic materials, a problem of shortage of rare earth resources becomes more and more serious. Especially in fields of electronic components, energy-saving and controlling motors, auto parts, new energy automobiles, wind power, etc., more heavy rare earth is required to increase coercivity. Therefore, how to reduce a usage amount of the rare earth, especially the usage amount of the heavy rare earth, is an important topic in front of us. After exploration, we develop a method for producing a neodymium-iron-boron rare earth permanent magnetic device having a high performance. The present invention is realized by a following technical solution. A neodymium-iron-boron rare earth permanent magnetic device, has alloy comprising R, Fe, B, and M, wherein R refers to one or a more rare earth elements, Fe refers to element Fe, B refers to element B, M refers to one or more elements selected from the element group consisting of Al, Co, Nb, Ga, Zr, Cu, V, Ti, Cr, Ni, and Hf. The method for producing the neodymium-iron-boron rare earth permanent magnetic device is as follows. 1. Alloy Smelting Process Smelting method of the alloys comprises an ingot casting process, which comprises heating raw materials of the neodymium-iron-boron rare earth permanent magnetic alloy to be an alloy in a molten state under a condition of vacuum or protective atmosphere; and then pouring the alloy in the molten state into a water-cooled mould under the condition of vacuum or protective atmosphere to form an alloy ingot. Preferably, the ingot casting process comprises moving or rotating a mould while pouring, in such a manner that an ingot thickness is 1˜20 mm. Preferably, an alloy smelting method comprises a strip casting process, which comprises heating and melting an alloy, and pouring the molten alloy on a rotating roller with a water cooling device via a tundish, wherein the molten alloy becomes an alloy slice after cooled by the rotating roller, a cooling speed of the rotating roller is 100-1000° C./S, and a temperature of the cooled alloy slice is 550-400° C. Preferably, the alloy smelting method comprises cooling the alloy slice again by collecting the alloy slice with a rotating cylinder after the alloy slice leaves a rotating copper roller. Preferably, the alloy smelting method comprises cooling the alloy slice again by collecting the alloy slice with a turntable after the alloy slice leaves a rotating copper roller, wherein the turntable is below the copper roller, and an inert gas cooling device with a heat exchanger and a mechanical stirring device are provided above the turntable. Preferably, the alloy smelting method comprises preserving heat of the alloy slice by a secondary cooling device after the alloy slice leaves the rotating copper roller and before the alloy slice is cooled again, wherein a period of heat preserving is 10˜120 min, and a temperature of heat preserving is 550˜400° C. 2. Coarsely Pulverization Process Coarsely pulverizing method of the alloy mainly comprises two methods, i.e., mechanical pulverization and hydrogen pulverization. The mechanical pulverization comprises pulverizing the alloy ingot smelted into particles having a grain diameter less than 5 mm with a pulverizing equipment, such as jaw crusher, hammer crusher, ball mill, rod mill, and disc mill, under a protection of nitrogen. Generally, the alloy slice is not pulverized by the jaw crusher and the hammer crusher. Coarse particles obtained by a previous process are directly milled into fine particles having a grain diameter less than 5 mm by the pulverizing equipment, such as the ball mill, the rod mill, and the disc mill under the protection of nitrogen. Another producing method of this process is hydrogen pulverization, which comprises: feeding the alloy slice or the alloy ingot obtained by the previous process into a vacuum hydrogen pulverization furnace, which is evacuated and filled with hydrogen, in such a manner that the alloy in the vacuum hydrogen pulverization furnace absorbs the hydrogen, wherein a temperature of hydrogen adsorption is usually less than 200° C., and a pressure of hydrogen adsorption is usually 50˜200 KPa; after absorbing the hydrogen, evacuating the vacuum hydrogen pulverization furnace again and heating to dehydrogenate the alloy, wherein a temperature of dehydrogenation is usually 600˜900° C.; and cooling the particles after dehydrogenation, under the condition of vacuum or protective atmosphere, wherein the protective atmosphere is embodied as an argon protective atmosphere. Preferably, the hydrogen pulverization comprises: feeding the alloy ingot or the alloy slice into the rotating cylinder, which is evacuated and then filled with hydrogen, in such a manner that the alloy absorbs the hydrogen; stopping filling the rotating cylinder with hydrogen until the alloy is saturated with hydrogen; keeping the state for more than 10 minutes; evacuating the rotating cylinder, then heating the alloy while rotating the rotating cylinder to dehydrogenate the alloy under the condition of vacuum, wherein the temperature of dehydrogenation is usually 600˜900° C.; and cooling the rotating cylinder after dehydrogenation. Preferably, the hydrogen pulverization relates to a continuous producing method of rare earth permanent magnetic alloy and its equipment. The equipment comprises a hydrogen adsorption chamber, a heating dehydrogenation chamber, a cooling chamber, chamber-isolating valves, a charging basket, a transmission device, a evacuating device; wherein the hydrogen adsorption chamber, the heating dehydrogenation chamber and the cooling chamber are respectively connected via the chamber-isolating valves, the transmission device is provided in upper portions of the hydrogen adsorption chamber, the heating dehydrogenation chamber and the cooling chamber, the charging basket is hanged on the transmission device, materials in the charging basket is transported to the hydrogen adsorption chamber, the heating dehydrogenation chamber and the cooling chamber in turn along the transmission device. When the equipment is working, the alloy is fed in a charging basket hanged on the transmission device, and the charging basket carrying the alloy is transported to the hydrogen adsorption chamber, the heating dehydrogenation chamber and the cooling chamber in turn, in such a manner that the alloy is processed with hydrogen adsorption, heating and dehydrogenation, and cooling in turn. A number of the hydrogen adsorption chamber is one or more. A number of the heating dehydrogenation chamber is one or more. Then the alloy is stored in a storage drum under the condition of vacuum or protective atmosphere. 3. Milling Process A method for producing alloy powder comprises milling by a jet mill. The jet mill comprises: a feeder; a milling chamber, wherein a nozzle is provided in a lower portion thereof, and a sorting wheel is provided in an upper portion thereof; a weighing system for controlling a powder weight and a feeding speed in the milling chamber; a cyclone collector; a powder filter; and a gas compressor. The working gas is embodied as nitrogen, and a pressure of compressed gas is 0.6˜0.8 MPa. When the jet mill is working, the powder obtained by the previous process is fed into the feeder of the jet mill firstly. The powder is added into the milling chamber under controlling of the weighing system. The powder is grinded by high-speed airflow sprayed by the nozzle. The powder grinded rises with the airflow. The powder meeting a milling requirement enters into the cyclone collector to be collected via the sorting wheel, and the coarse powder not meeting the milling requirement goes back to the lower portion of the milling chamber, under an effect of centrifugal force, to be grinded again. The powder entering into the cyclone collector is collected in a material collector in a lower portion of the cyclone collector as a finished product. Because the cyclone collector cannot collect all of the powder, a few fine powder is discharged with the airflow. This part of fine powder is filtered by the powder filter, and collected in a fine powder collector provided in a lower portion of the powder filter. Generally, a weight ratio between the fine powder and the whole powder is less than 15%, and a grain diameter of the fine powder is less than 1 μm. This part of powder has a rare earth concentration higher than an average rare earth concentration of the whole powder, so this part of powder is easy to be oxygenated, and is thrown away as waste powder. Preferably, a part of fine power in the atmosphere having an oxygen content less than 50 ppm and the powder collected by the cyclone collector are added into a two-dimensional or three-dimensional mixing machine to mix with each other, and be compacted into compacts in a magnetic field under the protective atmosphere. A mixing period is generally more than 30 minutes, and the oxygen content in the atmosphere is less than 50 ppm. Preferably, a fine powder collector is provided between the cyclone collector and the powder filter. The cyclone collector collects the fine powder discharged with the airflow, and 10% of the fine powder can generally be collected. This part of fine powder and the powder collected by the cyclone collector are added into the two-dimensional or three-dimensional mixing machine to mix with each other, and be compacted into compacts in the magnetic field under the protective atmosphere. Because of having a high concentration of rare earth, the fine powder is very suitable to be used as a rare-earth-rich phase in crystal boundaries, in such a manner that a magnetic performance is increased. To increase the magnetic performance, preferably, alloys of various compositions are respectively smelted, and the alloys are respectively milled into powders. Then the powders are mixed, and compacted into compacts in the magnetic field. 4. Compaction Process Compaction of neodymium-iron-boron rare earth permanent magnets is most different from compaction of common powder metallurgy in compaction under an oriented magnetic field, so an electromagnet is provided on a press. Because neodymium-iron-boron rare earth permanent magnetic powder tends to be oxygenated, some patents proposed that an environmental temperature while compaction is controlled between 5° C. and 35° C., a relative humidity is 40%-65%, and an oxygen content is 0.02-5%. To prevent the powder from being oxygenated, preferably, a compacting equipment comprises a protecting box, wherein gloves are provided on the protecting box, and the powder is processed with magnetic compaction under a protective atmosphere. Preferably, a cooling system is provided in a magnetic space in the protecting box, and a temperature of a magnetic compaction space can be controlled. Moulds are displaced in a microthermal space whose temperature can be controlled. The powder is compacted into compacts in a controlled temperature, and the temperature is controlled between −15° C. and 20° C. Preferably, the compacting temperature is less than 5° C. An oxygen content in the protecting box is less than 200 ppm, preferably, 150 ppm. An oriented magnetic field intensity in a chamber of the mould is generally 1.5-3T. The magnetic field is oriented in advance before magnetic powder is compacted into compacts, and the oriented magnetic field intensity remains unchanged while compaction. The oriented magnetic is embodied as a constant magnetic field, or a pulsating magnetic field, i.e., an alternating magnetic field. To decrease a compacting pressure, isostatic pressing is processed after the magnetic compaction, and then the material is fed into a sintering furnace to be sintered after the isostatic pressing. 5. Sintering Process The sintering process is after the compaction process. The sintering process is finished in a vacuum sintering furnace, and under the condition of vacuum or protective atmosphere. A protective gas is embodied as argon. A sintering temperature is 1000-1200° C. A heat preservation period is generally 0.5-20 hours. Argon or nitrogen is used to cool the material after heat preservation. Preferably, a sintering equipment comprises a valve and a transferring box with gloves provided in front of the vacuum sintering furnace. The compacts after being compacted are transported into the transferring box under the condition of protective atmosphere. The transferring box is filled with the protective gas. Under the condition of protective atmosphere, outer packings of the compacts are removed, and the compacts are fed into a sintering charging box. Then the valve between the transferring box and the sintering furnace is opened. The sintering charging box carrying the compacts is transported into the vacuum sintering furnace to be sintered by a transport mechanism in the transferring box. Preferably, a multi-chamber vacuum sintering furnace is used for sintering. Degasification, sintering, and cooling are respectively finished in different vacuum chambers. The transferring box with gloves is connected with the vacuum chambers via the valve. The sintering charging box passes through the vacuum chambers in turn. To increase the coercivity of magnets, the compacts are processed with aging process once or twice after sintering. An aging temperature of a first aging process is generally 400-700° C. A higher temperature of a second aging process is generally 800-1000° C., and a lower temperature of the second aging process is 400-700° C. The compacts are processed with machining and surface treatment after aging. Vacuum heat treatment technology of the present invention is as follows. The compacts are processed with machining into parts after sintering, according to a final size and shape of the rare earth permanent magnetic device or an approximate final size and shape of the rare earth permanent magnetic device. After machining, the parts are processed with oil removing, washing, and drying. Then the parts machined are placed into a charging box made of a material applicable for the vacuum heat treatment, such as metal, graphite and ceramic. One charging box can carry one or more parts, and metal nets or metal plates are provided between the parts, and between the parts and the charging box, to separate the parts, and the parts and the charging box. Materials comprising rare earth are provided in the charging box. Then a cover of the charging box is closed, and the charging box is fed into a vacuum heat treatment furnace to be processed with the vacuum heat treatment. Vacuum degree of the vacuum heat treatment is 5˜5×10 −4 Pa. A temperature of heat preservation is 800˜1000° C. A period of heat preservation is 2˜20 hours. The charging box is cooled with argon after heat preservation. Then the temperature is increased to 450-650° C. after cooling. After preserving heat for 0.5˜12 hours, the charging box is cooled with argon again. The vacuum heat treatment furnace carries one charging box or a plurality of charging boxes. The vacuum heat treatment furnace comprises one chamber, two chambers, three chambers, or more chambers. After the charging box is fed into the vacuum heat treatment furnace, the vacuum heat treatment furnace is evacuated. The charging box is heated, heat-preserved, and then cooled under the condition of vacuum once or more times. The parts are selectively processed with post processes, such as grinding, chamfering, sandblasting, electroplating, electrophoresis, spraying, and vacuum coating, to meet requirements of the parts, such as size, accuracy, and corrosion resistance. The present invention is applicable in producing rare earth permanent magnetic materials of high performance. The vacuum heat treatment technology is improved to significantly increase coercivity of rare earth permanent magnet, when heavy rare earth content is equal, in such a manner that usage amount of heavy rare earth is saved, and scarce resources are protected. These and other objectives, features, and advantages of the present invention will become apparent from the following detailed description, the accompanying drawings, and the appended claims. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT The embodiments are described as follows to further illustrate remarkable effects of the present invention. Embodiment 1 600 kg of alloy A, B, C, or D is taken to be smelted, and composition of the alloy is listed in Table 1. The alloy in a molten state is poured on a rotating cooling roller with a water cooling device to be cooled and form an alloy slice. Then the alloy slice is coarsely pulverized by a vacuum hydrogen pulverization furnace. The alloy is processed with a jet mill after hydrogen pulverization. An oxygen content in atmosphere of the jet mill is less than 50 ppm. Powder collected by a cyclone collector and fine powder collected by a fine powder collector are mixed by a two-dimensional mixing machine for 60 minutes under protection of nitrogen, and then fed into a pressing machine with an oriental magnetic field and the protection of nitrogen to be compacted into compacts. An oxygen content in a protecting box is 150 ppm. An intensity of the oriental field is 1.8T. A temperature in a chamber of a mould is 3° C. Each of the compacts has a size of 62×52×42 mm. A direction of an oriented magnetic field is embodied as a direction of a height, i.e. 42 mm. The compacts are packaged in the protecting box after compaction. The compacts are taken out from the protecting box, and processed with isostatic pressing, and pressure of the isostatic pressing is 200 MPa. Then the compacts are transported into a vacuum sintering furnace to be sintered, and sintering temperature is 1060° C. The compacts are processed with argon circulation cooling, until a temperature of the compacts is 80° C. Then the compacts are processed with machining, wherein the compacts are processed into four types of parts, i.e., bigger square slice (60×25×10), smaller square slice (30×20×3), sector (R30×r40, radian 60°, thickness 5), and concentric tile (R60×r55, chord length 20, height 30). After the parts are processed with oil removing, washing, and drying, the parts are placed into a charging box made of a material applicable for vacuum heat treatment, such as metal, graphite and ceramic, and a cover of the charging box is closed. Numbers of the parts carried by the charging box are shown in Table 2. Metal nets are provided between the parts, and between the parts and the charging box, to separate the parts, and the parts and the charging box. The charging box is fed into a vacuum heat treatment furnace to be processed with the vacuum heat treatment by a skip car able to move. Vacuum degree of the vacuum heat treatment is 5×10 −2 Pa. A temperature of heat preservation is 850° C. After heat-preserving for 10 hours, the charging box is cooled with argon to a temperature of 100° C. Then the temperature is increased to 480° C. After preserving heat for 4 hours, the charging box is cooled with argon to a temperature of 80° C. Finally, the charging box is taken out of the furnace. The parts are selectively processed with post processes, such as grinding, chamfering, sandblasting, electroplating, electrophoresis, spraying, and vacuum coating, to meet requirements of the parts, such as size, accuracy, and corrosion resistance. Testing results of magnetic performance are shown in Table 2. TABLE 1 Composition of alloy Num. Code Composition 1 A Nd30Dy1Fe67.9B0.9Al0.2 2 B Nd30Dy1Fe67.5Co1.2Cu0.1B0.9Al0.1 3 C (Pr0.2Nd0.8)25Dy5Fe67.4Co1.2Cu0.3B0.9Al0.2 4 D (Pr0.2Nd0.8)25Dy5Tb1Fe65Co2.4Cu0.3 B 0.9Al0.2Ga0.1Zr0.1 TABLE 2 Measuring results of magnetic performance of special heat treatment Magnetic Number of energy Size and part Surface product Remanence Coercivity Num. Code shape (piece/box) treatment (MGOe) (Gs) (Oe) 1 A Bigger 180 Electroplating 47.7 13980 17994 square slice 2 A Smaller 500 Electrophoresis 47.4 13910 17699 square slice 3 A Sector 400 Parkerising 47.9 13973 17551 4 A Concentric 300 Spray coating 47.7 13976 17787 tile 5 B Bigger 180 Electroplating 47.8 13971 17849 square slice 6 B Smaller 500 Electrophoresis 48.2 13998 17606 square slice 7 B Sector 400 Parkerising 48.0 13985 17630 8 B Concentric 300 Spray coating 48.1 14004 17987 tile 9 C Bigger 180 Electroplating 39.2 12590 28600 square slice 10 C Smaller 500 Electrophoresis 39.1 12560 29200 square slice 11 C Sector 400 Parkerising 39.0 12550 28700 12 C Concentric 300 Spray coating 39.2 12580 28600 tile 13 D Bigger 180 Electroplating 38.4 12600 28800 square slice 14 D Smaller 500 Electrophoresis 38.2 12580 29200 square slice 15 D Sector 400 Parkerising 38.4 12620 28900 16 D Concentric 300 Spray coating 38.3 12590 28800 tile Embodiment 2 600 kg of the alloy A, B, C, or D is taken to be smelted, and composition of the alloy is listed in Table 1. The alloy is processed with casting to form an ingot having a thickness of 12 mm. Hydrogen pulverization comprises feeding the ingot into a hydrogen-absorbing pot, which is evacuated and then filled with hydrogen. The ingot absorbs the hydrogen. Filling the rotating cylinder with hydrogen is stopped, after the alloy slice is saturated with hydrogen. Then the alloy, which has absorbed hydrogen, is fed into a rotating vacuum heat treatment equipment to be dehydrogenated under a condition of vacuum. The alloy is cooled by argon after dehydrogenation. Other processes are same as embodiment 1. Results are shown in Table 3. TABLE 3 Measuring results of magnetic performance of special heat treatment Magnetic Number of energy Size and part (piece/ Surface product Remanence Coercivity Num. Code shape box) treatment (MGOe) (Gs) (Oe) 1 A Bigger 180 Electroplating 47.6 13972 17490 square slice 2 A Smaller 500 Electrophoresis 47.3 13907 17195 square slice 3 A Sector 400 Parkerising 47.6 13965 17050 4 A Concentric 300 Spray coating 47.2 13967 17285 tile 5 B Bigger 180 Electroplating 47.7 13960 17344 square slice 6 B Smaller 500 Electrophoresis 48.2 13988 17105 square slice 7 B Sector 400 Parkerising 47.5 13972 17131 8 B Concentric 300 Spray coating 48.4 14001 17483 tile 9 E Bigger 180 Electroplating 39.4 12581 28502 square slice 10 E Smaller 500 Electrophoresis 39.3 12552 28701 square slice 11 E Sector 400 Parkerising 38.8 12540 28201 12 E Concentric 300 Spray coating 39.1 12570 28102 tile 13 F Bigger 180 Electroplating 38.4 12592 28301 square slice 14 F Smaller 500 Electrophoresis 38.3 12573 28703 square slice 15 F Sector 400 Parkerising 38.7 12613 28402 16 F Concentric 300 Spray coating 38.3 12585 28800 tile Comparison Example 1 600 kg of the alloy A, B, C, or D is taken to be smelted, and composition of the alloy is listed in Table 1. The alloy is processed with casting to form an ingot having a thickness of 12 mm. The alloy is processed with a jet mill after hydrogen pulverization. An oxygen content in atmosphere of the jet mill is less than 30 ppm. Powder collected by a cyclone collector and fine powder collected by a fine powder collector are mixed by a two-dimensional mixing machine for 30 minutes under protection of nitrogen, and then fed into a pressing machine with an oriental magnetic field and the protection of nitrogen to be compacted into compacts. An oxygen content in a protecting box is 150 ppm. An intensity of the oriental field is 1.8T. A temperature in a chamber of a mould is 3° C. Each of the compacts has a size of 62×52×42 mm. A direction of an oriented magnetic field is embodied as a direction of a height, i.e. 42 mm. The compacts are packaged in the protecting box after compaction. The compacts are taken out from the protecting box, and processed with isostatic pressing, and pressure of the isostatic pressing is 200 MPa. Then the compacts are transported into a vacuum sintering furnace to be sintered, and sintering temperature is 1060° C. The compacts are processed with aging treatment twice. Aging temperatures are respectively 850° C. and 580° C. Measuring results of magnetic performance are shown in Table 4. TABLE 4 Measuring results of magnet magnetic performance of ingot Weight of fine Weight of Weight of fine power added Magnetic energy Remanence Coercivity Num. Code power (Kg) powder (Kg) (Kg) product (MGOe) (Gs) (Oe) 1 A 530 40 40 47.3 13965 14563 2 B 535 35 35 46.9 14000 14400 3 C 540 30 30 37.5 12390 25320 4 D 540 30 30 37.7 12560 26500 Comparison Example 2 600 kg of the alloy A, B, C, or D is taken to be smelted, and composition of the alloy is listed in Table 1. The alloy in a molten state is poured on the rotating cooling roller with the water cooling device to be cooled and form an alloy slice. Then the alloy slice is coarsely pulverized by the vacuum hydrogen pulverization furnace. The alloy is processed with the jet mill after hydrogen pulverization. Follow-up processes are same as comparison example 1. Measuring results of magnetic performance are shown in Table 5. TABLE 5 Measuring results of magnetic performance of rapidly solidified alloy Weight of fine Weight of Weight of fine power added Magnetic energy Remanence Coercivity Num. Code power (Kg) powder (Kg) (Kg) product (MGOe) (Gs) (Oe) 1 A 535 35 40 48.0 14112 15563 2 B 545 30 35 47.7 14180 15500 3 C 545 30 30 38.0 12540 26230 4 D 545 30 30 38.6 12680 27800 The above embodiment 1, 2 are compared with the comparison example 1, 2. It is found that the coercivity of products obtained according to the present invention is significantly higher than the coercivity of products in the comparison examples. The coercivity of the alloy slice obtained according the present invention is higher than the coercivity of the ingot obtained according the present invention. The present invention is applicable in producing rare earth permanent magnetic materials having high performance. One skilled in the art will understand that the embodiment of the present invention as shown in the drawings and described above is exemplary only and not intended to be limiting. It will thus be seen that the objects of the present invention have been fully and effectively accomplished. Its embodiments have been shown and described for the purposes of illustrating the functional and structural principles of the present invention and is subject to change without departure from such principles. Therefore, this invention includes all modifications encompassed within the spirit and scope of the following claims.
A method for producing neodymium-iron-boron rare earth permanent magnetic materials mainly comprises processes of: alloy smelting, coarsely pulverization, milling, magnetic compaction, sintering, machining, vacuum heat treatment, and etc. Magnetic performance of permanent magnetic devices is increased by improving technologies of hydrogen pulverization, milling by jet mill, and vacuum heat treatment, in such a manner that usage amount of rare earth is decreased. The present invention is applicable in producing rare earth permanent magnetic materials having high performance.
7
BACKGROUND OF THE INVENTION In the production of oriented film, for example, the film is transported through an oven that will heat and/or cool the film. A typical oven consists of slot nozzles which provide convective heat transfer by air impinging on the film, and mechanical means (such as a tenter) for transporting and stretching the film. The tenter consists of clips that clamp to the edge of the film and rails that guide the clips through the oven. The distance between rails is typically adjustable to allow for the production of different width films and different stretch rates. In order to allow for the adjustment of the rails depending on the film width, the slot nozzles, which are arranged on either side of the plane of travel of the film, are positioned above and below the rails. As a result, nozzle-to-film distances are less than optimum, sometimes being as much as sixteen (16) inches apart. As the nozzle-to-film distance increases, the heat transfer coefficient and uniformity decreases, thereby resulting in an inefficient oven and poorer quality film. In response to problems similar to the foregoing, U.S. Pat. Nos. 2,270,155 and 2,495,163 disclose the use of nozzles having variable lengths according to the width of a cloth being treated. The nozzles include a fixed part corresponding to the minimum width of the cloth to be treated, and extensions slidably mounted on the fixed part, which are responsive to the movements of the chain-guide rails. As a result, the nozzles need not be located above and below the top and bottom rails, respectively, but instead can be located in the same planes as the rails. The present invention is directed to an improved telescoping slot nozzle for tenter frames as hereinafter described. SUMMARY OF THE INVENTION The problems of the prior art have been solved by the present invention, which provides telescoping slot nozzles for use with a rail assembly. Each nozzle includes a fixed portion and at least one telescoping portion slidably guided in the fixed portion. Metal-to-metal contact in the nozzle is avoided, thereby allowing the nozzles to operate at high temperatures. The configuration of the nozzle discharge opening can be easily modified to form an air knife, depending upon the particular application. Each nozzle is independent of the others, thereby facilitating retrofitting existing ovens and maintenance of individual nozzles. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a front cross-sectional view of a telescoping nozzle in accordance with a first embodiment of the present invention; FIG. 1a is an enlarged view of the portion of FIG. 1 encircled; FIG. 2 is a side view of the telescoping nozzle of FIG. 1; FIG. 3 is a side view of the telescoping nozzles of the present invention shown attached to a rail assembly; and FIG. 4 is a front cross-sectional view of a telescoping nozzle in accordance with a second embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION Turning now to FIG. 1, there is generally shown a telescoping slot nozzle 10. The nozzle 10 has a pair of slot nozzle side channels 6, 6' which are bent at their upper and lower ends in a U-shape so as to hold wear strips 62, 63, 66 and 67, preferably made of Teflon, and to form a track for purposes to be discussed below. The side channels 6, 6' are affixed to slot nozzle stiffener base 7 via a plurality of studs 2, 2' provided on the side channels 6, 6'. Return air channel 5 is substantially centrally located in the nozzle 10, and includes a plurality of guide shaft-receiving members 8 having apertures 9. Return air channel 5 is substantially U-shaped, having a pair of top flanges 21, 22 dimensioned so as to receive therebetween top support 100 (best seen in-FIG. 1a). An adjustable slot plate has a main body 3 extending over return air channel 5 and includes side bends 23, 24 which terminate in flange portions 25, 26, respectively. The slot plate 3 is adjustable during assembly to modify the dimensions of the nozzle gap, and is then sandwiched between two pieces of sheet metal 3a, 3b and secured in place (such as with bolts). As best seein in FIG. 1a, a space "A" is shown between slot plate 3 and sheet 3c allowing for linear adjustment of slot plate 3. Slot plate 3 has a plurality of spaced slotted holes for securing it in place once the linear adjustment is completed. The nozzle gap is defined by slot plate 3 and side channels 6, 6' to form fixed gap 30, 30'. One suitable dimension for each of fixed gaps 30, 30' is 0.39 inches, although it will be understood by those skilled in the art that the gap size can vary considerably depending upon the particular requirements of the application. The telescoping portion of nozzle 10 includes a U-shaped sliding exterior return air channel 12 coupled to sliding external extensions 16 and 16' via an end plate (not shown). Sliding exterior return air channel 12 slidingly fits about return air channel 5 as shown, and includes flange portions 27, 28 bent away from portions 21 and 22, respectively, of return air channel 5. The flange portions 27, 28 of sliding exterior return air channel 12 are confined within the spaces defined by the exterior of side walls 5a, 5b of the return air channel 5 and the bent portions 23, 24 of the slot plate 3. Sliding exterior return air channel 12 includes a centrally located guide shaft 17 (FIG. 2) extending longitudinally in said air channel 12 and affixed at one end of the air channel base portion 12a with a holding bracket 18 so that the guide shaft is in the same plane as the apertures 9 of guide shaft receiving members 8a, 8b affixed to the return air channel 5. The guide shaft is of a suitable diameter so as to be slidingly received by said aperture 9, and is preferably longer than the length of the air channel 12. Preferably at least two guide shaft receiving members 8a, 8b are provided for each guide shaft 17. Sliding external extensions 16, 16' are coupled to exterior return air channel 12 via a U-shaped end plate 13 (FIG. 2) so that a pair of slots 30, 30' are formed therebetween to slidingly receive side slot nozzle channels 6, 6' and through which air is expelled so as to impinge upon the web. A suitable slot width for the telescoping portion is 0.49 inches, although it again will be understood by those skilled in the art that the width can vary considerably depending upon the particular application. The slot width of the telescoping portion is slightly larger than the fixed gap width, since the telescoping portion fits within the framework of the fixed portion and therefore must accommodate its dimensions. With particular reference to FIG. 2, where like numerals correspond to elements previously described, nozzle plate cover 1 includes a plurality of studs for coupling of the nozzle to a header assembly 40 (FIG. 3). Gasket plate cover 4 holds a Teflon covered fiberglass gasket 41 in place as shown. Turning now to FIG. 3, where like numerals correspond to elements previously described, nozzle 10 is shown coupled to header assembly 40 and rail assembly 45. A right-angle bracket 42 is bolted to each side of nozzle 10 and to a telescoping nozzle support tube 44, preferably made of aluminum. All of the nozzles are coupled together by the support tube 44, although each nozzle can be removed individually. This is highly advantageous in the event any particular nozzle or nozzles has to be replaced, cleaned, modified, etc. Each support tube 44 is connected to a guide rod assembly 43 of rail 45. All connections are slotted in the tube direction to allow the rails to move angularly. It will be readily appreciated by those skilled in the art that as the rail assembly 45 as depicted in FIG. 3 moves laterally in accordance with the particular width of the web being treated, it carries with it the telescoping portions of nozzle 10. One important aspect of the present invention is the absence of any metal-to-metal contact in the nozzle 10. As a result, the nozzles are capable of efficient operation up to temperatures of about 500° F. To this end, Teflon or similar means is used between sliding metal surfaces to reduce friction and to minimize heat transfer therebetween. For example, flange portions 27, 28 of sliding exterior return air channels 12 are covered with Teflon wear strips 60, 61, as are the inner portions of each slot nozzle side channel 6, 6' that function as a track for exterior extensions 16, 16', as shown by elements 62-67 in FIG. 1. Elements 64 and 65 in particular are a Teflon-coated fiberglass cloth gasket that is sewn to a stainless steel hollow core mesh. The Teflon wear strips actually define the slot through which air is expelled from the telescoping portions of the nozzle. Also, the Teflon-coated fiberglass cloth gasket is placed between the return air channel 5 and the exterior return air channels 12. This gasket prevents air leakage and takes up any inconsistencies in manufacturing. The minimum and maximum dimensions of the telescoping slot nozzle of the present invention are variable, depending upon the particular tenter system for which they are designed. The only limitation in these dimensions is that the sum of the telescoping portion dimensions has to be less than the fixed portion dimensions. FIG. 4 illustrates a second embodiment of the present invention, where like numerals correspond to elements previously described. In this second embodiment, the configuration of one of the nozzles is in the form of an air knife. Specifically, one side of slot plate 103 includes an angled side bend 124 terminating in flange portion 126. A corresponding angled portion 106a' is formed on air bar channel side 106' to define with angled side bend 124 air knife 200. The slot plate 3 is adjustable during assembly to modify the dimensions of the air knife or of the nozzle gap formed on the other side by slot nozzle channel side 6 and side bend 23, or both. It will be readily appreciated by those skilled in the art that one or both discharge openings can be designed as air knives.
Telescoping slot nozzles for use with a rail assembly are disclosed. Each nozzle includes a fixed portion and at least one telescoping portion slidably guided in the fixed portion. Metal-to-metal contact in the nozzle is avoided, thereby allowing the nozzles to operate at high temperatures. The configuration of the nozzle discharge opening can be easily modified to form an air knife, depending upon the particular application. Each nozzle is independent of the others, thereby facilitating retrofitting existing ovens and maintenance of individual nozzles.
3
[0001] This is a non-provisional application claiming priority under 35 USC 119(e) of provisional application Ser. No. 61/795,099, filed Oct. 10, 2012. BACKGROUND OF THE INVENTION [0002] 1. Field of the Invention [0003] The invention relates an exterior mounted vehicle roof rack cargo box device. [0004] 2. Brief Description of Related Art [0005] Vehicle cargo box systems allow for storage and transport of items outside of the vehicle interior. These cargo boxes are typically mounted in a fixed position to the vehicle's roof by an apparatus designed to secure the cargo box from the rigors of driving. More specifically, hard-shelled cargo boxes protect their contents from the elements and from theft by employing a durable shell, equipped with seals between the cargo box's two halves, as well as by a locking system that prevents undesired entry. SUMMARY OF THE INVENTION [0006] The cargo box of the present invention has a housing shell body and a rail system. The housing shell body is divided into two halves, an top shell half and bottom shell half. The top shell half is ventilated to allow drying of internally stowed items. Systems of control surfaces that may be automated are attached to each vented opening, the purpose of which is, block external moisture such as rain from entering the interior of the cargo box's housing. A railing system is provided for attaching the housing shell body to the vehicle. The railing system allows the housing shell body to roll into various positions relative to the top of the vehicle and also allows the housing shell body to move downward off the rear (or front) of the vehicle it is attached to, via a set of spring loaded hinges. Internally, the housing shell body has compartments and fasteners used to secure any stowed items, as well as a set of UVC lights that disinfect the stowed items. BRIEF DESCRIPTION OF THE FIGURES [0007] FIG. 1 is a perspective view of the Cargo Box of the invention; [0008] FIG. 2 a is a perspective view of the top shell half showing the inside thereof; [0009] FIG. 2 b is a bottom perspective view of the bottom shell half; [0010] FIG. 3 a is a perspective view of the Cargo Box in a first position where the housing shell body is directly above the rail arm tracks; [0011] FIG. 3 b is a perspective view of the Cargo Box in a second position where the housing shell body is extended backwards beyond the rail arm tracks; [0012] FIG. 3 c is a perspective view of the Cargo Box in a third position where the housing shell body is tipped downward relative to the plain of the rail arm tracks; [0013] FIG. 4 is a perspective view of the primary rail arm; [0014] FIG. 5 a is a perspective view of the rail arm track; [0015] FIG. 5 b is a cross section view of the rail arm track; [0016] FIG. 6 is a perspective view of the vent closure doors according to one embodiment of the invention; [0017] FIG. 7 a is a perspective view of the vent closure door where the control surfaces are in an opened position; and [0018] FIG. 7 b is a perspective view of the vent closure door where the control surfaces are in a closed position. DETAILED DESCRIPTION [0019] The invention is a ventilated vehicle roof rack cargo box A. Referring to FIGS. 1 and 2 a - 2 b, the housing shell body 1 of the cargo box is a ridged, durable housing shell that holds a desired load or cargo. The main housing shell 1 is made up of two independent shell halves, i.e. a top shell half 2 and a bottom shell half 11 . [0020] The two shell halves are attached to one another by a set of hinges 23 located along juxtaposing edges of the bottom edge rim 8 of the upper shell half 2 and the upper edge rim 18 of the bottom shell half 11 when they are aligned. Positioned on the opposite side of the shell body from the hinges 23 is a latch 25 for opening and closing the housing shell body. [0021] The top shell half 2 is configured with air vents 28 at both a front end 6 and an opposing back end 7 to allow air to flow through the interior of the cargo box. The ventilation is desired to assist in the drying of any cargo or gear that gets wet during its use. The airflow through the cargo box is to be generated by the movement of the vehicle as it travels down the road, or through natural effects such as wind or convection currents. [0022] Internally, the cargo box housing shell may have built therein, or attached to each respective shell half, one or more different compartments 10 , 20 and fasteners 9 and 21 . These compartments and fasteners are for use in securing the items being stowed, as well as aligning each item for maximum exposure to the airflow throughout the interior of the cargo box. [0023] The cargo box A may be equipped with an automated vent closure door system 30 (see FIGS. 7 a and 7 b ) at front and back ends 6 and 7 , respectfully, of the housing shell for closing the air vents. This is done by moving control surfaces 32 into place to cover the air vents 28 . The automated vent closure system senses precipitation such as rain or the like and moves the control surfaces into place, functioning as a seal or precipitation guard to ensure that no external moisture is allowed to reach the cargo through the air vents. [0024] Attached to the interior walls of the cargo box there is optionally a set of germicidal wavelength, UVC lights 100 . The UVC lights sterilize bacteria and neutralize mold growth on the surface of the items stowed, thus reducing odor and helping to minimize the potential of skin infections that could result from human contact with bacterial growth on the cargo. [0025] Referring to FIGS. 3 a - 3 c, the housing shell body 1 is attached to a system of rails 37 that allow the housing shell body 1 to be slid into various positions on top of ( FIG. 3 a ) position 1 , and behind ( FIGS. 3 b and 3 c ), positions 2 and 3 , the vehicle that the cargo box is attached to. This railing system enables the housing shell body 1 to slide/roll back to the rear of the vehicle. Once in this position, utilizing a set of spring loaded hinges 60 , the housing shell body is allowed to then slowly fold down to position 3 shown in FIG. 3 c for ease of access to its contents at the rear end of the vehicle. [0026] This racking system is engaged by releasing a locking mechanism 62 or a release handle, preferably at the back end of the cargo box (see FIG. 1 ). Once the locking mechanism is released, a set of latches is disengaged along the rails and the cargo box is then free to roll back and drop into its lowered position FIG. 3 c . Once the desired cargo has been removed or re-stored in the cargo box, and access to the interior is no longer needed, the housing shell body 1 can easily (with the assistance of the spring loaded hinges) be raised back up to position 2 shown in FIG. 3 b, and slid into locking position 1 as shown in FIG. 3 a atop the vehicle. Housing Shell Body: [0027] Top and Bottom Shell Halves: [0028] The top and bottom shell halves, 2 and 11 respectively, are preferably constructed of ABS plastic. However, they can be made of any durable, formable material that can be molded or shaped into the desired shape. Construction materials may be, but are not limited to hard plastics, fiberglass, aluminum or sheet metal(s). [0029] The top shell half 2 has top 3 , left 4 and right 5 sides, as well as a front end 6 , and rear end 7 . The top shell half is open on a bottom portion thereof and the opening is defined by a bottom edge rim 8 . The individual surfaces may be concave or convex in their construction planes, or contain any arrangement of curves, creases or any other designable shapes that can be built into the construction materials. [0030] The top, left and right sides as well as the front and back ends of the upper shell half can be integral or connected by filleted, chamfered or butted edges and may be oriented at angles ranging from 45 to 135 degrees to one another. The overall dimensions of the upper shell can range from two to ten feet in length, one to five feet in width, and six inches to three feet in depth. The shells thickness will range from 1/32 of an inch up to ¾ of an inch depending on the rigidity of the construction material. [0031] As shown in FIG. 2 a, both the front end 6 and rear end 7 of the upper shell half have air vents 28 that are cut out of or molded into the upper shell half 2 (to be referred to as a port(s)). Each port 28 should be contained within the edges of the specific end's surface geometry but will not be limited to this. The ports will follow the contours of their respective end's surface geometry but may also be of any geometric shape. [0032] Located along one of the two side surfaces of the top shell half is a small hole cut into the surface. This small hole is designed to match for alignment and installation purposes, with a locking/latching mechanism 25 such as a cam lock that will lock the top shell half to the bottom shell half. [0033] The top shell half 2 is attached to the bottom shell helf via a set of hinges 23 . [0034] The bottom shell half 11 has a bottom side 12 , left 14 and right 15 sides, as well as a front 16 , and rear end 17 . These surfaces together will form five sides of an open box with on upward facing opening defined by an upper edge rim 18 for receiving gear. The individual surfaces may be concave or convex in their construction planes, or contain any arrangement of curves, creases or any other designable shapes that can be built into the construction materials. [0035] The five surfaces of the bottom shell half can be connected by filleted, chamfered or butted edges and may be oriented at angles ranging from 45 to 135 degrees to one another. The overall dimensions of the bottom shell can range from two to ten feet in length, one to five feet in width, and one inch to three feet in depth. [0036] Formed into the outside of the bottom surface of the bottom shell half are two grooves 19 or channels that run parallel to one another along the length of the bottom shell half 11 (see FIG. 2 b ). These two grooves serve as guide channels for the attachment of the railing system, to the underside of the bottom shell half 11 . The two channels are approximately one to six inches in width, with a depth ranging from 1/16 th of an inch up to three inches and preferably run the entire dimensional length of the bottom shell half. [0037] Located along the corresponding side surfaces to the top shell half is a small hole cut into the surface. This small hole is designed to match with and be complimentary to the interior half of the locking/latching mechanism such as the cam lock that will lock the top shell half to the bottom shell half, mentioned herein. [0038] The upper edge rim 18 of the bottom shell half 11 is designed such that, when the top shell half is aligned with the bottom shell half, the bottom shell's rim fits uniformly within the boundaries of the top shell's rim. This creates an overlap that prevents water from seeping into the bottom shell half. There may be a gap of 1/16 th of an inch up to one inch between the respective edges of each shell's rims when the two are aligned properly. [0039] Vent Closure Components: [0040] The invention includes one or more components to close the vents of the top shell half. They include vent closure doors to keep moisture out, anti-theft covers and debris screens. The following is a description of each component. [0041] Vent Closure Doors: [0042] The purpose of the vent closure doors 30 within the design assembly is to seal or block each vent 28 in the event that outside precipitation is encountered during use. [0043] The vent closure doors can be a number of different designs so long as they close the vents. [0044] The preferred vent closure door is a control surface 32 as shown in FIG. 6 . The control surface has a first metal sheet that defines a plurality of openings and a second metal sheet that defines a plurality of openings. The sheets are layered on top of each other. In a first position, as shown in FIG. 7 b, the layered sheets create a solid water impenetrable surface. In a second position, one of the sheets is moved relative to the other sheet so that the openings are lined up to permit air to flow through both sheets ( FIG. 7 a ). Similarly a method used for sealing each vent 28 is to move one or more control surfaces of the vent closure doors to a position such that they close both the front and rear vents 28 . Each individual perforated sheet is made of any ridged yet still ductile material such as hard plastics, resins or sheet metals. [0045] Each vent closure door as a whole has one or more sets of control surfaces attached to the top shell half in the vicinity of the ports 28 . The specific geometry of the vent closure door is such that when each control surface is moved into a position covering the vent, they will overlap one another creating one flat, solid surface. This flat surface will effectively shield the entire opening of each respective vent in the top shell. [0046] The control surfaces can be multiple surfaces aligned with one another so that when moved into place they overlap in front of each vent. Each set of vent closure doors spans the height and width of the port in the closed positions. [0047] The control surfaces of the vent closure doors themselves are designed as a flat surface that will move into place by either, swinging, folding or sliding, and have dimensions of one to five feet in length, one to thirty six inches in width and 1/32 to 1 inch thick. [0048] The movement of the vent closure doors at each end of the shell in ether the one or multiple control surface scenarios may be done manually or may be controlled by electronic components 33 such as sensors, motors, servos or actuators etc. ( FIG. 6 ) [0049] If the vent closure doors are to be controlled by electronics, the electronic components 33 can be a computer chip or timing circuit that receives a signal from a moisture sensor attached to the exterior of the top shell half or bottom shell half or some portion of the cargo box. The chip will then send a control signal to the motor or servo telling it which position to orient the control surfaces. This system is powered by either the vehicle battery or by an independent power source that is mounted to the housing shell body 1 . [0050] Other possible embodiments for closing the ports include one or more vent closure doors that are aligned on a set of tracks. The tracks permit the vent closure doors(s) to slide into place over the openings of each port much like the operation of a garage door. [0051] Anti-Theft Cover: [0052] In one embodiment there is included in the invention an anti-theft type cover. The purpose of the anti-theft cover within the design assembly is to prevent the removal of any stowed item through the front and rear ports. [0053] The anti-theft type cover is a prefabricated grid or grate such as a diamond pattern grating or any other such patterned grating that can be made of either hard plastics or metals. [0054] The anti-theft type covers 34 or debris screen 35 are designed to cover the entire opening of each vent and contour to the port's geometry. The edges of each anti-theft type covers extends ⅛ of an inch up to two inches past the edges of the ported openings. This extension is desired so that each anti-theft type cover can be securely mounted to the top shell. [0055] The anti-theft type covers are secured to the inside or outside of the top shell's vents in a manner that only allows it to be removed with access to the interior of the housing shell body. This may be done by using a 1/16 of an inch to ½ inch screw, rivet, bracket, or bolt and nut combo in the case of a semi-permanent mounting method, and welding or gluing as a permanent method. [0056] Other embodiments for anti-theft covers include a configuration of bars or rods that are attached in a similar fashion. Debris Screen: [0057] The purpose of the debris screen 35 within the design assembly is to completely cover each vent with a screen designed to keep smaller debris or bugs from entering the interior of the cargo box when the upper and lower shell halves are closed. [0058] The screen may be modeled after any typical household window screening, and may be made of any plastic or rust resistant metal. [0059] Each debris screen will span the entire opening of each port in the upper shell half, and will extend 1/16 of an inch to two inches beyond the perimeter of the ports opening for attachment purposes. [0060] The debris screen is affixed to each vent. This may be accomplished, for example, by having its excess or extended material securely wedged between the anti-theft port cover and the cargo box itself. This may be done by using a 1/16 of an inch to ½ inch screw, rivet, bracket, or bolt and nut combo. [0061] Gear Storage [0062] Garment Storage Apparatus: [0063] The purpose of the garment storage apparatus 10 within the cargo box is to hold sports gear, jerseys, shorts or any other garments within a breathable compartment in the top shell half 2 . This allows air to flow around the gear or garments and promotes drying. [0064] The garment storage apparatus can be made of, but is not limited to, any breathable mesh or netting that may or may not have elastic properties. It may also be a rigid or semi rigid container with the proviso that the container has multiple openings for permitting air to flow there through. [0065] A method of storing a garment has the steps of securing a garment inside of the garment storage apparatus or strapping a garment inside of the top shell half 2 with securing straps 9 . The securing straps are affixed to an interior surface of the top side of the top shell half. The garment storage apparatus may be sufficiently large so as to span the length and width of the interior of the top surface of the top shell half. [0066] The garment storage apparatus is secured to the top shell half in one or more locations along its sides and ends. This may be done by using a 1/16 of an inch to ½ inch screws, rivets, or bolt and nut combos, straps or any number of methods of fastening that allow for semi-permanent attachment. It will be situated between the left and right sides of the top shell and in between the front end and the rear end. [0067] Gear Storage Compartments: [0068] The purpose of the internal gear storage compartments 20 within the design assembly is to hold items in place while allowing adequate airflow in and around the objects being stowed with in the compartment. The airflow around the items helps to dry items that may have become wet prior to being stowed. [0069] The compartments are constructed of a flexible, breathable material such as nylon mesh. They can be in the form of mesh bags. Alternatively, the compartments can be constructed of any material that permits airflow directly to their contents. They may be a rigid box with air channels or openings. In the case of mesh bag compartments, the openings of the compartments are lined with elastic cord or straps that allow the opening to be drawn shut to keep the items securely inside. [0070] Several internal storage compartments 20 are located in the interior of the bottom shell half. Each compartment 20 is designed to secure stowed items so that they do not shift while the vehicle is in motion. [0071] The compartments may vary in size from 1 to 36 inches in width, 1 to 36 inches in length and 1 to 36 inches in depth. [0072] The placement of the compartments may be anywhere along the base of the bottom shell along the interior of the bottom surface. Each individual compartment is secured to the bottom shell half in one or more locations along its sides and ends. This may be done by using a 1/16 of an inch to ½ inch screw, rivet, bracket, or bolt and nut combo. Gear Securing Straps: [0073] The purpose of the gear securing straps 21 within the design assembly is to secure larger items in place while allowing adequate airflow in and around the objects being stowed. [0074] The straps 21 are constructed of a flexible elastic material such as elastic cord, but may also be a non-elastic cording such as nylon straps or a combination of both. Located in the interior of the bottom shell are several securing straps 21 . At each end of the straps is an apparatus meant to secure the strap to the inside of the bottom shell half by means of a hook and loop, button, snap, clip or any other method of semi-permanent attachment. These attachments will, in each case, have a corresponding or mating component that will be secured to any of the lower shell's interior surfaces. Each securing strap may vary from 10 inches, to upwards of 82 inches in length, and will be equipped with a clasp 22 or bracket allowing the strap to be lengthened or shortened to a desired length. [0075] Germicidal UVC Bulb: [0076] The purpose of the Germicidal UVC light system is to emit light within the ultra violet C or germicidal range, in order to kill off surface bacterial and mold. [0077] As shown in FIG. 1 , located along the inside surface of the top shell half 2 , preferably, both the right and left sides of the top shell half, is a UVC light source 100 . The light source is a UVC bulb or multiple bulbs angled so that they emit light into the interior of the upper and lower shells when the shells are closed together. [0078] The UVC bulbs emit a spectrum of light within the ultra violet germicidal range between a wavelength of 254 (nm) and 280 (nm). Each bulb is mounted to the inside surface of the top shell half by a bracket, secured to the surface itself by ether bolts, screws, rivets, glue or epoxy. [0079] The bulbs are situated along the sides of the top shell half at a distance of one to thirty six inches from the bottom edge of the side surface, and at any point along the length of the side. [0080] The bulbs 100 are controlled by either a computer chip or a timing circuit. The control unit or chip 203 receives a signal from an external sensor 101 such as a contact sensor or proximity sensor. [0081] This system also operates as a dead man switch, that is to say when the top shell half is opened, the sensor sends a signal to a control circuit that tells the system to turn off the bulbs. This feature is a safety feature designed to prevent direct human contact with the UVC light being emitted within the housing shell body. [0082] Shell to Shell Hinges: [0083] The purpose of the shell to shell hinges 23 within the design assembly is to attach both the top and bottom shell halves to one another. The hinge or set of hinges permits the top shell half to fold open or closed in relation to the bottom shell half. [0084] The hinges themselves may be made of any durable rust resistant material such as stainless steel or any hard plastic. [0085] The hinges are located along the edge of each shell's respective rim and serve to align the shells when closed. The hinges may number from one to upwards of six within the design of the invention. If one single hinge is used, the hinge should span the length of the hinge mounting side of the shell's rim so as to secure the shell from any undesired torque that the open half of the shell may encounter when opened and closed. In the case of using two hinges, the hinges will be positioned at opposing ends of the hinge mounting side of the shell's rim. In the case of implementing three or more hinges they should be aligned equidistant from one another along the length of the mounting side of the shells rim. [0086] The hinges may be locking or spring loaded so that when the housing shell body is opened, the hinges arrest the movement of the open upper shell half in order to keep the housing shell body from swinging back shut on itself. The hinges are preferably 1 to 84 inches in length and are secured to the shell body by means of screws, bolts or epoxies and glues. Railing/Racking System: [0087] The cargo box has a railing/racking system 37 for attaching the housing shell body 1 to a vehicle, not shown. The railing/racking system has essentially three basic parts, a primary rail arm, a secondary rail arm and a rail arm track. These parts will be described in more detail as follows: Rail Arm: [0088] The purpose of each primary rail arm section 38 within the design is to attach the housing shell body 1 to the rail arm track 41 . The primary rail arms hold roller brackets 49 therein (See FIG. 4 ). The roller brackets hold the primary rail arm to the rail arm track and guide. This configuration permits the housing shell body that is attached to the primary rail arm to move linearly along the railing system's rail arm track 41 . The roller brackets are mounted inside of the U shaped cross section of the rail. [0089] The second main function of the primary rail arm is to allow the housing shell body to fold down off the back end of the vehicle it's attached to ( FIG. 3 c ). This is done through the use of hinges 60 that attach the primary rail arm to a secondary rail arm 39 . [0090] The primary rail arm is a sliding and extending member of the rail system and is located outside of the main housing shell body 1 , and as such, is exposed to the elements and moisture. The primary rail arm is preferably made of a durable rust resistant metal such as aluminum or stainless steel, or any metal that has been coated with moisture and rust resistant coating. [0091] As shown in FIG. 4 , the primary rail arm has top, left and right sides. These three sides have a generally square u-shaped cross section with the arrangement in an open downward direction. The individual sides may be concave or convex in their construction planes, or contain any arrangement of curves, creases or any other designable shapes that can be formed into the construction materials. [0092] The three main sides of the primary rail arm can be connected by filleted, chamfered or butted edges and may be oriented at angles ranging from 45 to 135 degrees to one another. The three sides of the railing system are from 1 to 6 inches in width, 12 to 100 inches in length and 1/32 th of an inch to ¾ of an inch in thickness. All the dimensions of thickness are uniform throughout the cross section. [0093] There may be one or more primary rail arms. However, there are preferably two primary rail arms in the assembly mounted in an orientation that is parallel to each other. Each is attached to the outside of the bottom side 12 of the bottom shell half 11 . Each of the primary rail arms 38 are complimentary with and designed to fit within the grooves 19 on the outside of the bottom side 12 of the bottom shell half 11 . [0094] The primary rail arm is secured to the bottom shell half in one or more locations along the rail arm's top and side surfaces. This may be done by using a 1/16 of an inch to ½ inch screws, rivets, or bolt and nut combos. [0095] There are preferably two primary rail arm sections within the final railing system. Each individual primary rail arm is attached to a secondary rail arm 39 via heavy duty spring loaded rail hinges 60 . Secondary Rail Arm: [0096] The purpose of each of the secondary rail arms 39 within the design are to attach to the primary rail arms 38 by a set of rail arm hinges 60 as well as to the rail arm track 41 through a set of roller brackets 49 , similar to the roller bracket design of the primary rail arm shown in FIG. 4 . The secondary rail arms 39 remain connected to the rail arm track 41 and allow the housing shell body 1 attached to the primary rail arm 38 to fold down into its partial or substantially vertical position via the set of rail arm hinges 60 . [0097] The secondary rail arm is a sliding/rolling member of the rail system and is located outside of the housing shell body, and as such, it is exposed to the elements and moisture. The secondary rail arm is made of a durable rust resistant metal such as aluminum or stainless steel, or any metal that has been coated with moisture and rust resistant coating. [0098] The secondary rail arm has three sides: a top side, and left and right sides. These three sides have a square u shape cross section with the arrangement in an open downward direction similar to the primary rail arms. These individual sides may be concave or convex in their construction planes, or contain any arrangement of curves, creases or any other designable shapes that can be built into the construction materials. [0099] The three sides of the secondary rail arm can be connected by filleted, chamfered or butted edges and their construction planes may be oriented at angles ranging from 45 to 135 degrees to one another. The three sides of the railing system are 1 to 6 inches in width, 4 to 36 inches in length, and 1/32 th of an inch to ¾ of an inch in thickness. The secondary rail arm has the same or substantially the same cross sectional dimensions as the primary rail arm. [0100] There are preferably two secondary rail arms in the final assembly. The secondary rail arms are not directly attached to the lower shell half. The secondary rail arms are connected to the rail arm track 41 of the railing system via a set of roller brackets mounted inside of the U shaped cross section of the secondary rail arm's three sides. Guide Rail Track: [0101] The rail arm track 41 serves as a fixed linear track along which the housing shell body 1 and primary and secondary rail arms can travel. The rail arm track is fixed to the vehicle's existing roof or roof rack via a set of mounting brackets 63 . The cargo box is fixed to the rail arm track through the combination of the primary and secondary rail arms discussed above and their attached roller brackets 49 and rollers 50 . [0102] The rail arm track 41 is a fixed external member of the rail system, and, as such, it is exposed to the elements and moisture. The rail arm track is preferably made of a durable rust resistant metal such as aluminum or stainless steel, or any metal that has been coated with moisture and rust resistant coating. [0103] In a preferred embodiment, as shown in FIGS. 5 a and 5 b, the rail arm track's cross sectional design has a combination of two basic shapes. At its base, the cross section has an elongated rectangular shape 42 . The rectangle portion 42 is oriented so that its two longer sides run horizontally. Rising from the center of the top side 43 of the rectangle is a “T” shaped formation 45 that functions to hold the rail arm track to the roller brackets 49 of the primary and secondary rail arms. The exact cross-sectional design of the guide rail track may vary so long as it is complimentarily received by the first and secondary rail arms in such a manner as to securely allow the rail arms to slide along its entire length. For example, it may have a cross-sectional “I” shape. [0104] The cross sectional dimensions of the rail arm track are as follows. The rectangular section 42 has a width of 1 to 6 inches, a height of ¼ to 4 inches and is 24 to 120 inches in length, and the sides are 1/16 th of an inch to ¾ of an inch in thickness. The “T” section 45 extends up from the surface of the rectangle ¼ of an inch up to 3 inches and the “T” head ranges from ¼ of an inch to 3 inches wide. The entire length of the “T” section matches the length of the rectangular section it is integral with or attached to. Both the rectangle and “T” cross sections are preferably manufactured as one unit. The T formation runs the length of the rail arm track dividing the rectangle into two symmetrical halves. Running down each half of this division are two separate parallel linear patterns of holes 47 drilled into the lower surface 44 of the rectangular section. [0105] In an embodiment where the rectangular section is hollow and has an upper and lower portion, the linear holes are defined in both the upper and lower portions. [0106] The lower set of linear patterned holes has a diameter of 1/16 to ¾ of an inch and are drilled out of the lower surface of the rectangle so that the rectangular section defines the holes. The first hole in the linear pattern should preferably be located on center 1.5 to 5 inches from the end and ⅜ of an inch to 1¼ of an inch from the right side. All the remaining holes in the pattern are preferably spaced 4 inches on center from one another down the length of the rail arm track. The lower pattern of holes on the lower surface of the rectangle mirror the first pattern's dimensions using the center of the base of the “T” section for a mirror line. [0107] The upper set of linear patterned holes 47 all have a diameter of ¼ of an inch to 1 inch and are drilled out of the upper surface of the rectangle. The first hole in the linear pattern is located on center 1.5 to 5 inches from the end and ⅜ of an inch to 1¼ of an inch from the right side. All the remaining holes in the pattern are spaced 4 inches on center from one another down the length of the guide rail. The lower pattern of holes on the opposite half of the rectangle mirror the first patterns dimensions using the center of the base of the “T” section for a mirror line. [0108] All of the holes in the linear pattern on both the upper and lower sides line up concentrically with one another so that the mounting bolt may pass through both an upper and lower hole. The two sets of holes will serve as mounting holes for bolts used to attach to the vehicle mounting brackets. [0109] In another embodiment, the rectangular section is solid and the holes 47 run all the way through it. [0110] As shown in FIG. 5 a, cut into the rear end of the length of the T section is a notch 46 . This notch extends down into the T shaped track starting from the outside of the T head and extends ⅛ to 1 inch inward. The notch serves as a hooking component for the railing systems latching mechanism. Other types of physical stopping features that have the function of preventing the secondary rail arm from rolling off the rail arm track are also envisioned. Spring Loaded Hinges: [0111] The purpose of the spring loaded rail hinges 60 within the design are to allow the primary rail arm to hinge away from secondary rail arm in a swinging motion as shown in FIG. 3 c. The hinge allows the primary rail arm to fold downward from a collinear relation to secondary rail arm into a position relatively perpendicular to it. During the movement of each rail arm the spring of the hinge provides resistance against the movement of the primary rail arm in the downward direction and assistance to the motion when folding back upward into its original position. [0112] The spring loaded rail hinge is preferably constructed out of an extremely strong material that is able to support the weight of the housing shell body and any stowed cargo. The suggested construction material may be any rust resistant metal or metal coated with rust resistant coatings as well as any extremely strong plastics or resins. The spring loaded rail hinges are mounted externally or within the “U” shaped cross section of the upper primary and secondary rail arms. They may be secured to any face of the rail arm sections as long as the hinge is aligned to allow the rail arms to fold apart while keeping the plane of the side surfaces of each rail arm parallel to one another. Each hinge is mounted to the respective rail arms by ether epoxies, screws or a bolt and nut combination. Rail Arm End Caps: [0113] Each of the rail arms has end caps 40 shown in FIG. 4 . The purpose of the rail arm end caps within the design assembly is to completely cover the ends of each rail arm component. Covering each end of the rail arms in the railing system prevents debris from becoming lodged in the internal components of the railing system 37 . [0114] The rail arm end caps 40 are an external component of the railing system and as such they will be exposed to the elements. The rail arm end caps may be made of any durable plastics or resins suitable for long-term outdoor exposure. Each end cap is complimentary in shape and design to the geometry of the cross section of the railing system when fully assembled to fully close the ends of the rail arms. [0115] The end caps may be attached to the rail arms by ether glue, epoxy, friction fit or any other method of attachment. Bumper: [0116] The purpose of the bumper 65 within the design assembly is to prevent the primary rail arms from coming into contact with the rear end of the vehicle. As shown in FIG. 1 , the bumper 65 extends out past the plane between the two parallel rail arm sections 38 and 39 . [0117] The bumper is made of rubber, soft plastic or a rubber like material that is softer than any surface of the exterior of the vehicle. This material property is desired so that when the bumper makes contact with the vehicle, it does not leave scratches or marks on the surface where contact is made. [0118] There may be one or more bumpers within the design assembly. The bumper(s) may be of any geometric shape but, will have a surface that will be designed to make contact with the vehicle in one or more places. The bumper(s) may range in size from 1/16 of an inch to 48 inches long, 1/16 of an inch to 48 inches wide and 1/16 of an inch to 12 inches thick. [0119] The bumper itself may be attached to any of the underside surfaces of the main shell body or the side or end surfaces of one or both the primary rail arms. Roller Brackets: [0120] The purpose of the roller brackets 49 within the design assembly is to securely hold the rollers 50 that will make contact with the rail arm track 41 . Through the bracket and rollers the primary and secondary rail arms mount to the rail arm track allowing the cargo box to roll linearly along the rail arm track. [0121] The roller bracket is made of a durable rust resistant material such as any kind of ridged plastics, resins, or lightweight metal. The bracket is designed to fit inside both primary and secondary rail arms. The roller bracket defines a channel 51 in the rail arms for receiving the protruding T-section of the rail arm track. The general shape of the channel is complimentary to the shape of the T-section of the rail arm track. [0122] The number of roller brackets and rollers within the design assembly can number from 4 to 60. Each bracket is mounted inside of each of the primary and secondary rail arms. Roller Wheel: [0123] The roller wheel is shown in FIG. 4 . The purpose of each roller wheel 50 within the design assembly is to enable the roller bracket to roll along the rail arm tracks. [0124] Each roller wheel 50 is positioned on the roller bracket so that the wheels are pressed firmly against the rail arm track. Because of the contact that the wheel makes with the track, the wheel is constructed of a durable rubber or plastic material that enables the roller wheel to be deformed regularly without permanent plastic deformation of the wheel's original shape. Suggested materials for construction may be but are not limited to polyurethane or phenolic resin. [0125] The roller wheel is substantially disc shaped with a diameter of ¼ to 4 inches and a thickness of ¼ to 2 inches. Each roller wheel, when mounted within its corresponding bracket, is positioned so that it makes contact tangentially with the rail arm track. The roller wheels are oriented so that their axes of rotation are perpendicular to the extending length of the rail arm track. The roller wheels are mounted to the bracket so that they can turn freely. Release Handle: [0126] The purpose of the release handle 62 within the design assembly is to provide a handhold at the rear end of the cargo box's housing shell body 1 . This release handle houses an apparatus that, for example, engages and disengages a set of latches, locking the cargo box's railing system 37 into place. The purpose of the release handle is to release the housing shell body 1 so that it can roll along the rail arm track into one of its various positions shown in FIGS. 3 a - 3 c. [0127] The handle is an exterior component of the inventions design and, as such, is constructed of any durable, rust resistant material such as hard plastics and metals. In one embodiment, the handle has a main body that extends out from its center in one direction. This main body serves as a loop of material contoured to fit the grip of a person's hand. Located on the loop is a release button that can be depressed by the user when the handle is gripped. This release button releases a set of latches attached to the inside surface of the primary and secondary rail arms via a cable or mechanical mechanism. When the latching mechanisms are released the housing shell body is able to roll backwards and extend out off of the rear of the vehicle or over the vehicle trunk. Stopper: [0128] The purpose of the stopper 64 within the design assembly is to keep the railing system components from sliding apart from one another, unless desired by the operator ( FIG. 7 a ). [0129] The stopper is constructed of any rust resistant rigid material such as hard plastics or metals. [0130] The stopper attached to the rail's arms is modeled after a simple hook that is designed to sink into the notch 46 ( FIG. 4 ) on the rail arm track “T” shaped track 45 . In the instance where the stopper is a hook, it can be spring loaded so that it moves back into its locking position automatically. [0131] The hook stopper 64 is mounted through an axis to one of the inside surfaces of the primary and secondary rail arms so that it may swing up or down into its locked and unlocked positions. Railing to Vehicle Mounting Brackets: [0132] The purpose of the railing to vehicle mounting bracket 63 within the design assembly is to removably attach the rail arm track 41 to the existing roof rack or roof of the vehicle. [0133] Many different types of mounting brackets are contemplated with the proviso that they securely attach the rail arm track to the upper portion of a vehicle or to the vehicle's top rack. [0134] In one embodiment, each vehicle mounting bracket 63 is made up of the three main components: a worm, worm wheel arm, and worm drive yoke. The three components will be discussed individually and their assembled functionality will be discussed in the following paragraphs. Worm: [0135] The purpose of the worm within the mounting bracket assembly is to drive the worm wheel arm, raising and lowering it into a desired position. [0136] The worm will be constructed of any type of metal such as steel or any other material that is extremely strong and rigid. [0000] The worm will have two ends, each configured as a cylinder. The first cylinder will be the drive end. The drive end will have the length of its cylinder extending ⅛ to 1½ of an inch, with a diameter of ¼ to 1 inch. Set into this cylinder will be a series of channel cuts. Each cut will run parallel with the worm's cylindrical axes. Each channel cut will be centered along that same axis and be 1/64 to ¼ of an inch wide and 1/64 to ¼ of an inch deep. [0137] The second side of the worm will be the gear end. The gear end of the worm will have a screw pattern set into the exterior surface of the cylinder as would be found on any typical worm. The threading of the screw will match up with the teeth on the worm wheel arm. The gear end of the worm will be ¼ to 2 inches in diameter and will extend ½ to 4 inches in length. [0138] The worm will have a hole running through its center along its rotational axis that extends from the gear end up through the worm. This hole can be from ¼ of an inch long all the way to the full length of the worm. The hole will serve to keep the worm aligned within the worm drive yoke. Worm Wheel Arm: [0139] The purpose of the worm wheel arm within the mounting bracket assembly is to clamp down on the rails of the vehicle's existing roof rack in order to secure the cargo box atop the vehicle. [0140] The worm wheel arm will be an exposed component of the assembly and, as such, will be made of a rust resistant metal such as stainless machine steel or any other material that is extremely strong and rigid. [0141] The worm wheel arm will consist of two main sections. The first section will be the gear wheel. The gear wheel will be a circular section with a ⅛ to 1 inch hole at its center. Aligned concentrically around this center hole will be a set of gear teeth. These teeth will span 90° to 270° around the wheel. The teeth of the worm wheel's gear section will be designed to mesh with the screw threads of the worm. [0142] The second section of the worm wheel arm will be the arm extension. The arm will extend from the gear wheel such that the top surface of the arm and the circumference of the gear wheel are tangent to one another. The arm will extend away from the gears center line from 1 to 9 inches and will be ¼ to 4 inches wide and have a thickness of ¼ to 2 inches. At the end of the arm's extension the arm will bend at an angle of 20° to 160° for a length of ¼ to 1½ inches. [0143] The bend in the arm will act as a hook that can be positioned around the rails of the vehicle's existing roof rack in order to secure the invention from shifting forward or back ward atop the vehicle. Worm Drive Yoke: [0144] The purpose of the worm drive yoke within the bracket assembly is to hold the worm and worm wheel arm in a position so that the screw of the worm meshes with the gear teeth of the worm wheel arm. The secondary purpose of the worm drive yoke is to serve as a mount for the entire bracket assembly to the underside of the guide rail track. The worm drive yoke will be made of a durable rust resistant material such as aluminum block or any hard plastic or resin. [0145] The worm drive yoke will be a block with six sides. Each side will be connected by filleted, chamfered or butted edges and may be oriented at angles ranging from 45 to 135 degrees to one another. The yoke will support the worm wheel arm within a grove cut into the center of the yoke's right side. The groove will be 1/16 to 2 inches wide and up to 3½ inches deep. This groove will create the two arms of the yoke that will support the worm wheel arm on either side of the gear wheel section. [0146] The worm wheel arm will be mounted within the yoke by using a pin and hole attachment method that allows the worm wheel arm to swivel within the yoke. The hole will perpendicularly intersect the groove that is cut into the yoke's right side and will be situated ¼ to 3 inches from the top surface of the yoke and ½ to 3 inches from the right side surface of the yoke. [0147] The worm will be mounted in a hole that is set into the top surface of the yoke. The mounting hole will have an interior pin that will protrude up through the center of the hole. The pin will be designed as a male component with its female component being the hole that is bored into the end of the worm's shaft. This pin and hole arrangement will allow the worm to rotate on its central axis. [0148] The mounting hole will intersect the groove in the yoke allowing a section of the groove to be open through a length of the hole's wall. This opening will allow the screw threads of the worm to make contact with the teeth of the worm wheel arm. Electronic Systems: Top to Bottom Shell Sensor: [0149] The purpose of the top to bottom shell sensor 200 within the design assembly is to detect whether or not the cargo box's housing shell body is open or closed. This sensor can be any device that can send a signal to the control chip 203 , such as a pressure switch or magnetic proximity sensor. The sensor will draw power from the power source outlined below and should be connected to a power supply. Electrical Power Supply: [0150] The purpose of the electrical power supply 201 within the design assembly is to supply the proper voltage and amperage of electricity to the control chip 203 , sensors 202 , UVC lights 100 , and servos 204 . The power needed to run all the electrical components within the design can come from an independent power supply such as solar, wind, or battery power device, mounted to or within the cargo box. [0151] An alternative to the independent power supply is to use the vehicle's battery as the source of power for the operation of the electronic components. Rain Sensor: [0152] The purpose of the rain sensor 202 within the design assembly is to detect any precipitation that comes into contact with the sensor's surface during use. Control Chip: [0153] The purpose of the control chip 203 within the design assembly is to receive signals from the sensor(s). The control chip then determines the correct signal to send out to the servos controlling the control surfaces 32 of the vent closure doors 30 . Servos: [0154] The purpose of the servos 204 within the design assembly is to receive a control signal, and orient the control surfaces 32 of the vent closure door 30 , accordingly. Circuit Assembly: [0155] The rain sensor 202 is an electrical sensor. A rain drop will establish an electrical contact between the two configurations of positive and negative electrodes on the sensor's surface. Once this happens a signal is able to be sent through the completed circuit to the control chip. Once the rain sensor is tripped an internal timer will be initiated within the control chip and a signal will be sent to the servo controlling the control surfaces of the vent closure doors orienting them in the closed position. When the timer reaches an allotted time, the sensor will be set back into a standby mode, if the sensor is not tripped again within a brief timing period the control chip will send a signal reopening the control surfaces of the vent closure doors, keeping them in that position until the sensor is tripped again.
The invention is a ventilated vehicle roof rack carrier such as a cargo box for transporting items such as athletic equipment or other personal items on top of a car. The cargo box has a rigid housing shell. The housing has a top shell and a bottom shell. The top shell and the bottom shell are connected together by one or more hinges. The top shell further has at least two opposing vents for drawing air into the housing shell body and allowing air to exit the housing shell body. The cargo box also has a means in communication with the housing for attaching the housing to the vehicle. The means for attaching is a rail system with engagement means for attaching the rail system to the vehicle. The rail system further has a first articulating rail and a second articulating rail oriented in parallel relationship to each other. The pair of articulating rails are mounted to the lower shell and permit the housing to slide beyond a top surface of the vehicle and hinge downward relative to the top surface of the vehicle.
4
CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the priority benefit under 35 U.S.C. §119(e) of U.S. Provisional Patent Application No. 61/176,349 filed May 7, 2009, by Remes et al., the disclosure of which is incorporated herein by reference. FIELD OF THE INVENTION The present invention relates generally to techniques for dissociating ions in mass spectrometric analysis, and more particularly to a method and apparatus for improving the efficiency of collision induced dissociation (CID) in a quadrupole ion trap. BACKGROUND OF THE INVENTION Collision induced dissociation (CID) is a widely-used technique for the controlled fragmentation of precursor ions in a quadrupole ion trap (QIT). CID is commonly performed by applying a dipolar oscillatory excitation voltage to opposite QIT electrodes, also referred to as supplementary excitation. When the excitation voltage has a frequency at or near an ion's frequency of motion, energy from this field will be absorbed by the ion, increasing the ion's kinetic energy. The increased kinetic energy is converted into internal energy via collisions with the buffer gas, which can cause the ion to dissociate. As the ion is excited, the amplitude of its oscillatory motion grows larger. In a pure quadrupolar field with no buffer gas collisions, the ion amplitude would grow linearly with time, where the slope of this growth is determined by the magnitude of the resonant excitation field. In a pure quadrupolar field, the electric field, and thus the force on an ion, varies linearly with its position, as in Equation 1, below: E x = - Φ 0 r 0 2 ⁢ x ( 1 ) where E x is the electric field in the x direction, Φ 0 is the voltage difference between opposite rods, and r 0 is the field radius. However, all QITs incorporate some proportion of higher order non-linear field components due to the truncation of the hyperbolic surfaces, the adaptation of one or more electrodes with ejection apertures, and departures from ideal surface geometry and electrode spacing caused by manufacturing errors and tolerances. As an example, the electric field contribution from an octopolar field, for comparison, is given in Equation 2. E x = - 2 ⁢ Φ 0 r 0 4 ⁡ [ x 3 - 3 ⁢ xy 2 ] ( 2 ) In an octopolar field (or other higher order field), the force on an ion varies with position in a non-linear fashion. “Cross terms” also are to be found in these fields, where the force depends on the ion position in the y or z dimensions in addition to its position in the x dimension. The influence of higher order fields causes the amplitude growth of an ion's motion during excitation to be non-linear with time, and at large displacements the frequency of ion oscillation changes. Due to the resonant nature of the excitation process, the effect of the resonance excitation field is diminished as the ion frequency shifts away from the frequency of the excitation voltage. The ion may be subsequently returned to a resonance condition as the result of collisions with the buffer gas, which reduce the ion's amplitude of motion and cause the ions frequency to shift back to its original value. The amplitude of ion motion and the frequency of ion oscillations will fluctuate in a beating pattern as the ion comes into and out of resonance with the supplementary excitation field, as illustrated in FIG. 1 . The transfer of ion kinetic energy into ion internal energy via buffer gas collisions has been extensively modeled in the mass spectrometry literature, and the outcome of a collision has been shown to depend on the relative kinetic energy of the ion/neutral encounters, as well as the internal energy of the ion. When collisions occur with high relative kinetic energy and the ion has low internal energy, the ion internal energy will tend to increase. In contrast, when collisions have lower relative kinetic energy and the ion has high internal energy, the ion internal energy will tend to decrease. Therefore, when the ion shifts out of resonance with the supplementary excitation field and collisions occur, the ion kinetic energy is quickly lost, resulting in reduction of internal energy deposition in subsequent collisions. This phenomenon results in decreased ion fragmentation efficiency, thereby reducing the number of product ions formed in a given time and requiring longer times (relative to fragmentation in a hypothetical pure quadrupolar field) to achieve a targeted abundance of product ions. Against this background, there is a need in the mass spectrometry art for a method and apparatus for performing CID in a QIT with improved dissociation efficiency, thereby enhancing instrument sensitivity and/or throughput. SUMMARY Embodiments of the present invention provide a modified technique for performing CID in a QIT. According to this technique, the amplitude of the RF trapping voltages applied to QIT electrodes is monotonically varied over a prescribed range during the excitation period, which correspondingly changes the Mathieu parameter q and the secular frequencies of the trapped ions. The variation in trapping voltage amplitude compensates for the shift in the frequency of motion of the excited ions attributable to the influence of non-linear field components, which allows more energy from the excitation field to be transferred to the ions in a given time, resulting in higher average kinetic energies of the excited ions. In this manner, higher maximum fragmentation efficiencies may be obtained, or a targeted level of fragmentation may be achieved in less time relative to the conventional CID operating mode, wherein the RF trapping voltage is maintained substantially invariant during the excitation period. Depending on the specific characteristics of the dominant non-linear field component, the variation of the RF trapping voltage amplitude may be either downward or upward. BRIEF DESCRIPTION OF THE DRAWINGS In the accompanying drawings: FIG. 1 is a graph depicting motion of an ion excited by conventional CID in a QIT, showing in particular the beating pattern arising from the influence of higher order fields. FIG. 2 is a perspective view of a two-dimensional QIT mass analyzer in which the CID techniques of the present invention may be implemented; FIG. 3 is a timing diagram showing the application of radio frequency (RF) and excitation voltages during the excitation period; and FIG. 4 is a graph comparing the variation of fragmentation efficiency with excitation duration in cases where (i) the RF voltage amplitude is held constant during the excitation period, and (ii) the RF voltage amplitude is monotonically varied during the excitation period. DETAILED DESCRIPTION OF EMBODIMENTS Embodiments of the invention are described below in connection with their implementation in a particular QIT design, namely the four-slotted stretched two-dimensional QIT described in U.S. patent application Ser. No. 12/205,750 by Schwartz entitled “Two-Dimensional Radial-Ejection QIT Operable as a Quadrupole Mass Spectrometer”, the disclosure of which is incorporated herein by reference. It should be understood that this QIT configuration is presented by way of providing a non-limiting example of an environment in which the presently disclosed CID techniques may be implemented, and that embodiments of the present invention may be effectively used in connection with many variations of the QIT design, including three-dimensional QITs, cylindrical QITs, and rectilinear QITs. Furthermore, the QIT in which CID is performed need not be employed for mass analysis of the product ions formed by CID; for example, the product ions may be ejected from the QIT to a downstream mass analyzer for subsequent processing and/or mass analysis. Still further, alternative implementations of the present method may be utilized in connection with ion traps having a primarily non-quadrupolar (e.g., predominantly octopolar) trapping field. FIG. 2 is a perspective view of a QIT 200 . QIT 200 includes four elongated electrodes 205 a,b,c,d arranged in mutually parallel relation about a centerline 210 . Each electrode 205 a,b,c,d has a truncated hyperbolic-shaped surface 210 a,b,c,d facing the interior volume of QIT 200 . In a preferred implementation, each electrode is segmented into a front end section 220 a,b,c,d , a central section 225 a,b,c,d , and a back end section 230 a,b,c,d , which are electrically insulated from each other to allow each segment to be maintained at a different DC potential. For example, the DC potentials applied to front end sections 220 a,b,c,d and to back end sections 230 a,b,c,d may be raised relative to the DC potential applied to central section 225 a,b,c,d to create a potential well that axially confines positive ions to the central portion of the interior of QIT 200 . Each electrode 205 a,b,c,d is adapted with an elongated aperture (slot) 235 a,b,c,d that extends through the full thickness of the electrode to allow ions to be ejected therethrough in a direction that is generally orthogonal to the central longitudinal axis of QIT 200 . Slots 235 a,b,c,d are typically shaped such that they have a minimum width at electrode surface 210 a,b,c,d (to reduce field distortions) and open outwardly in the direction of ion ejection. Optimization of the slot geometry and dimensions to minimize field distortion and ion losses is discussed by Schwartz et al. in U.S. Pat. No. 6,797,950 (“Two-Dimensional Quadrupole QIT Operated as a Mass Spectrometer”), the disclosure of which is incorporated herein by reference. Electrodes 205 , a,b,c,d (or a portion thereof) are coupled to an RF trapping voltage source 240 , excitation voltage source 245 , and DC voltage source 250 , all of which communicate with and operate under the control of controller 255 , which forms part of the control and data system. Controller 255 may be implemented as any one or combination of application-specific circuitry, specialized or general purpose processors, volatile or nonvolatile memory, and software or firmware instructions, and its functions may be distributed among two or more logical or physical units. RF trapping voltage source 240 is configured to apply RF voltages of adjustable amplitude in a prescribed phase relationship to pairs of electrodes 205 a,b,c,d to generate a trapping field that radially confines ions within the interior of QIT 200 . In a typical mode of operation, the RF trapping voltage source applies sinusoidal voltages of equal amplitude and opposite phase to aligned pairs of electrodes, such that at any given time point one aligned electrode pair receives a voltage opposite in polarity relative to the voltage applied to the other aligned electrode pair. In one illustrative implementation, excitation voltage source 245 applies an oscillatory excitation voltage of adjustable amplitude and frequency across at least one pair of opposed electrodes to create a dipolar excitation field that resonantly excites ions for the purposes of isolation of selected species, collision induced dissociation (CID), and mass-sequential analytical scanning. In alternative implementations, the oscillatory excitation voltage is applied to a single electrode. This mode of excitation, sometimes referred to as monopolar excitation, actually produces a combination of dipolar and quadrupolar excitation. DC voltage source 250 is operable to apply DC potentials to electrodes 205 a,b,c,d or sections thereof, and/or to end lenses 280 and 285 , to generate a potential well that axially confines ions within QIT 200 . As described in the aforementioned Schwartz et al. patent application, electrodes 205 a,b,c,d may be symmetrically outwardly displaced (“stretched”) relative to the hyperbolic radius r 0 defined by the electrode surfaces in order to reduce the undesirable impact of the non-linear fields caused by the slots, while keeping the centerline RF potential to a minimum. However, this trap geometry still produces higher-order field components that potentially interfere with the resonant excitation process. This detrimental effect is reduced in embodiments of the present invention by monotonically varying the amplitude of the RF trapping voltages during resonant excitation to prolong the time during which the excited ions are in resonance with the exciting field. FIG. 3 is a timing diagram depicting the application of the RF trapping and resonant excitation voltages to QIT 200 during an MS/MS analysis cycle. As shown, the CID or excitation period is preceded by a trapping period, during which ions (which may be formed in any suitable ion source and transported to ion trap 200 by a conventional arrangement of ion optic elements) are injected into and trapped within the interior volume of QIT 200 , and an isolation period, during which ions having mass-to-charge ratios (m/z's) outside of a selected range are ejected from QIT 200 . Techniques for isolating a selected ion species in QIT 200 , e.g., by application of a notched multi-frequency ejection waveform, are well known in the art and hence need not be discussed herein. At the beginning of the CID excitation period, the amplitude of the RF trapping voltage is set by controller 255 to a value A start , and the excitation voltage is applied across electrodes of QIT 200 . The excitation voltage will typically take the form of a simple oscillatory (e.g., sinusoidal) waveform having a frequency f. The frequency f may be set equal to a fraction (e.g., an integer fraction) or non-fractional value of the frequency v of the RF trapping voltage, and will determine the value of the Mathieu stability parameter q at which resonance will occur. In one illustrative example, f is set equal to 1/11*v, which produces resonant excitation of ions at about q=0.25. The amplitude of the excitation voltage will typically be held constant during the excitation period, but may in certain implementations be varied during excitation. The value of the excitation voltage amplitude may be set in accordance with a calibrated relationship based on the mass-to-charge ratio (m/z) of the selected precursor ions. During the CID excitation period, controller 255 monotonically varies (i.e., exclusively increases or decreases) the amplitude of the RF trapping voltages to counteract the effect of the higher order field components and prolong the resonance condition. The direction of the variation that produces the desired effect will depend on the sign and order of the non-linear field components, which determine the direction of secular frequency change with increasing amplitude of ion motion. In the example depicted in FIG. 3 , the RF trapping voltage amplitude is monotonically decreased over the CID excitation period from an initial value of A start to a final value of A end . While the RF trapping voltage amplitude is shown as decreasing in a continuous linear fashion, in other implementations controller 255 may vary the amplitude in a stepwise or non-linear manner. The duration of the excitation period, which may be set manually or via an automated process, will typically be in the range of 5-50 milliseconds (ms). Selection of the optimal values of A start and A end will depend on the m/z of the ion species of interest (i.e., the ion species chosen for MS/MS or MS n analysis), as well as consideration of the precursor ion m/z range, the excitation time, and the specific characteristics, and relative amplitudes of the non-linear field components (and their effect on the variation of ion frequency with amplitudes of motion). In the example cited above, where f=1/11*v, A start and A end may be set to place an ion species of m/z 524 (MRFA) at a q of 0.248 and 0.252, respectively. A start and A end may be regarded as defining (in accordance with the well-known relationship between q, m/z, and the RF trapping voltage amplitude) a scan range of m/z values of ions brought into resonance with the excitation field during variation of the RF trapping voltage amplitude, disregarding the effects of nonlinear field components. The scan range will typically be approximately 2-10 Th (m/z units). The aforementioned example, wherein the amplitude is varied to ramp the q of an m/z 524 ion between 0.248 and 0.252, represents a scan range of about 6 Th. For a typical excitation period duration of 10 ms, the resultant scan rate during excitation is about 0.6 Th/ms. The instrument-specific optimal values of A start and A end may be empirically determined for a set of calibrant ions in a calibration procedure, and the determined values (or a functional representation thereof) may be stored by controller 255 so that the RF trapping amplitude may be varied during CID using the empirically-derived optimized values. At the completion of the excitation period, the excitation voltage is terminated and the amplitude of the RF trapping voltage is reduced to allow for cooling of the product and residual precursor ions. The ions may then be scanned out of QIT 200 in order of the m/z's to produce a mass spectrum by ramping the RF trapping voltage while applying a resonant ejection voltage, in accordance with the resonant scanning technique well known in the art. Alternatively, further stages of ion isolation and CID (i.e., MS n analysis) may be performed prior to acquiring the mass spectrum. Further alternatively, the product ions may be transferred to another mass analyzer for acquisition of the mass spectrum. The effect of monotonically varying the RF trapping voltage amplitude during the CID excitation period has been investigated by performing a series of MS/MS experiments on a specially modified Thermo Scientific ion trap mass spectrometer. FIG. 4 depicts the variation of fragmentation efficiency of an m/z 524 (MRFA) precursor ion with excitation period duration under conditions where (i) the RF trapping voltage amplitude is held substantially constant during excitation, and (ii) the RF trapping voltage amplitude is decreased monotonically during excitation in accordance with an embodiment of the invention. Decreasing the RF voltage amplitude during excitation causes the fragmentation efficiency to rise more quickly with duration, and to reach a plateau having a higher value of efficiency (about 60% vs. about 50% for the constant RF trapping voltage amplitude condition). Thus, a targeted degree of fragmentation can be attained more quickly when the RF trapping voltage amplitude is decreased during excitation; for example, a targeted value of 50% is reached at about 5 ms duration, vs. about 10 ms for the constant RF amplitude condition. The increased fragmentation rate reduces the required fragmentation time improving overall cycle time and throughput. Alternatively, greater numbers of product ions may be produced for a given excitation duration, thereby increasing sensitivity relative to conventional CID operation. In alternative embodiments of the invention, controller 255 is configured to monotonically vary the frequency v of the RF trapping voltage or the frequency f of the excitation voltage during the excitation period in order to equivalently prolong resonance and improve fragmentation efficiency. Since the Mathieu parameter q of an ion has an inverse dependence on the square of the trapping voltage frequency (v 2 ), the negative effects of the higher-order field components may equally be avoided by appropriately varying the trapping voltage frequency or excitation frequency during the excitation process. These frequency variations may be employed in place of or in addition to variation of the trapping voltage amplitude. Selection of the optimal start and end values of v or f will depend on the m/z of the ion species of interest, as well as consideration of the precursor ion m/z range and the specific characteristics and relative amplitudes of the non-linear field components. In a typical implementation, the start and end values of v or f define a scan range between 2-10 Th, centered on the m/z of the ion species of interest. It is to be understood that while the invention has been described in conjunction with the detailed description thereof, the foregoing description is intended to illustrate and not limit the scope of the invention, which is defined by the scope of the appended claims. Other aspects, advantages, and modifications are within the scope of the following claims.
A technique is disclosed for conducting collision induced dissociation (CID) in a quadrupole ion trap (QIT) having higher order field components. In order to compensate for the shift in the frequency of motion with amplitude of the excited ions arising from the influence of higher-order field components, the amplitude of the RF voltages applied to the QIT is monotonically varied during the excitation period to prolong the condition of resonance, resulting in higher average kinetic energies of the excited ions. Thus, higher fragmentation efficiencies may be obtained, or a targeted level of fragmentation may be achieved in less time relative to conventional CID.
7
BACKGROUND [0001] The present exemplary embodiment relates to a cleaning wipe which has been impregnated with a liquid cleaning composition. More specifically, the present embodiment relates to an ink jet cleaning wipe which is single or multi layer fabric substrate impregnated with a washing solution for cleaning ink jet heads. Although described with application to the cleaning of ink jet printer heads, it is to be appreciated that the present exemplary embodiment is also amenable to other like applications. [0002] The use of inkjet printing systems has grown dramatically in recent years. This growth may be attributed to substantial improvements in print resolution and overall print quality coupled with appreciable reduction in cost. Today's inkjet printers offer acceptable print quality for many commercial, business, and household applications at costs fully an order of magnitude lower than comparable products available just a few years ago. Notwithstanding their recent success, intensive research and development efforts continue toward improving inkjet print quality, while further lowering cost to the consumer. [0003] Various ink jet recording methods have been developed, including those using thermal and piezoelectric print heads. Thermal inkjet technology employs heat to force ink through the small nozzles in the printhead. When the ink is “boiled”, it expands and forms a bubble, which is ejected from the nozzle in the printhead. Piezoelectric printheads, on the other hand, produce droplets using electromechanical means rather than heat. In a piezoelectric head, a crystal fluctuates according to electrical signals, squirting the ink droplet out of the nozzles. [0004] Although both print heads can produce excellent results, print quality can degrade if the print head nozzles become clogged or dirty. Particularly in thermal print heads in which heat energy is used, foreign substances are apt to deposit on the face plate surface of the head by the action of heat on residual ink. These deposits impair the formation of ink droplet and result in reduced print quality. In particular, the heater in the print head is repeatedly heated to provide for ink ejection. This continuous heating causes decomposition products of the ink to be deposited on the surface of the print head nozzles as well as debris due to evaporation, resulting in a reduction in print quality. [0005] In addition, the use of quick drying ink, which reduces smearing of the ink after deposition, along with small nozzles leaves the print heads susceptible to clogging. These clogs result from not only dried ink, but also from dust, paper fibers, as well as solids (e.g. pigments, etc.) suspended within the ink itself. New pigment based inks also present potential clogging problems. Dispersants in the ink, used to keep pigment particles from flocculating, tend to form a film on the print head. This film attracts and binds paper fibers, dust and other contaminants from both the ink and elsewhere. [0006] It has been recognized that the application of a servicing solvent will help to mitigate the problem of dried ink by redissolving the dried ink as well as removing dust and other contaminants from the print head. Thus, ink jet recording head cleaning cartridges incorporating such solvents have been proposed. However, a need remains for a simple and economical method for cleaning the face plates of a print head using a disposable wipe without compromising the mechanical and/or electrical integrity of the ink jet cartridge. BRIEF DESCRIPTION [0007] In one embodiment, there is provided a cleaning wipe for cleaning the print head of a ink cartridge, the wipe including a water insoluble substrate and a cleaning solution, wherein the cleaning solution includes water, an aqueous organic solvent, and a surfactant, wherein the wipe is impregnated with the cleaning solution. [0008] In a second embodiment, there is provided a process for making a cleaning wipe for cleaning the print head of a ink cartridge, the process comprising the steps of: providing a water insoluble substrate; providing a cleaning solution comprising water, an organic solvent, and a surfactant; and impregnating the substrate with the cleaning solution. DETAILED DESCRIPTION [0009] The disclosed embodiments provide a cleaning wipe impregnated with a liquid cleaner for cleaning and removing debris from an ink jet cartridge print head. [0010] The substrate for the wipe is generally an absorbent or adsorbent material. A wide variety of materials may be used for the substrate. It should have sufficient wet strength, non-abrasivity, loft and porosity. Examples include non-woven substrates, woven substrates, hydroentangled substrates and sponges. [0011] Preferably, the substrate is a non-woven sheet, which is at least one layer, made of wood pulp, a synthetic fiber, or a blend of wood pulp and a synthetic fiber, without limitation, such as polyester, rayon, nylon, polypropylene, polyethylene, and other cellulose polymers. Non-woven materials may include non-woven fibrous sheet materials which include meltblown, coform, air-laid, spun bond, wet laid, bonded-carded web materials, hydroentangled (also known as spunlaced) materials, and combinations thereof. These materials can comprise synthetic or natural fibers or combinations thereof. One suitable material is polypropylene. A binder may or may not be present. Manufacturers of suitable substrate materials include Kimberly-Clark, E.I. du Pont de Nemours and Company, Dexter, American Nonwovens, James River, BBA Nonwovens and PGI. [0012] Woven materials, such as cotton fibers, cotton/nylon blends, or other textiles may also be used herein. Regenerated cellulose, polyurethane foams, and the like, which are used in making sponges, may also be suitable for use herein. [0013] The substrate's liquid loading capacity should be at least about 50%-1000% of the dry weight thereof, most preferably at least about 200%-800%. The substrate is typically is produced as a sheet or web which is cut, die-cut, or otherwise sized into the appropriate shape and size. Likewise, the wipes will preferably have a certain wet tensile strength which is preferably about 25 to about 250 Newtons/m, more preferably about 75-170 Newtons/m. [0014] The substrates, which are now referred to simply as wipes, can be individually sealed with a heat-sealable or glueable thermoplastic overwrap (such as polyethylene, Mylar, and the like). More preferably the wipes can be packaged as numerous, individual sheets which are then impregnated or contacted with the liquid cleaning ingredients of the invention for more economical dispensing. Even more preferably, the wipes can be formed as a continuous web during the manufacturing process and loaded into a dispenser, such as a canister with a closure, or a tub with closure. The closure is to seal the moist wipes from the external environment and to prevent premature volatilization of the liquid ingredients. Without limitation, the dispenser may be formed of plastic, such as high density polyethylene, polypropylene, polycarbonate, polyethylene terephthalate (PET), polyvinyl chloride (PVC), or other rigid plastics. [0015] The continuous web of wipes could preferably be threaded through a thin opening in the top of the dispenser, most preferably, through the closure. A means of sizing the desired length or size of the wipe from the web would then be needed. A knife blade, serrated edge, or other means of cutting the web to desired size can be provided on the top of the dispenser, for non-limiting example, with the thin opening actually doubling in duty as a cutting edge. Alternatively, the continuous web of wipes could be scored, folded, segmented, or partially cut into uniform or non-uniform sizes or lengths, which would then obviate the need for a sharp cutting edge. Further, as in hand tissues, the wipes could be interleaved, so that the removal of one wipe advances the next, and so forth. [0016] The bottom and top layers may have different textures and abrasiveness. Differing textures can result from the use of different combinations of materials or from the use of different manufacturing processes or a combination thereof. A dual texture substrate can be made to provide the advantage of a more abrasive side for cleaning difficult to remove soils. A softer side can be used for more delicate or less soiled surfaces. The substrate should not dissolve or break apart in water. [0017] The cleaning solution of the present embodiments includes water, an aqueous organic solvent and a surfactant. [0018] The aqueous organic solvent in the cleaning solution aids in the removal of debris from the face plate as well as prevents the cleaning solution from prematurely drying. An aqueous organic solvent with low viscosity is preferable because it aids the penetration of the washing solution into the ink jet head. [0019] Specific examples of the aqueous organic solvent include, but are not limited to, polyvalent alcohols and polyalkylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, 1,5-pentane diol, glycerin, and thiodiglycol; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, and propylene glycol monomethyl ether; pyrrolidone, N-methyl-2-pyrrolidone, dimethylsulfoxide, sulfolane; as well as alcohols such as ethanol, isopropanol, butanol, and benzyl alcohol; and alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine, and the like. [0020] Among these compounds, glycol ethers are preferable since they have comparatively low viscosity and are effective in improving the penetrability so that the washing solution can be widely spread over the inside of the print head in an efficient manner. A preferred aqueous organic solvent for use in the present embodiments includes a blend of diethylene glycol, diethylene glycol monobutyl ether and triethanolamine. The amount of aqueous organic solvent may be up to about 25% by weight of the cleaning solution, but is preferably from about 2 to about 15% by weight. [0021] Suitable surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. Among these, nonionic surfactants are preferable as they suppress the increase in the electroconductivity of the washing solution. [0022] Preferred nonionic surfactants include non-foaming acetylene glycol derivatives including ethylene oxide adducts of acetylene glycol. Such compounds are available under the name SURFYNOL® from Air Products and Chemicals, Inc. A particularly preferred compound is an ethylene oxide adduct of ethylene glycol having a ethylene oxide content of 65% by weight, available under the name SURFYNOL® 465 and having the following formula wherein m+n=10. These surfactants are exceptional wetting agents as well as strong defoamers, making them particularly suited for use in the present embodiments. [0023] Specific examples of other suitable nonionic surfactants include polyoxyethylenealkyl phenyl ethers such as polyoxyethylenenonyl phenyl ether, polyoxyethyleneoctyl phenyl ether, and polyoxyethylenedodecyl phenyl ether; polyoxyethylenealkyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene/polyoxypropylene block copolymers, ethylene oxide adducts of glycerin, polyoxyethylenesorbitan fatty acid esters, and fatty acid alkylolamides. [0024] The amount of surfactant in the cleaning solution may vary from about 0.1 to 5% by weight, preferably about 0.5 to 2.5%. [0025] The principal ingredient in the cleaning solution is water, which should be present at a level of at least about 70%, more preferably at least about 80%, and most preferably, at least about 90%. Distilled, deionized, or industrial soft water is preferred so as not to contribute to formation of a residue and to avoid the introduction of undesirable metal ions. [0026] Two examples of preferred formulations are presented in Table 1. Formula 2 was found to be preferred as it left little or no residue while providing comparable or superior cleaning results. The amount of each component is in weight percent. TABLE 1 Component Formula 1 Formula 2 Water 77.0 91.7 Diethylene glycol 10.0 5.0 Diethylene glycol monobutyl 10.0 2.0 ether Triethanolamine 1.0 0.5 Surfynol 465 2.0 0.8 [0027] In practice, the liquid cleaner is impregnated, dosed, loaded, metered, or otherwise dispensed onto the wipe. This can be executed in numerous ways. For example, each individual wipe could be treated with a discrete amount of liquid cleaner. More preferably, a mass treatment of a continuous web of wipes with the liquid cleaner will ensue. In some cases, an entire web of wipes could be soaked in the cleaner. In other cases, while the web is being spooled, or even during the creation of the nonwoven material, the liquid cleaner could be sprayed or otherwise metered onto the web. A mass, such as a stack of individually cut and sized wipes could also be impregnated in its container by the manufacturer, or by the user. [0028] The exemplary embodiment has been described with reference to the preferred embodiments. Obviously, modifications and alterations will occur to others upon reading and understanding the preceding detailed description. It is intended that the exemplary embodiment be construed as including all such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Cleaning wipes for cleaning the print head of an ink catridge wherein the wipe includes a substrate impregnated with a cleaning composition including water, an organic solvent, and a surfactant. The wipe leaves little or no residue on the print head resulting in improved printing performance and does not chemically interact with common print cartridge materials.
1
BACKGROUND OF THE INVENTION This invention relates to an exhaust gas purification system for an engine for activation of a catalyst at the time of starting the engine and suppressing deterioration of a catalyst due to influence of exhaust gas heat at a high temperature. In general, since a catalyst used for an exhaust gas purification system of this type is scarcely activated at a low temperature, the catalyst may be disposed at the upstream position of an exhaust passage so as to produce an activation of the catalyst at the time of starting the engine at a low temperature, but if the catalyst is disposed at the upstream position of the exhaust passage, deterioration of the catalyst is caused by the influence of exhaust gas heat at a high temperature of exhaust at the time of operating the engine at a high load, and a problem arises in its durability. Therefore, as disclosed, for example, in Japanese Patent Laid-Open Publication No. 210116/1982, there is prior art of technique for enhancing purification ratio of exhaust gas and improving durability by arranging two catalysts at a predetermined interval in an exhaust passage, providing a bypass for bypassing the catalyst at the upstream position, further providing a changeover valve at the inlet side of the catalyst at the upstream position, closing the bypass by the changeover valve when exhaust gas is at low temperature to introduce the exhaust gas to the catalyst at the upstream position, closing the inlet of the catalyst at the upstream position by the changeover valve and introducing the exhaust gas to the catalyst at the downstream position through the bypass when the exhaust gas is at relatively high temperature to cool it through the bypass. According to the above-described prior art, at least two catalysts are required in the exhaust passage. Particularly, in recent V-type and horizontal type engines for controlling exhaust gas purification at respective banks, at least two catalysts must be provided on one bank, and hence there is a problem in which its cost is expensive. SUMMARY OF THE INVENTION An object of this invention is to provide an exhaust gas purification system for an engine which proceeds to activate a catalyst at the time of starting the engine at a low temperature to improve an exhaust emission, prevents deterioration of the catalyst at a high temperature to improve durability of the catalyst and decreases a cost of the product. In order to achieve the above object, this invention provides an exhaust gas purification system for an engine having, at least two banks of said engine, an intake manifold connected to an intake port provided on said bank (LB, RB) for inducing air-fuel mixture into a cylinder, a pair of exhaust pipes connected to an exhaust port provided on said bank for emitting an exhaust gas from said cylinder, an O 2 sensor provided in said exhaust pipe at the downstream position of said exhaust port for detecting an concentration of O 2 , and a catalyst inserted in said exhaust pipe at the downstream position of said O 2 sensor for purifying said exhaust gas, an improvement of the system which comprises a changeover valve provided in said exhaust pipe between said O 2 sensor and said exhaust port, a pair of bypasses connected to said exhaust pipes for communicating said exhaust gas each other, an inlet of said bypass provided at an upstream position of said O 2 sensor for introducing said exhaust gas to the other exhaust pipes, an outlet of said bypass provided at a position of said O 2 sensor for directly sensing said concentration in said exhaust gas from the other exhaust pipes, and said changeover valve is controlled to close said bypass when a temperature of said catalyst is lower than a predetermined value and to open said bypass when said temperature of said catalyst is higher than said predetermined value so as to improve activity of said catalyst in a cold state. According to the arrangement as described above, the changeover valves inserted to the exhaust pipes close the bypasses when a catalyst temperature is low to introduce exhaust gas directly to the catalyst inserted to the exhaust pipe connected to the bank. As a result, the catalyst is heated by the exhaust gas heat to proceed the activation of the catalyst. On the other hand, when the catalyst temperature is high, the changeover valve closes one of the inlet of the catalyst to introduce the exhaust gas to the other inlet of the catalyst in the other exhaust pipe through the bypass. Since the exhaust gas is cooled while flowing through the bypass, deterioration of the catalyst at a high temperature is suppressed to improve durability. The nature, utility, and further features of this invention will be more clearly apparent from the following detailed description with respect to preferred embodiments of the invention when read in conjunction with the accompanying drawings, briefly described below. BRIEF DESCRIPTION OF THE DRAWINGS In the accompanying drawings: FIG. 1 is an overall view of an engine control system illustrating an embodiment of an exhaust gas purification system for an engine according to this invention; FIG. 2 is a circuit diagram of a controller of the exhaust gas purification system of the invention; and FIG. 3 is a flow chart showing a changeover valve control routine of the embodiment of the invention. DETAILED DESCRIPTION OF THE INVENTION The embodiments of this invention will be explained with reference to accompanying drawings. In FIG. 1, numeral 1 indicates an engine body, a horizontal opposed type engine, for example, in the drawing. An intake port 2a and an exhaust port 2b are formed at cylinder heads 2 provided on left and right banks LB and RB of the engine body 1. An intake manifold 3 is connected to the intake port 2a, and a throttle passage 5 having a throttle valve 5a provided therein is connected at the upstream position of the intake manifold 3 through an air chamber 4. An air cleaner 7 is mounted at the upstream position of the throttle passage 5 through an intake passage 6, and the air cleaner 7 is connected to an air intake chamber 8 of an intake air inlet. An idle speed control valve (ISCV) 10 is interposed in an air bypass 9 for bypassing the upstream position with the downstream position of the throttle valve 5a. On the other hand, an L (left) exhaust manifold 11 and an R (right) exhaust manifold 12 are connected on the banks to the exhaust port 2b, an L (left) exhaust pipe 13 and an R (right) exhaust pipe 14 are connected to the exhaust manifolds 11 and 12, and then to mufflers 15a and 15b. An L catalyst 16a and an R catalyst 16b are respectively interposed at positions near the exhaust ports 2b of the respective banks LB and RB in the exhaust pipes 13 and 14. Inlets 17a and 18a of exhaust bypasses 17 and 18 are connected between the catalysts 16a, 16b of the exhaust passages 13, 14 and the exhaust manifolds 11 and 12. The exhaust bypasses 17 and 18 are extended perpendicularly to each other to the other exhaust pipes 14, 13. The outlets 17b and 18b of the bypasses 17 and 18 are connected between the inlets 18a, 17a of the other bypasses 18, 17 opened with the other exhaust pipes 14, 13 and the catalysts 16b, 16a. Changeover valves 19a, 19b are respectively arranged in the inlets 17a, 18a of the bypasses 17, 18 opened with the exhaust pipes 13, 14. The changeover valves 19a and 19b are respectively cooperatively connected to an L diaphragm actuator 21a and an R diaphragm actuator 21b through a link lever 20. The diaphragm actuators 21a and 21b are respectively partitioned into two chambers by diaphragms in such a manner that a diaphragm spring is mounted in one to form spring chambers connected to a left changeover solenoid valve 22a with the pipe for controlling the left changeover valve and a right changeover solenoid valve 22b with the pipe for controlling the right changeover valve and the other to form an atmospheric chamber communicating with the atmosphere. The changeover solenoid valves 22a and 22b for controlling the changeover valves selectively communicate the spring chambers of the diaphragm actuators 21a, 21b to an atmosphere port opened with the atmosphere or a negative pressure port for communicating with a negative pressure pipe 23 connected to the intake manifold 3, and are controlled to be switched by a control signal to be output from a controller (ECU) 50 to be described later. A surge tank 24 is inserted in the negative pressure pipe 23, and a check valve 25 to be opened when the negative pressure of the intake manifold 3 is larger than that of the surge tank 24 is inserted therein. When the spring chambers of the diaphragm actuators 21a and 21b become the atmospheric pressure by the control operation of the changeover solenoid valves 22a and 22b for controlling the changeover valves 19a, 19b, the changeover valves 19a, 19b close the inlets 17a, 18a of the bypasses 17, 18 and open the exhaust pipes 13, 14 communicating with the exhaust manifolds 11, 12 of the banks LB and RB. On the other hand, when the spring chambers of the diaphragm actuators 21a, 21b become negative pressure, the changeover valves 19a, 19b open the inlets 17a, 18a of the bypasses 17, 18 and close the exhaust pipes 13, 14 communicating with the exhaust manifolds 11, 12 of the banks LB and RB. An injector 26 is disposed directly at the upstream position of the intake port 2a of each cylinder of the intake manifold 3, an ignition plug 27a to be exposed at an end thereof with a combustion chamber is mounted in each cylinder of the cylinder head 2, and an igniter 28 is connected to the ignition coil 27b connected to the ignition plug 27a. An intake air sensor (a hot wire air flow meter in FIGS. 1 and 2) 29 is disposed directly at a downstream position of the air cleaner 7 of the intake passage 6, and a throttle sensor 30 is connected to the throttle valve 5a. Further, a knock sensor 31 is mounted at the cylinder block 1a of the engine body 1. A coolant temperature sensor 33 is disposed in a coolant passage 32 for connecting both the banks LB and RB of the cylinder block 1a. A left O 2 sensor 34a and a right O 2 sensor 34b are respectively disposed directly at upstream sides of the catalysts 15a, 16b of the exhaust pipes 13, 14, and a catalyst temperature sensor 35 is provided therewith at the right catalyst 16b. A crank rotor 36 is supported to a crankshaft 1b supported to the engine body 1, and a crank angle sensor 37 is opposed to the outer periphery of the crank rotor 36. Further, a cam angle sensor 39 is opposed to a cam rotor 38 operatively connected to the cam shaft 1c of the engine body 1. The crank angle sensor 37 and the cam angle sensor 39 are not limited to magnetic sensors such as electromagnetic pickups, but may be optical sensors. On the other hand, projections (or slits) are formed on the outer peripheries of the crank rotor 36 and the cam rotor 38. The ECU 50 calculates the r.p.m. of the engine and the ignition timing from a period of an interval of pulses for detecting the projections (or slits) from the crank angle sensor 37, and determines the cylinder from an interrupt of the pulse for detecting the protrusion (or slit) from the can angle sensor 39. In FIG. 2, numeral 50 designates a controller (ECU) made of a microcomputer, which has a CPU 51, a ROM 52, a RAM 53 a backup RAM 54 and an I/O interface 55 connected through a bus line 56. A regulator 57 is contained in the ECU 50. The regulator 57 is connected to a battery 59 through a relay contact of an ECU relay or a driver 58. The relay coil of the driver 58 is connected to the battery 59 through an ignition switch 60. When the ignition switch 60 is closed, the contact of the driver 58 is closed, the voltage of the battery 59 is supplied to the regulator 57, and a stabilized voltage is supplied to sections of the ECU 50. On the other hand, a backup voltage is always applied from the regulator 57 to the backup RAM 54. A fuel pump 62 is connected to the battery 59 through a relay contact of a fuel pump relay 61. The battery 59 is connected to an input port of the I/O interface 55 of the ECU 50 to monitor a battery voltage, and the intake air sensor 29, the crank angle sensor 37, the cam angle sensor 39, the throttle sensor 30, the coolant temperature sensor 33, the right O 2 sensor 34b, the left O 2 sensor 34a, the knock sensor 31 and the catalyst temperature sensor 35 are connected thereto. The igniter 28 is connected to the output port of the I/O interface 55, and the right changeover solenoid valve 22b, the left changeover solenoid valve 22a, the injector 26, the ISCV 10 and the relay coil of the fuel pump relay 61 are connected with it through the driver 58. A control program, various fixed data are stored in the ROM 52. Output signals of the sensors, data-processed and data calculated by the CPU 21 are stored in the RAM 53. When the ignition switch 60 is closed, the CPU 51 first energizes the fuel pump relay 61 according to the control program stored in the ROM 52 to drive the fuel pump 62, controls a fuel injection amount, an ignition timing, etc., based on the output signals of the sensors, reads the catalyst temperature Tc and controls the changeover operations of both the changeover solenoid valves 22a, 22b. Then, control of the changeover valves by the ECU 50 will be described with reference to a flow chart of FIG. 3. In the flow chart of FIG. 3, when the ignition switch 60 is closed and power is applied to the ECU 50, at step (hereinafter referred to as "S") 101, by a routine to be executed at each predetermined period of time, a temperature Tc of the right catalyst 16b detected by the catalyst temperature sensor 35 is first read. At S102, the catalyst temperature Tc is compared with a preset active temperature Tcs. In the case of Tc<Tcs, the flow advances to S103, while in the case of Tc≧Tcs, the flow advances to S105. When the flow advances to S103, an I/O port output value G1 to the exciting coil of the left changeover solenoid valve 22a is set to "0". Then, at S104, an I/O port output value V2 to the exciting coil of the right changeover solenoid valve 22b is set to "0", and the routine is terminated. When the I/O port output values G1 and G2 to the changeover solenoid valves 22a, 22b become "0", the atmosphere ports of the changeover solenoid valves 22a, 22b are opened to introduce the atmosphere to the spring chambers of the changeover solenoid valves 21a, 21b. The diaphragm actuators 21a, 21b retract the link lever 20 by the energizing force of the diaphragm spring. Thus, the changeover valves 19a, 19b operatively connected to the link lever 20 close the inlets 17a, 17b of the bypasses 17, 18 and open the exhaust pipes 13, 14 connected to the exhaust manifolds 11, 12 of both the banks LB and RB of the engine body 1 (as indicated by a solid line in the drawing). As a result, since the exhaust gases discharged from the exhaust ports 2b of the banks LB and. RB flow to the catalysts 16a, 16b disposed at a near distance directly at the downstream position, the temperatures of the catalysts 16a, 16b immediately rise by the exhaust gas heat to fasten the activation of the catalysts 16a, 16b, thereby enhancing the exhaust purification ratio thereby to improve an exhaust emission. On the other hand, in the case of Tc≧Tcs, the flow advances to S105, the I/O port output value G1 to the exciting coil of the left changeover solenoid valve 22a is set to "1". Then, at S106, the I/O port output value G2 to the exciting coil of the right changeover solenoid valve 22b is set to "1", and the routine is terminated. When the I/O port output values G1 and G2 to the changeover solenoid valves 22a, 22b become "1", the negative pressure ports of the changeover solenoid valves 22a, 22b are opened to introduce the negative pressure from the intake manifold 3 into the spring chambers of the diaphragm actuators 21a, 21b through the surge tank 24. As a result, the diaphragms 21a, 21b project the link lever 20 against the energizing forces of the diaphragm springs, the changeover valves 19a, 19b operatively connected to the link lever 20 open the inlets 17a, 18b of the bypasses 17, 18 and close directly at the downstream positions of the inlets 17a, 18a of the exhaust pipes 13, 14 (as indicated by two-dotted broken lines in the drawings). Then, the exhaust gas is introduced from the exhaust manifolds 11, 12 operatively connected to the exhaust ports 2b of both the banks LB and RB to the other exhaust pipes 14, 13 by bypassing the exhaust bypasses 17, 18, and fed to the catalysts 16b, 16a disposed in the exhaust pipes 14, 13. As a result, since the exhaust gas is cooled while flowing through the bypasses 17, 18, the temperatures of the catalysts 16a, 16b are not abnormally raised to prevent deterioration and damage of the catalysts. This invention is not limited to the particular embodiment described above. For example, the changeover valves 19a, 19b are linked, and the changeover operations of both the changeover valves 19a, 19b may be controlled by one actuator. In the embodiment described above, the catalyst temperature is detected directly by the catalyst temperature sensor. However, the catalyst temperature may be estimated based on the operating state of the engine. For example, when a load is high or an air-fuel ratio is lean in a state that a coolant temperature is higher than a set value in an engine warm-up complete state, the catalyst temperature becomes high and hence the catalyst temperature can be estimated according to the conditions. The high load state may be judged according to whether a basic fuel injection amount Tp (a value to be determined according to an intake air amount or an intake manifold negative pressure and r.p.m. of the engine) representing the load state, a fuel injection amount Ti (a value obtained by correcting the basic fuel injection amount Tp by various correction items), and a throttle opening or an intake air amount per one stroke are set values or more or not. In the embodiment described above, the exhaust pipes 13, 14 and the mufflers 15a, 15b are independently provided at the downstream positions of the catalysts 16a, 16b. However, this invention is not limited to the particular embodiment. For example, the exhaust pipes may be combined at the downstream positions of the catalysts 16a, 16b and one muffler may be disposed at the downstream position of the joint of the pipes. Control of air-fuel ratio when the exhaust gas from one bank LB (RB) is introduced to the catalyst 16b (16a) of the other bank RB (LB) is improved if an air-fuel ratio feedback correction coefficient of the bank LB (RB) side is set based on the detected value of the O 2 sensor 34b (34a). According to the present invention as described above, when the catalyst temperature is low, the exhaust gas at a high temperature is introduced to the catalyst. Therefore, the activation of the catalyst proceeds to enhance the exhaust purification ratio, thereby improving an exhaust emission at the time of starting the engine at a low temperature. If the temperature of the catalyst is high, the exhaust gas cooled through the bypass is introduced to the catalyst. Therefore, deterioration and damage of the catalyst at the high temperature are suppressed to improve durability. Further, since it is not necessary to increase the number of the catalysts, a decrease in the cost of the product can be realized. While the presently preferred embodiments of the present invention have been shown and described, it is to be understood that these disclosures are for the purpose of illustration and that various changes and modifications may be made without departing from the scope of the invention as set forth in the appended claims.
The exhaust gas purification system for an engine with two banks provides a pair of bypasses for interchangeably communicating with each of the exhaust pipes from the two banks. A changeover valve is inserted at the junction point of the bypass and is inserted at the junction point of the bypass and the exhaust pipe for changing the flow of the exhaust gas. When the catalyst temperature is lower than a predetermined value, the exhaust gas flows directly into the catalyst. When the catalyst temperature is higher than the predetermined value, the exhaust gas flows into the bypasses for cooling the exhaust gas and then into the other side catalyst. Therefore, the activity performance of said catalyst is improved in both cold and hot states.
5
BACKGROUND OF THE INVENTION Current Therapy for Vascular Occlusive Diseases: Thrombosis and many related peripheral obstructive diseases are the result of abnormal activation of normal clotting mechanisms. Normal blood clotting is the result of a highly amplified chain reaction triggered by exposure of soluble factors and platelets to tissue factors, collagen and certain metabolites or hormones such as adenosine diphosphate (ADP), adrenaline and thromboxane. The clotting mechanism makes use of two systems: (a) soluble factors in the blood which activate each other in a serial manner causing hydrolysis of fibrinogen to fibrin which forms an insoluble crosslinked network, and (b) the circulating thrombocytes (platelets) which respond to the activating stimuli by releasing their own activators and by aggregating with each other. In normal clotting the soluble and platelet systems interact, with activation of one reinforcing the activation of the other. Abnormal activation of these systems can give rise to peripheral obstructive diseases. . While the pathogenesis is very complex, current models involve a lesion of the vein or artery wall, local activation of the clotting system, recruitment of activated soluble factors and platelets into the region, homeostasis, local ischemia, and reinforced activation recruitment. The platelet plays a central role in the formation and extension of clot in both venous and arterial thrombosis. In venous thrombosis, the activation of platelet initiates shape changes and release reactions of platelet contents such ADP, arachidonic acid derivatives, clotting factors which promote platelet recruitment and aggregation and activate coagulation cascade leading to fibrin formation. The activated platelet also provides an activated surface (platelet factor III) which serves as a binding site for soluble clotting factors thereby increasing their interaction and further accelerating the rate of fibrin formation. Current therapy for venous thrombosis relies mainly on the inhibition of fibrin formation; little attention was given to inhibition of the platelet which plays central role in activation. Conventional therapy for venous thrombosis makes use of heparin which actively neutralizes several of the activated soluble clotting factors. Conventional therapy also makes use of the so-called "oral anticoagulants" (dicumarol and related compounds) which inhibit the synthesis of these factors. Direct platelet activation is not affected by these drugs. In arterial thrombosis, platelets adhere to injured or diseased vessel wall and transform their shapes, release ADP and other platelet granule content, convert arachidonic acid to thromboxane A 2 , which promotes more platelet aggregation and vasconstriction and consolidation of platelet plugs. The use of antiplatelet drugs is, therefore, the mainstay of treatment and prevention of arterial thrombosis. Two classes of drug target the platelet and are used to treat arterial thrombosis: aspirin and dipyridamole. Aspirin inhibits the activation of arachidonic acid, which is one of the pathways for platelet activation. This offers some protection against activation. Dipyridamole is a phosphodiesterase inhibitor which increases the platelets' cyclic AMP level. This offers further protection against activation. Extensive clinical trials on the use of these agents in arterial thombosis showed minimal therapeutic effects. Ca 2+ Entry Blockers Are Effective Anticoagulants: The above information suggests that it would be useful to be able to further inhibit the platelet contribution to the aggregation process. The present invention shows that increases in cytoplasmic Ca 2+ concentration are central to the activation process. For instance, it has been demonstrated that platelets from patients with peripheral obstructive diseases have defects in their Ca 2+ handling which gives rise to higher cytoplasmic and sequestered Ca 2+ levels. This results in increased probability of recruitment of the platelet into the growing thrombus or diseased area. This Ca 2+ handling defect can be corrected according to the present invention by medication with Ca 2+ entry blockers; clinical improvement in the patient results. Currently-available methods are not capable of assessing these abnormalities because such testing methods are too insensitive to the Ca 2+ handling defect. As disclosed herein, the action of the Ca 2+ channel blockers is readily demonstrated using a fluorescent probe technique for the measurement of platelet-sequestered Ca 2+ . Discovery of Ca 2+ Entry Blockers; Cardiac and Smooth Muscle Effects: A large number of compounds, termed generically "Ca 2+ -channel blockers" has seen widespread use in the control of angina and treatment of myocardial infarction. These are presently divided into three groups: (1) nifedipine and related 1,4-dihydropyridines, (2) verapamil and methoxyverapamil (D600), and (3) diltiazem and cinnarizine and related diphenylmethyl alkylamines. A cardiac-inhibitory function of verapamil was discovered by Fleckenstein (Fleckenstein, A., Tritthart, H., Fleckenstein, B., Herbst, A. and Grun, G., A new group of competitive Ca antagonists (Iproveratril, D600, Prenylamine) with high potent inhibitory effects on excitation-contraction coupling in mammalian myocardium (1969), Pfluegers Arch. 306:R25) who showed that this compound had inhibitory actions similar to the removal of extracellular Ca 2+ . Subsequently, he demonstrated that this action was shared with methoxyverapamil and nifedipine. He suggested that the compounds be termed "Ca 2+ antagonists" and showed that the effects of these agents were to block the slow inward Ca 2+ current during systole. Subsequently, the compounds were shown to inhibit Ca 2+ influx into smooth muscle. These properties make the compounds very suitable for control of angina and treatment of myocardial infarction. The Ca 2+ -channel blockers apparently exert their actions primarily at membrane potential-dependent Ca 2+ channels. In smooth muscle, which can be stimulated both by membrane depolarization and noradrenaline or acetylcholine, the Ca 2+ channel blockers are generally less effective against receptor-activated channels, sometimes requiring four orders of magnitude higher doses for 50% effectiveness. The literature shows that a given Ca 2+ channel blocker will show different ED 50 s for different tissues and that a given tissue will have different ED 50 s for different channel blockers. The present invention deals with the use of calcium channel blockers in diseases arising from platelet hyperactivation. Contemporary knowledge in the art has failed to establish a definite effect of the calcium channel blockers on the platelet and has a number of explanations each attributable to the conditions of the study and intricacies of the tested system. The test of Ca 2+ -handling abnormalities used in the present application is more specific to the diseased state and to the mechanism of progression of peripheral obstructive disease. We have discovered and hereby disclose method of treating peripheral obstructive diseases in patients requiring such treatment in which a Ca 2+ channel blocker is administered to the patient for a period of time and in therapeutic quantities effective to relieve the disease symptoms and mitigate or remove the obstruction. Also disclosed is a sensitive diagnostic procedure for assessing defection, abnormal Ca 2+ handling of platelets which is indicative of certain peripheral obstructive diseases and, in turn, a means to assess a patient's response to Ca 2+ channel blockers in the therapy of such diseases. Method for correcting the Ca 2+ handling characteristics of blood platelets are also described. DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram (after Fuster, V. and Cheseboro, J. H. (1981), Current Concepts of Thrombogenesis: Role of Platelets, Mayo Clin. Proc. 56:102-112) showing the mechanisms by which platelets are activated. The primary activating factors shown on the left give rise to calcium influx into the cytoplasm and calcium release to the cytoplasmic from internal stores. This is the primary intracellular trigger for aggregation. The directions of action are given by the arrows. The dotted lines indicate positive feedback interactions. For example, increased cytoplasmic calcium concentration brings about ADP release which, in turn, brings about increased cytoplasmic calcium concentration. FIG. 2 is a schematic diagram showing how the fluorescent probe chlorotetracycline (CTC) indicates accumulation in the dense tubules. The probe is capable of making calcium complexes both in the aqueous base, in the cytoplasm and in the lumenar (aqueous spaces) of the dense tubules and mitochondria. These complexes make a small contribution to the total sample fluorescence. These calcium complexes combine to the corresponding membrane surfaces. The fluorescence contribution of the membrane bound Ca 2+ -CTC species is much higher than that of the corresponding aqueous species. The relative size and contribution of the fluorescent signal from each species is indicated by the relative size of the symbols. Uncomplexed CTC can cross the membranes; Ca 2+ -CTC cannot; thus the CTC accumulates in regions of high Ca 2+ concentration and its fluorescence is a measure of the free Ca 2+ concentration there. FIG. 3 shows four fluorometer records illustrating the use of the CTC fluorescent technique and the calculation of CTC ratio. Increasing fluorescence is plotted in the vertical direction and time is given in the horizontal direction. Curve A is for platelets from a patient with venous thrombosis; Curve B is for platelets from a healthy volunteer; Curve C is for metabolically-inhibited platelets from the same healthy volunteer; Curve D is a control experiment in which no platelets are added. The experiment was done at 37° C. with a Perkin Elmer (model MPF-3L) Fluorometer equipped with a top-mounted motor-driven plastic stirring rod and plastic cuvette. Excitation and emission wavelengths were 380 nm and 520 nm, respectively. The medium was calcium and magnesium-free Tyrode solution containing 138 mM CaCl, 3 mM KCl, 5.5 mM glucose, 12 mM NaHCO 3 , 0.4 mM NaH 2 PO 4 with the pH adjusted to 7.35. Abbreviations and final concentrations are: P=platelet suspension; S=saline; 10 uM CTC; 2 mM Ca 2+ . FIG. 4 shows the distribution of the CTC ratios observed in 18 patients with venous thrombosis. This figure shows the decrease in the CTC ratio with nifedipine therapy and shows the lack of effect of standard therapy (heparin or dicoumarol) alone. FIG. 5 shows the distribution of CTC ratios observed in 13 patients with arterial thrombosis and shows that the ratios are decreased by nifedipine therapy. FIG. 6 shows the distribution of CTC ratios observed in 17 patients with immune thrombocytopenia and 8 patients with vasculitis. The figures shows that the CTC ratios are decreased by nifedipine therapy. FIG. 7 shows the distribution of the CTC ratios observed in 16 patients with myelofibrosis and shows that the CTC ratios are decreased by nifedipine therapy. FIG. 8 shows that the nifedipine therapy-normalized CTC ratios are observed to increase towards abnormal values after discontinuation of nifedipine therapy. DETAILED DESCRIPTION OF THE INVENTION Mechanism by which Nifedipine and Other Ca 2+ Channel Blockers Correct Diseases Involving Platelet Hyperactivation: While not wishing to be bound to any theory or mode of operation, our work demonstrates the efficacy of nifedipine in reducing the internal Ca 2+ levels in circulating platelets in patients with thyromboembolic disease which, in turn, returns the platelet aggregation characteristics to normal. The rationale is based on the following unique observations: (a) the level of Ca 2+ stored in the organelles of the platelet can be readily determined by a simple technique using the fluorescence of the probe chlorotetracycline (CTC) which is coaccumulated with the sequestered Ca 2+ (Haynes, D. H., Jy, W., Ahn, Y. S. and Harrington, W. F. (1983), The use of Nifedipine in the treatment of thrombosis, U.M. PHARM-Rept. 83/1 #PB 84 129055, National Technical and Information Service and Jy, W. and Haynes, D. H. (1984), Intracellular Ca 2+ storage and release in the human platelets: chlorotetracycline as a continuous monitor (submitted for publication)), (b) that the level of sequestered Ca 2+ observed under nonstimulated or sub-threshold stimulated conditions increased with increasing Ca 2+ permeability of the plasma membrane, (c) that the resting level of sequestered Ca 2+ is elevated in patients suffering from thrombosis or related platelet disorders (d) that the process of physiological activation of the platelet depends on the release of internally sequestered Ca 2+ to the cytoplasm (Fuster & Cheseboro, 1981; Haynes et al, 1983; Jy and Haynes, 1984) as well as Ca 2+ influx across the plasma membrane, (e) that increased levels of sequestered Ca 2+ render the platelet more sensitive to stimulation by physiological agents, (f) that treatment of the patients with Ca 2+ channel blockers decreases both the levels of sequestered Ca 2+ and the rate of Ca 2+ influx both under subcritical and critical levels of stimulation, (g) that the circulating platelets are probably subjected to a large range of subcritical activating stimuli in the circulation of the thrombosis patient and that this opens a fraction of the Ca 2+ channels, increases the cytoplasmic Ca 2+ concentration, increases the levels of stored Ca 2+ and generally predisposes the platelet to activation in the region of the growing thrombus where the strength of the stimuli is near critical or supercritical, (h) that treatment of the patient with calcium channel blockers antagonize the effects of chronic subcritical stimulation (the most important effect shown in the applicants' work) and increases the threshold for recruitment of platelets into the growing thrombi, (i) that this protective effect is not measured sensitively by the currently available aggregation tests, such as ADP- or collagen-stimulated aggregation, and (j) that the effects described above give rise to an increased rate of clinical improvement. The effectiveness of the Ca 2+ channel blockers in reducing the rate of platelet depositions onto thrombi derives from the central role which Ca 2+ plays in the activation process. The novelty of the present invention is demonstrated by the fact we have demonstrated that medication with the calcium channel blockers reduce. the levels of stored and cytoplasmic calcium. It was not possible to observe direct effects on the deranged platelets using standard methods since these rely on massive stimulation during the course of the measurement, and thus obscure the difference between abnormal and normal platelets. On the other hand, the CTC test described below and our studies with the cytoplasmic Ca 2+ indicator Quin 2 showed a direct and dramatic effect which has extremely good predictive value with regard to the course of the patient's symptoms. Reference to FIG. 1 shows that the levels of stored and cytoplasmic Ca 2+ are primary determinants of the process of aggregation. This figure summarizes the mechanisms discussed by Fuster and Cheseboro (1981) in their review article on the mechanism of thrombosis formation and platelet aggregation. The figure shows that all of the physiological stimulants, i.e., ADP, thrombin, collagen and epinephrine, cause activation by increasing Ca 2+ influx and by releasing internally stored Ca 2+ . The ratio between Ca 2+ influx and release of the stores may differ with the different activators. However, Ca 2+ influx does bring about increased cytoplasmic Ca 2+ concentrations which can cause release of internally stored Ca 2+ . Elevated cytoplasmic Ca 2+ also brings about ADP release and prothrombin activation which further stimulate Ca 2+ influx into the platelet and neighboring platelets, thereby increasing the degree of aggregation and recruiting new platelets into the clot. The autocatalytic nature of this process would be expected to give rise to a sharp dependence on cytoplasmic Ca 2+ concentration. The platelet also contains a prostaglandin system which seems to serve as a mechanism for strengthening the response to stimulation. The Ca 2+ -induced phospholipase liberates arachidonic acid which is converted to thromboxane A 2 which is believed to increase the cyclic AMP level of adenylate cyclase activity resulting in the decreased rate of Ca 2+ extrusion. This would make it more difficult for the platelet to lower the cytoplasmic Ca 2+ level and would thus decrease the probability that a stimulated platelet could recover normal Ca 2+ homeostasis. Ca 2+ channel blockers suitable for use in the present invention are selected from the following representative compounds: Nifedipine, Procardia®, Pfizer Laboratories, Pfizer, Inc. (see The Merck Index, 10th Edition, registry No. 6374 and U.S. Pat. No. 3,485,847) Diltiazem, Cardizem®, Marion Laboratories, Inc. (see The Merck Index, 10th Edition, registry No. 3189 and U.S. Pat. No. 3,562,257) Verapamil, Calan®, Searle Pharmaceuticals (see The Merck Index, 10th Edition, registry No. 9747 and U.S. Pat. No. 3,261,859) Isoptin®, Knoll Pharmaceutical Company Niludipine (BAY A 7168), Bayer AG Nimodipine (BAY E 9736), Bayer and Miles Pharmaceuticals Lidoflazine, Janssen Pharmaceuticals Bepridil, C.E.R.M, Roim, France, Wallace Laboratories Prenylamine, Farbenwerke Hoechst or Hoechst Roussel Pharmaceutical Inc., Summerville, N.J. 08876 Flunarizine, Ortho Pharmaceuticals, Janssen Pharmaceuticals Fendiline, Dr. Thieman, GmbH Caroverine, Mitsubishi Chemical Industries, Ltd. Cinnarizine, Stugeron®, Janssen Pharmaceutical Ltd., U.K. Perahexiline, Merrill International Terodiline, Bicor®, Kabr Vitrum A.B., Sweden Nitrendipine, Miles Pharmaceuticals Nisoldipine, Miles Pharmaceuticals Nicardipine, Syntex Diseases arising from platelet hyperactivation as described herein include the following: peripheral vascular occlusive diseases, thrombosis, stroke, vasculitis, myelofibrosis, vasculitis, immune thrombocytopenia, venous thrombosis, arterial thrombosis, collagen-vasculitis, vasculitis lupus, and platelet disorders. Other conditions believed to be responsive to the treatment of the present invention include auto immune disorders involving platelets, other peripheral vascular diseases involving platelets, and atherosclerosis. Understanding the fundamental methodology one skilled in this art will recognize other conditions and disease states susceptible to treatment with Ca 2+ channel blockers. Comparison with Conventional "Antiplatelet" Therapy Consisting of Dipyridamole or Aspirin: Consideration of FIG. 1 shows why treatment with these antiplatelet drugs is not completely successful and why the standard in vitro tests used to measure calcium channel blocker efficacy as an antiplatelet drug have been unsuccessful. The current antiplatelet drugs work only by protecting against the cyclic AMP effects "which give rise to a decreased rate of Ca 2+ extrusion" (Fuster and Cheseboro, 1983). Aspirin works by inhibiting the conversion of the archidonic acid to thromboxane A 2 step. Dipyridamole works by increasing the cyclic AMP level. Both of these agents give rise to an increased rate of Ca 2+ extrusions when compared to untreated platelets. However, these agents do not decrease the rate of Ca 2+ influx. The Ca 2+ extrusion system is easily overwhelmed in the course of normal activation and it is probably just as easily overwhelmed in the abnormal platelet by weaker stimuli. The applicants' work shows that the Ca 2+ channel blockers are able to diminish Ca 2+ influx into the diseased platelets. This property has not been directly assessed by other workers because Ca 2+ influx studies are more difficult to do. Also, standard activation studies are considered by most workers to be superior since they encompass the overall reaction. But, as mentioned above, the autocatalytic nature of the activation process tends to make all activation processes approach the same maximal level regardless of strength of the initial stimulus and despite the possible blocking of a large fraction of the channels. Almost complete blocking of all of the channels would be necessary to suppress effects of a super-threshold stimulus. Significant effects of the channel blockers on diseased platelets might have been seen if the level of stimulus threshold had been specifically tested, but this type of detailed study is not common practice and is beyond the present state of the art. The novelty of the findings reported herein lies in both detection of the abnormality in the demonstration of its correction. The ability of channel blockers to decrease the Ca 2+ influx and thus reduce the levels of releasable Ca 2+ is readily seen by the chlorotetracycline (CTC) method. The return of the nifedipine-treated platelets to normal Ca 2+ homeostasis is shown to result in an increase in the rate of reversal of the disease. EXPERIMENTAL METHODS The Chlorotetracycline Method of Assessing Plasma Membrane Leakiness: The Ca 2+ sensitive fluorescent probe chlorotetracycline (CTC) has been applied widely in biological systems to monitor active Ca 2+ transport. A large increase in fluorescence accompanies active Ca 2+ transport. (Caswell, A. H. and Hutchison, J. P. (1971), Visualization of Membrane-bound cations by a fluorescent technique, Biochem. Biophys. Res. Commun. 42:43-49; Caswell, A. H. (1972), The migration of divalent cations in mitochondria visualized by a fluorescent chelate probe, J. Memb. Biol. 7:345-364; Caswell, A. H. and Warren, S. (1972), Observation of calcium uptake by isolated sarcoplasmic reticulum employing a fluorescent chelate probe, Biochem. Biophys. Res. Commun. 46:1757-1763; and Gershergorn, M. C., and Thaw, C. (1982), TRH mobilizes membrane calcium in thyrotropic cells as monitored by chlorotetracycline, Am. J. Physiol. 243:E298-E304). Our previous work with isolated sarcoplasmic reticulum (SR) has shown that CTC fluorescence can be used to report the free internal Ca 2+ concentration obtained by the Ca 2+ -Mg 2+ -ATPase pump (Millman, M. S., Caswell, H. H. and Haynes, D. J. (1980), Kinetics of chlorotetracycline permeation in fragmented ATP-ase-rich sarcoplasmic reticulum, Membrane Biochemistry 3:291-315). We have modeled the phenomenon showing that CTC accumulated in the organelle to an extent proportional to the free internal Ca 2+ concentration. The (Ca-CTC) + complex binds to the internal surface of the organelle membrane. Thus the fluorescence increase is proportional to the free internal Ca 2+ concentration ([Ca 2+ ] i ) in the SR lumen. Our studies of the human platelet have shown that the Ca 2+ -sensitive fluorescent probe CTC can be easily used to monitor the Ca 2+ movement in human platelets. As shown in FIG. 2, (Ca-CTC) + complex accumulates in the dense tubules and mitochondria. The fluorescence signal has been shown to be a linear measure of the level of free Ca 2+ in the dense tubules and in the mitochondria with probe sensitivity to Ca 2+ concentrations in these organelles in the millimolar range. Experiments using low concentrations of the Ca 2+ -ionophore A23187 showed that the level of free internal Ca 2+ in the organelle depends upon the cytoplasmic level which in turn depends upon the passive permeability of the plasma membrane. CTC in the cytoplasmic compartment does not report to changes in the cytoplasmic Ca 2+ concentration ([Ca 2+ ]cyt), which is held in the micromolar to sub-micromolar range by an extrusion system located in the plasma membrane. Thus plasma membrane leakiness or low levels of activation of the Ca 2+ channels of the plasma membrane will increase the cytoplasmic Ca 2+ level, increasing the dense tubular and mitochondrial sequestered Ca 2+ level and increasing the CTC signal. Quality Control and Reproducibility: The quality of the normal platelet samples from healthy volunteers was routinely determined before experimentation. No spontaneous aggregation was found upon stirring. All normal samples had to show normal aggregation kinetics. The ED 50 for collagen and ADP-induced aggregation of normal platelets was 15--15 ug/ml and 1-3 uM, respectively. This compares with literature values of 30 ug/ml (Chesney, C. M., Harper, E. and Colman, R. W. (1972), Critical role of the carbohydrate side chains and collagen in platelet aggregation, J. Clin. Invest. 51:2693-2701) and 3 uM (MacMillan, D. C. (1966), Secondary clumping effect in human citrated platelet rich plasma produced by adenosine diphosphate and adrenaline, Nature (London), 211:140-144), respectively. The CTC assay itself was also used as a criterion of quality. The responses shown in FIG. 3 were observed to be more sensitive measures of platelet quality than the above-cited tests. After approximately 24 hours of storage, the slow amplitudes shown in FIG. 3 increase while the size of the response to A23187 decreases. As will be shown below, platelets isolated from patients suffering from thrombosis gave a CTC response typical of aged or A23187-treated platelets from normal samples. Washed Platelet Suspension: Blood was drawn from patients and normal volunteers into ACD (acid-citrate-dextrose). The red cells were removed by centrifugation at 150 g for 15 minutes. Platelet concentrate was prepared by centrifugation at 900 g for 20 minutes. The platelets were washed twice and suspended in calcium and magnesium-free Tyrode solution containing 138 mM NaCl, 3 mM KCl, 5.5 mM glucose, 12 mM NaHCO 3 , 0.4 mM NaH 2 PO 4 with the pH adjusted to 7.35 with HCl and checked on an hourly basis according to the method of (Mustard, J. F., Perry, D. W., Ardlie, N. G. and Pakham, M. A. (1972), Preparation of suspension of washed platelets from humans, Br. J. Haematol. 22:193-204. This medium was used in all experimentation. The platelet concentrate was adjusted to give 20% transmittance for aggregation experiments and 50% transmittance for CTC fluorescence experiments. The data corresponded to 0.1 g/ml protein concentration. Storage was at room temperature and experimentation was at 37° centrigrade. All samples were studied within 4 hours of blood drawing. Fluorescence was measured in a Perkin Elmer (model MPF-3L) fluorometer equipped with a thermostatically controlled cell holder (T=37° C.). Reactions were carried out in a 1 cm plastic cuvette; mixing and stirring were achieved by a top mounted motor-driven plastic stirring rod. The excitation beam was polarized horizontally by a single polarizer (Chen, 1966) to reduce the light scattering effects. The fluorometer collects emitted light over a wide angle and control experiments showed that inner filter effects were negligible. In these experiments, the platelets were incubated with 10 μM chlorotetracycline at room temperature for 30 minutes before introduction into the fluorometer. The excitation and emission monochrometers were set at 380 nm and 520 nm, respectively. Platelet aggregation was measured by the turbidimetric method (according to Born, G.V.R. (1962), Aggregation of blood platelets by adphosine diphosphate and its reversal, Nature 194: 927-929). The extent of platelet aggregation was determined by monitoring transmittance changes in a Beckman spectrophotometer (Model DB-G) at 600 nm. This instrument was similarly equipped with a plastic cuvette and motor-driven stirring rod. Abnormal Platelets Show Abnormal CTC Response, Indicating Plasma Membrane Leakiness to Ca 2+ : FIG. 3 is a series of experiments showing that abnormal platelets have higher levels of Ca 2+ in their dense tubules and mitochondria than do normal platelets. The curves show thet typical CTC fluorescence response to Ca 2+ addition for abnormal (Curve A) and normal (Curve B) platelets. Curve B illustrates a standard protocol, showing the results of serial addition of platelets, CTC and Ca 2+ . The platelet addition gives rise to only a small light scattering artifact. Addition of CTC results in a rapid rise in fluorescence, followed by a slow increase with a t 1/2 of 4-5 minutes. The rapid change is due to the fluorescence of CTC in the aqueous phase and CTC bound to the outer surface of the plasma membrane. At the low external Ca 2+ concentrations, the corresponding Ca 2+ complexes make only a small contribution (cf. FIG. 2). The slow fluorescence increase has been shown to arise primarily in the binding of CTC and its Ca 2+ complexes to the inner surfaces of the organelles. The control experiments (Curve D) in the absence of platelets show that only 20-25% of the rapid response is due to CTC in the aqueous phase. No slow phase was observed. Information about Ca 2+ handling by the platelets is obtained by observing the response to the Ca 2+ addition. Curve B shows that the addition of Ca 2+ to a final concentration of 2 mM gives rise to two phases of increase: (a) An instantaneous phase corresponding to the binding of the (Ca-CTC) + complex on the outside surface, and (b) a slower plase (t 1/2 -6-8 min) due to increases in internal Ca 2+ which, in turn, give rise to increase (Ca-CTC) + binding to the internal membranes. The slow phase has been shown to be due to active uptake of Ca 2+ from the cytoplasm into the mitochondria and dense tubules. It is largely blocked by 1 hour pretreatment with NaN 3 , oligomycin and trifluoperazine (Curve C). Previous work has shown that the cytoplasmic level is coupled to the external level by pumps and leaks in the plasma membrane. This, in turn, is coupled to the mitochondrial and dense tubular levels. Thus, elevating the external Ca 2+ concentration increases the rate of Ca 2+ influx and increases the cytoplasmic level. This allows for increased uptake by the organelles. We have found that patients suffering from thromboembolism (venous and arterial) and immune thrombocytopenia, vasculitis and myelofibrosis have elevated levels of Ca 2+ in their dense tubules and mitochondria, indicating a leaky plasma membrane. Curve A shows a result obtained with a patient suffering from arterial/venous thrombosis. The fast phases are not affected by the disease, but the slow phases are greatly increased in amplitude. A similar result (not shown) is obtained when a normal platelet sample was pretreated with 20 nM A23187, a Ca 2+ ionophore which makes plasma membrane permeable to Ca 2+ (Jy and Haynes, 1984). Both the mechanism of the CTC response and the comparison show that the abnormal platelets have an increased uptake of Ca 2+ into the organelles. Experiments using the cytoplasmic Ca 2+ monitor Quin 2 show that the abnormal platelets have increased cytoplasmic Ca 2+ levels. Experiments, reported below, show that the plasma membrane defect can be corrected by administration of Ca 2+ channel blockers is vitro and in vivo. Platelets from Patients with Thrombosis Show Increased Ca 2+ Uptake: The ratio of the slow change to the fast change observed upon Ca 2+ addition (FIG. 3) was taken as a measure of the Ca 2+ handling abnormality. Table I shows that the value of this parameter in the thrombosis patients is 2.3-2.5 times the level observed in healthy controls. Parameter I is the ratio of the amplitudes of the slow phase to the fast phase. This parameter controls for possible differences in platelet composition. Experiments show a large elevation of organelle-associated Ca 2+ in platelets from patients with arterial or venous thrombosis. Table I shows that stimulation with collagen (Parameter II) produces a correspondingly larger decrease in fluorescence, as compared to normal controls (1.3-2.4 fold). This suggests that the dense tubules in these abnormal platelets are capable of releasing more Ca 2+ to the cytoplasm, suggesting a greater sensitivity towards activating agents. Table I also demonstrates that the abnormal platelets show a greater transmittance when stimulated by collagen. However, this increase (abnormal/normal equals 1.3-1.5) was only marginally siginificant due to the large variability of the abnormal patients. No differences in aggregation rate were observed. This supports the above observation that standard tests are insensitive to hypercoagulability disorders and that the CTC technique is a much more sensitive measure of the same. TABLE I__________________________________________________________________________COMPARISON OF THE CALCIUM HANDLING ABILITY AND AGGREGATIONBETWEEN NORMAL CONTROL AND THROMBOSIS PATIENTS Normal Control Arterial Thrombosis Venous Thrombosis n = 26 n = 13 n = 18__________________________________________________________________________I. Ca.sup.2+ jump 0.35 ± 0.08 0.88 ± 0.27 0.79 ± 0.29 slow phase/fast phaseII. Collagen stimulated -12.8 ± 1.1 -18.4 ± 1.6 -16.9 ± 2.1 Ca.sup.2+ release (F)III. Aggregation 18.5 ± 3.2 27.6 ± 7.0 24.8 ± 4.6 (ΔT %)__________________________________________________________________________ Collagen stimulated Ca.sup.2+ release and aggregation were evoked by addition of 20 μg/ml collagen to platelets in Tyrodes solution containing 2 mM Ca.sup.2+. Ca 2+ Handling Abnormalities of Patient with Thrombosis Is Correctable by In Vitro Treatment with A Nifedipine Analog: Table II shows that the abnormal CTC response of a patient suffering from arterial and venous thrombosis (Patient A) was correctable by treatment with a nifedipine analog in vitro. The isolated platelets were preincubated with the calcium entry blocker Y108-068 (a nifedipine analog) at 50 uM concentration for 30 minutes and were then tested for the three CTC parameters. The table shows that both the CTC ratio and the collagen-stimulated Ca 2+ release were returned to normal values by the Ca 2+ channel blocker. Platelet aggregation studies on this sample showed normal extents of aggregation stimulated by ADP and collagen for this patient. The effect of Y108-068 on the extent of aggregation was small. Clinical Improvement with Nifedipine Administration in A Thrombosis Patient: Patient A: Below, we describe the clinical course of Patient A who was treated with nifedipine. Patient A was a 68-year old man with myelofibrosis and myeloid metaplasia and was suffering from recurrent deep vein thrombosis (DVT). He was presented to us with massive DVT involving his left thigh, the size of which was 4 times larger than the right with severe erythema, a large hemorrhagic bullae from ischemia. Venogram and CAT scan confirmed large thrombi in the left iliac and femoral vein. No abnormal mass was identified on the CAT scan. He also experienced pleuritic chest pain consistent with pulmonary emboli on the lung scan. Heparin therapy (10,000-20,000 unit/hr) did not improve the DVT. A filter was inserted to prevent further pulmonary emboli. While on heparin he developed another large DVT on the right thigh. DIC screens were negative. Coagulation studies showed prolonged PTT from heparin. Platelets were large and bizarre with a count of 100,000/cumm. Patient A was administered the calcium channel blocker Procardia®(nifedipine) 10 mg T.I.D. As shown below, this resulted in dramatic improvement of both the Ca 2+ handling parameters of his plaetlets and of his condition. Table II shows that within 10 hours of initiation of nifedipine therapy, the CTC ratio and collagen-stimulated release parameters were within the normal range. Within 24 hours after nifedipine therapy, pain improved requiring less narcotics. Improvement of erythema, tenderness and swelling was obvious on the third day of therapy. In fifth day patient condition was improved to be transferred to the referring physician. TABLE II__________________________________________________________________________CHANGES IN CALCIUM INFLUX AND RELEASE AFTER NIFEDIPINETREATMENT: PATIENT A Control Group: Patient Data: mean ± S.D. Pre-treatment Post-treatmentCTC Parameter (n = 26) -52 hrs. -4 hrs. 10 hrs. 72 hrs.__________________________________________________________________________ calcium influx(a) (Ratio: slow/fast) 0.35 ± 0.08 0.51* 0.54*(0.28)** 0.27 0.27(b) Collagen stimulated -12.8 ± 1.1 -37* -26.5*(12.5)** -12 -12.5 calcium release__________________________________________________________________________ The table gives data obtained with platelets isolated from Patient A at the indicated time and studied using the CTC technique. The amplitude is tabulated for the slow phase of fluorescence increase observed upon addition of 2 mM calcium platelets (0.05 mg protein/ml) preincubated with 10 μM CTC. Parameter (b) is the ratio of amplitude of this phase to th corresponding rapid phase. Parameter (c) is the decrease in fluorescence observed upon addition of collagen to a final concentration of 20 gm/ml. *Significantly greater than control group (P < 0.05). **Result obtained with in vitro treatment with calcium blocker Y108068 at 50 μM concentration. The correlation of the CTC response of the isolated platelets with clinical improvement supports the further use of the CTC test as a measure of normalization of the platelet Ca 2+ homeostasis by this drug. Below, we report the results of treatment of a large number of patients suffering from peripheral obstructive diseases. The results show improvement of the Ca 2+ handling after nifedipine treatment and lack of such improvement when nifedipine is not administered. Medication with Nifedipine Normalizes Ca 2+ Handling in Patients with Deep Vein Thrombosis: Following the initial studies with Patient A, 18 patients with deep vein thrombosis were studied. These patients were receiving standard therapy consisting of heparin or oral anticoagulants. FIG. 4 shows that treatment with nifedipine plus standard therapy brings about improvement in the Ca 2+ handling of the platelets while the standard therapy alone brings about no improvement. A total of 18 patients were studied. Their mean value of the CTC Ca 2+ handling parameter was 0.79±0.29. Eight patients were medicated with nifedipine (10-20 mg T.I.D.) and the course of improvement of calcium handling was monitored. The treatment brought the calcium handling parameter to normal values for all of the patients except one. The right-hand portion of the figure shows the course observed for four patients who did not receive nifedipine. In this group, none of the CTC ratios returned to normal within seven days. Medication with Nifedipine Normalizes Ca 2+ Handling in Patients with Arterial Thrombosis: Thirteen patients suffering from arterial thrombosis, some receiving antiplatelet drug such as persantin or aspirin, were studied. The mean value of the CTC parameter was 0.88±0.27. FIG. 5 shows the response of the CTC parameter to medication with nifedipine (10-20 mg T.I.D.) for four patients. Nifedipine reduced the CTC values, bringing them into the normal range within seven days for all patients. These results are shown in FIG. 6. Clinical improvement was observed in all patients. Medication with Nifedipine Normalizes Ca 2+ Handling in Patients with Immune Thrombocytopenia and Vasculitis Lupus: The CTC test was applied to 17 patients with immune thrombocytopenia and eight patients with vasculitis associated with systemic lupus erythemotosis and other collagen vascular disorders. The mean values of their CTC ratios were 0.62±0.22 and 0.71±0.16, respectively. Six patients in these categories were medicated with nifedipine (10 mg T.I.D.). FIG. 7 shows that nifedipine therapy returned the CTC ratio to normal in three of these patients. Increased platelet counts were also observed in some of the patients of this group. Medication with Nifedipine Normalizes Ca 2+ Handling in Patients with Myelofibrosis: The CTC test was applied to 16 patients with myelofibrosis. The mean value of the CTC ratio was 0.69±0.27. Five patients were medicated with nifedipine (10-20 mg T.I.D.). This treatment normalized the CTC Ca 2+ handling parameter in four of the five patients, measured at seven days (FIG. 7). The treatment also increased platelet counts in two of the patients. FIG. 8 shows the results for six patients whose CTC values were normalized by nifedipine administration. After the value had stabilized in the normal range, nifedipine therapy was discontinued. The CTC parameter was observed to rise in all patients. This is further proof that the normalization of the Ca 2+ handling by these abnormal platelets is due to nifedipine, and is not a consequence of the standard therapy.
Calcium (Ca 2+ ) channel blockers, such as nifedipine and verapamil, are used in the treatment of thromboembolic diseases such as stroke and peripheral vascular occlusive diseases, especially arterial and venous thrombosis, vasculitis, myelofibrosis disease and hemolytic anemias. Such diseases arise from platelet hyperactivation and the Ca 2+ channel blockers restore the platelets to their normal aggregation characteristics. Diagnostic procedures for detecting platelet hyperactivation and defective calcium handling/transport indicative of certain peripheral obstructive diseases using chlorotetracycline as a detectable fluorescent probe as a means of assessing a patient's response to Ca 2+ channel blockers in the therapy of such diseases are also described.
8
BACKGROUND OF THE INVENTION The present invention is directed to an improvement of the Traveling Wave Amplifier (TWA) (a/k/a Distributed Amplifier) shown in FIG. 1 . Typically there are several FET devices ( 1 ) where the gates and drains of the FETs are connected with transmission lines, ( 3 ) and ( 2 ) respectively. The gate-to-gate transmission lines are designed to cancel reflections due to the capacitances of the FET gates, and incrementally absorb the energy from the input signal. Similarly, the drain-to-drain transmission lines are designed to cancel reflections due to capacitances of the FET drains and also to sum the amplified signal with the correct delay from each FET. The result, for a well-designed amplifier, is flat gain response and low input and output reflection over a wide band. Termination networks ( 4 ) and ( 5 ) provide low-frequency match at the input and output respectively. The bandwidth of the amplifier is determined by the capacitances of each individual FET as well as the realized gain per FET of the amplifier. For any particular device, in order to increase the bandwidth, one must either design for lower gain, or use additional devices. Recently it has become common practice to obtain additional bandwidth by replacing each FET device in the amplifier with a Cascode pair ( 1 ) and ( 2 ) as shown in FIG. 2 . This practice improves bandwidth by reducing the effect of the so-called “Miller Capacitance” of each device. But this practice also increases the device count by a factor of 2, requires a more complicated bias network, and can be difficult to stabilize. OBJECT AND ADVANTAGES The object of the present invention is to provide enhanced, stable, bandwidth for a TWA amplifier topology with minimal number of devices in a circuit that is simple to fabricate for both hybrid and monolithic realizations. SUMMARY OF THE INVENTION Referring to FIG. 3 , the enhanced bandwidth is achieved by designing the drain-to-drain and gate-to-gate transmission lines as coupled pairs, thereby coupling some energy back to the input from the output. The result is a small amount of distributed regenerative feedback (DRF) which provides a controlled degree of high frequency peaking. When optimized for flat gain, the frequency slope and phase of the feedback-induced peaking is set to closely match the natural gain roll-off from device parasitic elements. The |S 21 | bandwidth can thereby be increased without the need for increasing device count or by resorting to a Cascode configuration. The simplicity of the amplifier of the present invention is enhanced due to: (1) reduced device count; and (2) Simplified layout owing to the fact that the gate and drain terminals of microwave FET devices are physically close to each other. Therefore, the gate-to-gate transmission lines are most conveniently placed physically close to the drain-to-drain transmission lines for both the hybrid and MMIC realizations. This close proximity of the transmission lines produces the desired regenerative feedback. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic of a prior art traveling wave amplifier. FIG. 2 is a schematic of a prior art Cascode traveling wave amplifier. FIG. 3 is a schematic of the present invention. FIG. 4 is a schematic of the present invention to illustrate gain analysis. FIG. 5 is a schematic of the present invention to illustrate feedback analysis. FIG. 6 is a graphical representation of the gain response and feedback response of the present invention. FIG. 7 is a schematic of an alternate embodiment of the present invention. DETAILED DESCRIPTION The prior art traveling wave amplifiers and Cascode traveling wave amplifiers are illustrated schematically in FIGS. 1 and 2 . As explained in the Background of the Invention section above, these configurations suffer from defects that are solved by the present invention. Referring to FIG. 3 , the amplifier circuit is shown to include a plurality of semiconductor amplifier devices ( 1 ) each having an input electrode or gate (g) and output electrode or drain (d), a plurality of coupled transmission line pairs ( 2 ), and input and output termination networks ( 3 ) and ( 4 ). In the preferred embodiment, illustrated in FIG. 4 , there are 2 FET devices, ( 10 ), ( 12 ), and a coupled transmission line pair ( 14 ) connected between the FET gate terminals ( 11 ) and drain terminals ( 13 ), in keeping with the object of wide bandwidth with low device count. In operation, a signal is fed to the input electrode of ( 10 ), and subsequently to the input electrode of the next semiconductor, ( 12 ), through the gate-to-gate transmission line ( 17 ), ( 18 ) which provides the correct time delay to cause cancellation of reflections from the device input electrodes, and finally into the input termination network ( 19 ) providing for a low reflection at the amplifier input terminal. The output electrodes of the semiconductor devices are likewise connected through the drain-to-drain transmission line ( 16 ), ( 20 ) with a time delay designed to provide both-reflection and cancellation from the FET output electrodes, and signal summation of the amplified FET outputs. The gate-to-gate transmission line ( 17 ), ( 18 ) is designed to be physically in close proximity to the drain-to-drain transmission line ( 16 ), ( 20 ) to allow some of the amplified signal present on the drain-to-drain line to couple back to the gate-to-gate line. The amplitude of feedback signal is determined by the physical separation of the drain transmission lines from the gate transmission lines. The phase of the feedback signal is determined by the length of the line pair. For the purpose of computing the precise effect of the coupling by computer modeling, the coupled transmission lines can be described by the so-called even-mode and odd-mode impedances, (Z 0 e , Z 0 o ), and the phase length at a specified frequency as shown in FIG. 5 . The graph in FIG. 6 shows a computer simulation of a computer-optimized DRF amplifier made with commercially available FET devices. This circuit has been computer-optimized for flat gain from DC to 40 GHz. Referring to the circuit of FIG. 5 , the amplitude and phase of the feedback signal can be analyzed by “breaking the loop” at the input and thereby computing the signal returned to the input by the amplifier network. This is also shown in the graph in FIG. 6 . The amplitude of the feedback signal is shown by the trace labeled ( 50 ), and the phase of the feedback signal is shown by the trace labeled ( 52 ). It is shown in this plot that the amplitude increases towards the high frequency end of the band, and the phase tends toward 0°. This in-phase feedback effectively enlarges the input signal as the amplifier gain is rolling off, resulting in enhanced bandwidth. FIG. 7 illustrates one alternative embodiment of the present invention. In this embodiment, a plurality of FET amplifiers ( 101 ), ( 102 ), ( 103 ) are utilized. One skilled in the art may use this technique with the variation of using coupled-inductor models ( 105 ) in place of the coupled-line pairs. This alternate embodiment is the same technique with a different, and less accurate, method of computing the terminal parameters of the gate-to-gate and drain-to-drain coupling networks using self and mutual inductances as shown in FIG. 7 . One skilled in the art will recognize that the foregoing merely represents embodiments of the present invention. Many obvious modifications may be made thereto without departing from the spirit or scope of the present invention as set forth in the appended claims.
An improved traveling wave amplifier is disclosed. The improvements to the traveling wave amplifier disclosed include designing the drain-to-drain and gate-to-gate transmission lines as coupled pairs thereby coupling energy back to the input from the output. The result is increased bandwidth without an increase in device count or resorting to a cascade configuration.
7
FIELD OF THE INVENTION The invention relates to the continuous casting of steel. More precisely, it relates to the field of slags or cover powders which are deposited on the surface of the steel in the continuous casting mould, for the purpose of preventing the metal from being reoxidized by ambient air and being cooled by radiation, of trapping the non-metallic inclusions which have settled out, and for lubricating the walls of the mould while the cast product is being extracted. DESCRIPTION OF THE RELATED ART It will be recalled that these cover powders are composed of a basis powder, comprising especially oxides such as silica, lime, alumina and magnesia, and of various additives. Among these, mention may be made of sodium oxide, fluorspar, carbonates, etc. These powders are deposited on the surface of the liquid steel in the mould in order to form a layer of a few cm in depth. Near the powder/metal interface, the powder becomes liquid, enabling it to infiltrate between the wall of the mould and the solidifying skin of the cast product, and thus to perform its lubricant role. As the powder becomes consumed, it is replenished by hand or by the use of automatic devices, such as the one described in document FR 2,635,029. In this latter case, it is preferable for the powder not to have too fine a particle size, so as to reduce the risk of the pipes conveying it into the mould becoming clogged up. Thus, powders are very often used whose particles consist of hollow spheres of relatively coarse average particle size (greater than 100 μm) which are manufactured by atomization. Even if, strictly speaking, these materials can no longer really be termed pulverulent materials, they too will be designated in the rest of the text by the term "powder", as those practised in the art are wont to do. For the purpose of reducing the rate of melting of the powder, and therefore the rapidity with which it is consumed, free carbon is mixed with its constituents, this being in the form of graphite or channel black for example. The free-carbon contents (as opposed to the combined-carbon contents included in other constituents of the powder, such as carbonates) are generally of the order of a few % by weight. It has been observed that part of this carbon passes from the powder into the liquid metal, therefore causing its carbon content to increase. In the most common cases, this increase does not impair the quality of the cast product. However, in recent years there has been a significant increase in the requirements with regard to ultra-low-carbon steels, that is to say those having carbon contents below 50 ppm, or even less. At this requirement level, the approximately 4 to 10 ppm recarburization of the liquid metal, which is usually observed when powder containing even only 1 to 2% by weight of free carbon is used, can no longer be neglected. It would therefore be highly advantageous to make available to the steelmaker cover powders which no longer lead to recarburization of the metal, or to significantly less recarburization than with the usual powders, but which would nevertheless preserve sufficiently slow melting while at the same time remaining at a reasonable cost level. In document FR 2,314,000 it has been proposed to use powders having no free carbon, in which the latter is replaced by particles of metal nitrides, such as boron, silicon, manganese, chromium, iron, aluminium, titanium and zirconium nitrides. Preferably, the nitride content is between 2 and 10% by weight of the powder. This content must therefore be relatively high in order for such a carbon-free powder to have properties equivalent to those of the usual carbon-containing powders. However, the presence of a large quantity of nitride runs the risk of causing an appreciable uptake of nitrogen by the cast steel. Now, the applications of ultra-low-carbon steels quite often require the nitrogen content also to be kept at very low levels (less than 30 ppm, for example), and this nitrogen uptake may also be as troublesome as the carbon uptake which it was desired to avoid. Moreover, the average particle size of these powders was relatively fine, and therefore not very suitable for dispensing them automatically. Finally, nitrides are expensive compounds, the addition of which in large quantities raises the cost of the powder appreciably. For these reasons, it seems that these powders have not been the subject of extensive industrial development. SUMMARY OF THE INVENTION The object of the invention is to provide steel-makers, especially those casting steels having an ultra-low carbon content and possibly an ultra-low nitrogen content, cover powders which do not lead to unacceptable recarburization and renitriding of the metal, while at the same time maintaining satisfactory preservation properties and a reasonable cost. For this purpose, the subject of the invention is a mould cover powder for continuous casting of steel, especially ultra-low-carbon steel, of the type including a basis powder and particles of at least one metal nitride, characterized in that its free-carbon content (%C free ) lies between 0 and 1% by weight, in that it is manufactured by atomization and in that it is in the form of granules of diameter lying between 20 and 800 μm. According to one embodiment of the invention, the said nitride is silicon nitride and its weight content (%Si 3 N 4 ) is equal to: %Si.sub.3 N.sub.4 =0.5-0.28×%C.sub.free ±0.10 As will be understood, the invention consists in using, as a compound for controlling the rate of melting of the powder, no longer carbon alone or a nitride alone at high contents, but a mixture of carbon and one or more metal nitrides, especially silicon nitride, or possibly one or more nitrides alone but always at relatively low contents. This is made possible by the fact that the powder is manufactured by an atomization process. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT The invention will be better understood on reading the following description. One of the essential conditions for a cover powder to be able to perform its role satisfactorily is that the particles which control its rate of melting be uniformly distributed therein. The inventors have discovered that, using the powders according to the prior art containing nitrides but no carbon, which are manufactured by conventional processes, such as compacting, pelletizing, grinding or extrusion, and which had a relatively fine particle size (300 μm at most, and generally 45 μm on average), this uniformity could not be guaranteed. It was then necessary to compensate for its deficiencies by an addition of nitrides greater than would have been necessary in theory. In this way it was certain that any fraction of the powder would have a nitride content sufficient for it to provide its at least acceptable rate of melting. Having discovered this, it was necessary to find a means of guaranteeing satisfactory uniformity of the powder, by virtue of which means it would be conceivable to decrease the amounts of nitrides to be introduced. The inventors thus realized that the process of manufacturing the powder by atomization would allow the desired result to be achieved. The principle of this process, applied to the powders according to the invention, is as follows. Firstly, the principal raw materials of the powder are weighed and dry-mixed. Next, the mixture is introduced into a vessel for dispersion with a certain percentage of water and of atomization assistants in order to form a pulp called a slip. The nitrides and optionally the free carbon involved in the composition of the powder according to the invention are added at this stage, together with the atomization assistants. This slip is introduced into a transfer vessel and then pulverized in an atomizing tower by a high-pressure pump. The mist thus obtained is dried in a stream of air at 600° C. and the pulverized droplets become granules around which the carbon and nitride particles are uniformly distributed. The various operating parameters of the installation, coupled with the intrinsic characteristics of the slip, make it possible to control the particle size of the powder. In the case of the invention, the average diameter of the granules must preferably be of the order of from 300 to 500 μm and, in order to form the powder intended to be added to the mould, only granules having a diameter lying between 20 and 800 μm will be employed. Another advantage of this atomization production is that the granules, because of their size, are perfectly suited to being added to the mould by means of automatic devices. The excellent uniformity of the distribution of the nitrides, which ensure that the powder has the desired rate of melting, has the consequence that, for the same performance, a smaller nitride addition is necessary than in the powders of the prior art. It is thus possible, for an acceptable additional cost, to completely dispense with adding free carbon, which, as was stated, it is desirable to reduce as far as possible when the powder is intended for the casting of ultra-low-carbon steels. In order to find the best possible compromise between the various technical and economic requirements (knowing that the risk of renitriding the liquid metal and the cost of the powder increase with the content of nitrides), it is usually chosen not to completely dispense with adding free carbon, and to substitute it only partly with an addition of nitrides, in a quantity sufficient to maintain the rate of melting of the powder at the desired value. In this regard, the maximum permissible free-carbon content may be fixed at 1% by weight. The metal nitrides which can be used by themselves or as a mixture in the powders according to the invention are essentially boron nitride BN, silicon nitride Si 3 N 4 , aluminium nitride AlN, titanium nitride TiN, manganese nitride MnN, zirconium nitride ZrN, iron nitride Fe 4 N and chromium nitride Cr 2 N. However, it would seem that, from among these compounds, it is silicon nitride which overall has the most favourable properties in terms of cost and performance. In particular, its metallic element passing into the liquid steel during the decomposition of the powder has, in most of the cases where it is used, only an insignificant metallurgical influence, something which would not always be the case, for example for boron nitride. In the case where silicon nitride is used, the weight content of the powder of this element, "%Si 3 N 4 ", should obey the following relationship, "%C free " designating the free-carbon content: %Si.sub.3 N.sub.4 =0.5-0.28%C.sub.free ±0.10 By way of example, mention may be made of the case of a cover powder which has, in weight per cent, the following composition (the balance to 100% consisting of volatile materials): SiO 2 : 33.5%±2.5 CaO total : 31.5±2.5 Al 2 O 3 : 4.8%±1.5 F: 7.2%±1.7 Na 2 O: 11.9%±2.0 MgO: 1.2%±1.0 C free : 0.60% in the form of channel black Si 3 N 4 : 0.35% The silicon nitride particles added to the other components of the powder preferably have an average diameter less than or equal to 5 μm and a specific surface area of from 2.5 to 3.5 g/m 2 . These additions of carbon and silicon nitride give the powder a rate of melting of approximately 5 mg/s (measured at 1300° C. in a tube furnace in a controlled oxidizing atmosphere), i.e. equivalent to that which would be exhibited by a conventional reference powder, which would consist of 1.8% of free carbon and no silicon nitride and would in other respects have a composition identical to the powder according to the invention which has just been described. With this reference powder, recarburization of the liquid steel of the order of from 4 to 8 ppm is observed. With the powder according to the invention which has just been described, the maximum recarburization observed does not exceed 4 ppm and is often below the limits of analytical accuracy. Moreover, no significant renitriding of the steel is observed with this powder according to the invention, nor any silicon uptake either. Of course, the application of these cover powders according to the invention is in no way limited to the casting of ultra-low-carbon steel: they can be used for casting other types of steels. Likewise, without departing from the spirit of the invention, it is possible to add to the powder other components intended to fulfil particular functions, such as reducing agents (aluminium, silicocalcium, etc.), insofar as their presence does not unfavourably affect the lubricating ability of the powder.
A powder for covering an ingot mold for the continuous casting of steel, in particular steels with ultra-low carbon content. The powder comprises a base powder and particles of at least one metal nitride, its free carbon content (%C free ) being between 0 and 1% by weight, it being produced by atomization, and having the form of granules of between 20 and 800 μm in diameter. In one application of the invention, the nitride is silicon nitride, and its weight content (%Si 3 N 4 ) is equal to: %Si 3 N 4 =0.5-0.28×%C free ±0.10.
1
FIELD OF THE INVENTION The present invention relates to cover plates used to cover open trenches or other holes. More particularly, the invention is an improved method and device for enabling a user to lift, move and store such plates. BACKGROUND OF THE INVENTION In today's modern society buried pipes, wires and fiber optic cables are becoming more and more common. Underground vaults and large covered containers are also becoming more common. Although underground locations provide a convenient out of the way place to run pipes, wires and fiber optic cables, installing and maintaining these pipes, wires and cables pose special problems due to the trench required to house them. Often the trench, which may be quite deep, must be left open for a number of days and nights while the work is being completed. If not covered, trenches and open vaults or containers interfere with traffic and pose a safety risk to pedestrians. Further, failure to cover a trench or vault will expose existing cables or splices to the elements of nature or vandals. Finally, a trench lacking the proper covering is more likely to cave in from wind or water erosion. For these reasons, the trenches, holes or vaults are typically covered with large metal trench plates or cover plates. The plates are generally constructed of steel and although varying in thickness are usually about 1"-2" thick and 4-8 feet wide and 8-20 feet long. Due to the plate's size and composition they weigh thousands of pounds. Presently, two common methods exist for picking up these cover plates. The first, and most common method, requires a worker to place a chain through a pair of centrally located, pre-cut hole in the cover plate. This method poses problems because a worker must upwardly lift the plate a sufficient distance to place the chain under the plate and through the pre-cut holes. Placing the chain under the plate is difficult and dangerous, as the plate, which weighs thousands of pounds, must be pried up and held in place while a worker positions the chain under the plate. Many injuries have occurred from the heavy plate dropping on a workers arm or hand. The chain, once in position, is then hooked to a crane's cable line or back-hoe and lifted into place. The second method, although safer for the plate movers, comprises a spring loaded loop fastened to the plate. When in position over a trench the loop is forced upward by the force of the spring. During lifting, the crane's cable line attaches to the exposed loop. This spring loaded device is not without disadvantages. The spring loaded loop is designed to retract into the plate upon sufficient downward force. Sometimes, however, this feature malfunctions and does not recess when contacted. Such failure causes damage to automobile tires and may damage the extended spring loaded loop. Similarly, pedestrians or bicyclists may collide with and be injured by the protruding loop. Additionally, in an effort to conserve space, the steel cover plates are often stacked one on top of another. In this configuration plates possessing only holes are nearly impossible to separate while plates with the spring loaded loop stack unevenly, especially when the spring mechanism is malfunctioning. SUMMARY OF THE INVENTION This invention provides a means for lifting cover plates using an easily accessible one point attachment site thereby solving the problems associated with prior trench plate lifting apparatus and methods. The present invention is an apparatus preferably consisting of a square metal plate insert having a top, bottom and four side surfaces for insertion into a cover plate. A square aperture centered and rotationally offset ninety degrees from parallel with the edges of the plate extends through the top and bottom surfaces of the insert thereby creating an aperture through the insert. Two pins, running in bores, extend from one side surface of the insert, across the aperture and back into the insert a distance sufficient to adequately secure the pins in the insert. The pins enter the insert perpendicular to one of the sides and intersect the aperture a sufficient distance from opposite aperture corners to allow each pin to run through a link of chain. A single length of chain having ends connected to each of the pins provides a flexible means of attaching a lifting hook, with a crane or back-hoe providing the lifting force. The chain is of such length and size to fit within the confines of the aperture side surfaces and the top and bottom surfaces of the plate. Keeping the chain of such length and size means that no portion of the plate or insert therein extends beyond the flat top or bottom surfaces thereof. This prevents injury to those passing over the plates, and allows a user to stack them flat and level. Each metal plate insert is secured into the center of a cover plate. Locating the insert in the center of the cover plate aids in keeping the plate level during lifting. Securing the plate insert into the cover plate secures the pins inside the bores in the plate insert. Accordingly, it is an object of the present invention to provide a one point, easily accessible, safe and secure pick-up point for use when lifting a cover plate. The present invention may be inserted into an existing cover plate or incorporated into new cover plates. These and other objects, features, and advantages of the present invention over the prior art will become apparent from the detailed description of the drawings which follows, when considered with the attached figures. DESCRIPTION OF THE DRAWINGS The invention is best understood with reference to the drawings, in which: FIG. 1 is a perspective view of the plate insert as secured in a cover plate; FIG. 2 is a perspective view of the plate insert; FIG. 3 is sectional perspective view of the plate insert; FIG. 4 is a top view of the plate insert; and FIG. 5 is a side view of the plate insert. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT In general, the present invention is a cover plate 7 having an easily accessible one-point pickup point. In a preferred form, a plate insert 9 comprising a metal plate having an aperture 12 therein is positioned in a trench or cover plate 7. The insert 9 includes means for connecting the insert 9 to a crane or similar lifting mechanism. Preferably, these means comprise a length of chain 10 connected to the insert 9 via two pins 14, 15. In particular, two bores 16, 17 extend into a side 30 of the plate. The two pins 14, 15 are positioned in the bores 16, 17 and extend across the plate insert aperture 12. The length of chain 10 is secured at each end to the exposed portions of the pins 14, 15. The entire plate insert 9 is centered and secured in a centrally located aperture in the trench plate or cover plate 7. The cover plate 7 is then easily, quickly and safely moved by attaching a line from a back hoe, crane or other lifting mechanism to the chain 10. As illustrated in FIG. 1, the plate insert 9 of the present invention is shown secured in the cover plate 7. As illustrated in FIGS. 1-5, the plate insert is comprised of a plate insert 9 with the aperture 12 centered in the plate. The plate insert 9 has a top and bottom surface 18, 26 and four side surfaces 30, 32, 34, 36. The aperture 12 is preferably square and rotationally offset ninety degrees from parallel with the edges of the top and bottom surfaces 18, 26 of the plate insert 9. The plate insert 9, as described above, is preferably square and preferably composed of A36 steel plate. Each side of the plate insert 9 preferably measures seven inches and is of the same thickness as the cover plate 7 into which it is inserted. Each side of the centered square aperture 12 preferably measures two inches. Two opposite corners of the aperture 12 are drilled, creating an one-half inch semi-circular bore 22, 23 through the plate insert 9. These two semi-circular bores 22, 23 provide a channel for a link of chain 10, as best seen in FIG. 4. Cable mounting means are connected to the insert 9 and extend into the aperture 12. Preferably, the cable mounting means comprises two pins 14, 15 extending through bores 16,17 insert 9 and spanning the aperture 12 The bores 16, 17 are drilled 17/8 inch from the side surfaces 32, 36 and centered between the top surface 18 and the bottom surface 26 into one of the two sides surfaces 30, 34 furthest from the bored corners 22, 23 of the aperture 12. The two bores 16, 17, also measuring one-half inch in diameter, extend parallel to each other into the plate five inches or a distance sufficient to securely anchor two one-half inch 1018 steel pins 14, 15 which are inserted into the bores. The pins 14, 15 extend the full length of the bores 16, 17, spanning the aperture 12 and terminating flush with the side surface 30 of the plate insert 9. Flexible cable means are attached to the cable mounting means and for connection to a lifting mechanism. Preferably, this means comprises a single length of link chain 10 secured between each section of pin 14, 15 spanning the aperture 12. The chain 10 is preferably 5/16 inch G80 or G100 alloy chain able to withstand a lifting force of over 22,500 pounds. One pin 14, 15 runs through the last link on each end of the chain 10 as seen in FIG. 2 and FIG. 3. The length of chain 10 is of such length to be completely contained within the aperture 12 and the top and bottom surfaces 18, 26 of the plate insert 9. The plate insert 9 is positioned and secured inside a cover plate 7 by creating an aperture of a size similar to the outside dimensions of the plate insert 9 in the center of the cover plate. Preferably, the insert 9 is secured to the cover plate 7 by welding. Once the plate insert 9 is secured the pins 14, 15 may not be removed from the plate insert due to their obstruction by the cover plate. In use, a worker attaches a lifting mechanism (not shown), such as a hook on a crane or back-hoe, to the chain 10. The attachment, performed by single person, is fast, safe and requires no special devices or tools. The operator of the crane or back-hoe lifts and positions the cover plate 7. Once in position, the user releases the chain 10 from connection to the lifting apparatus, allowing the chain 10 to fall into the aperture 12. When the chain 10 is located in the aperture 12, the chain is located out of the way of automobile, bicycle and pedestrian traffic. In fact, nothing which would interfere with traffic protrudes from the cover plate 7, as the cover plate 7 presents a flat upper and lower surface, as illustrated in FIG. 5. This fact also allows a user to stack numerous plates 9 on top of another. Further, unlike prior plates incorporating a spring-loaded loop which must always be oriented "top-side" up, the plates of the present invention may be oriented such that either the "top" or "bottom" surface faces upwardly since both surfaces are flat. At the same time, the plate can easily be picked up and moved when either side faces upwardly. When the cable mounting means comprises a chain, a user can attach a lifting mechanism to the chain in a variety of orientations. This allows a user to pick up the plate in a variety of positions. For example the user may connect the lifting mechanism to the center of the chain to pick up the plate flat, or may connect the lifting mechanism towards one end of the chain to lift the plate at an angle. While the preferred means for connection comprises a length of chain 10 connected to two pins, other means, including but not limited to cable, wire, strapping, or a solid cross brace may be employed. Also, two smaller chains might be substituted for the single large chain described above. Furthermore, the cable mounting means may comprise a single pin or three or more pins in various configurations, instead of two pins 14, 15. Moreover, the pins need not span the aperture 12. For example, the pins might simply extend outwardly from the insert 9 into the aperture 12 and be connected to the chain 10 via welding or with a eyelet located on the end thereof. Also, both ends of the chain need not be anchored to the insert. One end of the chain 10 might be anchored to the insert 9 and the other simply comprise an oversized loop of metal to which a crane hook or similar item may be connected. The plate insert 9 may be located, instead of at the center of the cover plate 7, near one of the sides of the cover plate. This alternative embodiment may cause the plate to tilt when lifted and facilitate stacking the cover plates 7 on their sides. While the insert 9 described above has a square outer perimeter, the insert 9 may have a variety of other shapes such as round, triangular or rectangular. Further, the aperture 12 in the insert 9 need not be square, but may have a variety of other shapes. Preferably, the aperture is simply large enough to house a chain 10 or similar means for connection to a lifting mechanism, and at the same time be small enough that a person's foot, a bicycle tire or the like does not become readily lodged therein. The insert 9 need not have the same thickness as the plate 7 in which it is located. While it is possible for the insert 9 to have a thickness greater than the plate 7, this is not normally desirable because the insert 9 then extends outwardly of the flat surfaces of the plate. 0n the other hand, it is possible for the insert 9 to be thinner than the plate 7. The dimensions of the insert 9, aperture 12, pins and bores, as well as their locations, need not be exactly as described above. Such is merely illustrative of one specific version which has been found useful. It is possible to construct a plate 7 in accordance with the present invention without an insert 9. In particular, a manufacturer may form an aperture in a plate and connect the cable mounting means and flexible cable means directly thereto. For example, the manufacturer may make bores in the plate and slide the pins therein and weld them to the plate. While this invention is designed and described for use in connection with a trench plate or cover plate 7, it may be used as a quick, safe and convenient pick up apparatus for many other types of plates, covers, lids or weighty items. It will be understood that the above described arrangements of apparatus and the method therefrom are merely illustrative of applications of the principles of this invention and many other embodiments and modifications may be made without departing from the spirit and scope of the invention as defined in the claims.
The present invention is a device providing a safe and convenient attachment point for connecting a lifting apparatus to a trench or cover plate. The invention consists of an insert for location in the plate, the insert having at least two secured pins extending across an aperture centered in the insert. A single length of chain is secured at each end to the portions of the pins spanning the aperture. The chain is of such length and size to fit within the aperture without extending outward from the upper and lower surfaces of the insert. The insert is positioned in an existing cover plate of similar thickness or incorporated into the manufacture of new cover plates. A lifting mechanism is attached to the chain for safe and quick lifting of the cover plate.
4
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates generally to vehicle wheels and in particular to a wheel which is drawn, formed and stamped from light metal alloy blanks and a method of manufacturing such a wheel wherein several parts thereof may be formed from a single blank. 2. Description of the Prior Art Various types of vehicle wheels are well known in the prior art and generally include a center section (sometimes referred to as a spider, flange or web) and a rim section. For example, a common type of automobile wheel is shown in the Ash U.S. Pat. No. 2,551,783 wherein the rim section comprises a pair of separate rim halves each having a drop center and welded together along an annular weld seam at the rim drop center. The center section of the wheel shown in the Ash patent includes an outer, annular flange which is welded to the rim drop center. A disadvantage in constructing such a wheel is that the rim halves are formed from flat strips of metal which are welded together at their ends to form hoop-like bands and thus require additional manufacturing steps. Alternatively, wheels may be produced from flat blanks by one or a combination of operations including die forming, die stamping, extruding, hot rolling, cold rolling, spinning and drawing. For example, the Parent et al. U.S. Pat. No. 3,222,765 discloses a method of producing a wheel from a flat blank by spinning and die forming operations. However, such methods often result in substantial amounts of waste material when the parts are cut to their final configurations. Another method of forming wheels from flat blanks is shown in the Albertson et al. U.S. Pat. No. 3,262,191 wherein disk and rim sections having tapered thicknesses are produced in single, continuous power roll forming operations. Vehicle wheels have also been constructed of various materials, the most common of which are steel and light alloy metals, such as aluminum and magnesium. In view of the current emphasis on minimizing vehicle weight for greater fuel economy, the light alloy wheel constructions are preferred. For example, 14 inch steel automobile wheels weigh approximately 17 pounds each whereas cast aluminum wheels of the same size weigh approximately 13 pounds each and drawn, formed and stamped aluminum wheels according to the present invention weigh approximately 9.5 pounds each. In addition to their weight advantage with respect to steel wheels, aluminum wheels tend to dissipate brake heat faster and may be polished or brushed to provide an aesthetically pleasing finished appearance which is resistant to rust and corrosion. Steel wheels, on the other hand, must be painted, plated or otherwise protected to prevent rusting. Accordingly, nonplated steel wheels are often provided with hubcaps while aluminum wheels may be designed to exhibit a satisfactory finished appearance without wheel covers, hubcaps and the like. Furthermore, heat-treated aluminum has a better strength-to-weight ratio than steel. Hence, aluminum wheels are used extensively in high performance applications where strength and weight are crucial, such as for competition racing. Although cast aluminum wheels are well known and are generally lighter than steel wheels of comparable size, they suffer from several drawbacks. First of all, the molds for casting aluminum wheels tend to be relatively expensive as is the casting process itself. Secondly, substantial amounts of labor are generally required to machine and polish the wheels after casting. Thirdly, it is often difficult to achieve the necessary airtightness in a cast wheel without extensive grinding and polishing or coating with an air-impervious material, all of which add to the cost of such wheels. Finally, in the casting and cooling process the metal alloy may become brittle or fracture. Thus, light alloy wheels formed in two or more interconnected sections in many respects offer the best available wheel construction for strength, lightness and ease of manufacture. However, heretofore there has not been available either a vehicle wheel or a method of forming a vehicle wheel which combines the advantages and features of the present invention. SUMMARY OF THE INVENTION In the practice of the present invention a vehicle wheel is provided which includes a center section having a hub opening and a plurality of lug bolt openings. A rear rim half is integrally formed with the center section and extends rearwardly therefrom. A front rim half is adapted to receive the center section in a close fitting engagement and is welded thereto. A method of forming the wheel is provided which includes the steps of drawing, forming and stamping the center section and rear rim half from a flat blank. The front rim half is formed from another flat blank and a drop comprising excess material is cut from a formed blank in making the front rim half. The drop is then further processed to form additional parts of the wheel. In two embodiments of the present invention the drop is used to form spoke fellies and hub sections for a non-suspension wire wheel. In three other embodiments of the present invention the drop is used to form a wheel cover or facia. OBJECTS OF THE INVENTION The principle objects of the present invention are to provide a vehicle wheel; to provide such a wheel which comprises a light metal alloy; to provide such a wheel which comprises an aluminum or magnesium alloy; to provide such a wheel which is drawn, formed and stamped from a flat sheet blank; to provide such a wheel wherein a drop from the blank is utilized to form other parts; to provide such a wheel wherein the drop is used to form a spoke felly and a hub section for a non-suspension wire spoke wheel; to provide such a wheel wherein the drop is used to form a facia plate; to provide such a wheel wherein material waste is minimized; to provide such a wheel wherein a center section and a rear rim half are integrally formed from a single blank; to provide such a wheel wherein a front rim half is formed from another blank; to provide such a wheel which is relatively lightweight; to provide such a wheel which is relatively strong; to provide such a wheel which is efficient in operation, economical to manufacture, capable of a long operating life and particularly well adapted for the proposed usage thereof; to provide a method of forming such a wheel wherein material blanks are drawn, formed and stamped; to provide such a method wherein a center section and a rear rim half are integrally formed from a single blank; to provide such a method wherein a front rim half is formed from another blank; to provide such a method wherein a drop is cut from the second rim half; to provide such a method wherein the drop is used for a spoke felly and a hub section for wire spoke wheels; to provide such a method wherein the drop is used for a wheel cover or facia; and to provide such a method to efficiently and economically produce wheels with a minimum amount of material waste. Other objects and advantages of the invention will become apparent from the following detailed description taken in connection with the accompanying drawings wherein are set forth by way of illustration and example certain embodiments of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a fragmentary cross section of a basic wheel embodying the present invention which is incorporated in all of the disclosed embodiments. FIG. 2 is a fragmentary cross section of a wheel embodying the present invention with a spoke assembly. FIG. 3 is a fragmentary cross section of a wheel comprising a first alternative embodiment of the present invention with a modified spoke assembly. FIG. 4 is a front elevation of a wheel comprising a second alternative embodiment of the present invention with a facia. FIG. 5 is a fragmentary cross section of the wheel comprising the second alternative embodiment of the present invention taken generally along line 5--5 in FIG. 4. FIG. 6 is a fragmentary cross section of a wheel comprising a third alternative embodiment of the present invention with a modified facia. FIG. 7 is a fragmentary cross section of a wheel comprising a fourth alternative embodiment of the present invention with a further modified facia. FIG. 8 shows a flat plate of aluminum alloy stock with a cut line for a circular blank. FIG. 9 is a cross section of a blank for the present invention being drawn on a punch press. FIG. 10 is a cross section of the blank being formed on a punch press. FIG. 11 is a fragmentary cross section of the blank being stamped on a punch press. FIG. 12 is a fragmentary cross section of a combination center section and rear rim half for the wheel embodying the present invention. FIG. 13 is a fragmentary cross section of a blank for a front rim half showing cut lines for a drop. FIG. 14 is a fragmentary cross section showing the original drop configuration in phantom and a portion of the drop forming a felly in solid lines. DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS 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 which may be embodied in various forms. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention in virtually any appropriately detailed structure. The terms "rear" and "front" refer to the left and right respectively of the vehicle wheels embodying the present invention as oriented in FIGS. 1, 2, 3 and 5-7. The terms "inner" and "outer" and derivatives thereof refer to respective directions which are oriented radially with respect to the vehicle wheels embodying the present invention. The term "coaxial" means with respect to the rotational axes of the vehicle wheels embodying the present invention. Referring to the drawings in more detail, the reference numeral 1 generally designates a wheel comprising a preferred embodiment of the present invention. The wheel 1 generally comprises a coaxial center section 2 and a coaxial rim section 6 with a coaxial rear rim half 3 and a coaxial front rim half 4. The center section 2 is integrally formed with the rear rim half 3 and includes a hub opening 5. A plurality of lug bolt openings 11 are positioned radially outwardly from the hub opening 5 in a circular bolt pattern concentric with the hub opening 5. The lug bolt openings 11 extend through forwardly-convex lug embossments 10 stamped in the center section 2. Any desired number of lug bolt openings 11 may be provided, although most passenger vehicles include four, five or six lug bolts per wheel. The lug bolt openings 11 include chamferred outer edges 12 which aid in centering the wheel 1 when it is mounted on a vehicle. Positioned radially outwardly from the lug bolt openings 11 is a coaxial outwardly-convex ridge 16. From the ridge 16 the center section 2 sweeps outwardly and rearwardly through a transition portion 17 to a coaxial, cylindrical, center section mating portion 21 with a substantially sharp, angular intersection 22 including a radially extending stop 23. The intersection 22 may be considered to demarcate the wheel center section 2 and the rear rim half 3, although they are continuous and integrally formed. Extending rearwardly from the intersection 22 is a rear half 25 of a coaxial recessed area or drop center 26. Positioned radially outwardly and axially rearwardly from the recessed area rear half 25 is a coaxial rear rim bed 29. The rear rim half 3 terminates at a coaxial rear flange 31 which extends radially outwardly and axially rearwardly from the rear rim bed 29. The front rim half 4 terminates at a substantially square rear edge 37. Extending forwardly therefrom is a combined front mating portion 36 and recessed area front half 38. The front mating portion 36 has an inside diameter substantially equal to the outside diameter of the rear mating portion 21. Thus, the rear mating portion 21 is telescopically received in the front mating portion 36 in a close-fitting engagement. The square rear edge 37 of the front rim half 4 abuts the stop 23 whereat the rim halves 3, 4 are welded at a weld joint 39. The angular intersection 22 between the center section 2 and the rear rim half 3 facilitates proper placement of the front rim half 4 by providing a positive stop 23 for the front rim half rear edge 37 to register against. A V-shaped groove 40 is formed between the rear rim half 3 and the front rim half rear edge 37 for receiving the weld joint 39 to facilitate the establishment of an airtight seal between the rim halves 3, 4 as required for use with tubeless tires. A coaxial front rim bed 43 extends forwardly from the recessed area front half 38 and is positioned radially outwardly therefrom. The front rim half 4 terminates at a coaxial, annular front flange 45 extending forwardly and radially outwardly from the front rim bed 43. The elements of the wheel 1 described thus far and as shown in FIG. 1 are mostly common to all of the disclosed embodiments of the present invention which vary in appearance depending upon the desired aesthetics. The wheel 1 as shown in FIG. 2 includes a non-suspension spoke assembly 51. The spoke assembly 51 generally includes a coaxial spoke felly 52, a coaxial hub section 53 and a plurality of spokes 54 a,b,c,d interconnecting the felly 52 and the hub section 53. The spoke felly 52 includes an inner edge 55 and extends radially outwardly therefrom to a rear bend 56 from which the felly 52 curves forwardly to a coaxial, frustoconical felly wall 57 which opens forwardly. Connected to the forward end of the felly wall 57 is a front bend 58 from which the felly 52 curves radially outwardly and axially rearwardly to a front edge 59. A plurality of inwardly-convex dimples 60 extend from the felly wall 57 in a radially spaced and axially staggered pattern. The felly 52 is attached (e.g. by rosette welding or adhesive) to the wheel 1 at three locations: (1) between the transition portion 17 and the felly inner edge 55; (2) between the front rim 4 adjacent its rear edge 37 and the felly rear bend 56; and (3) between the front rim half front flange 45 and the spoke felly front edge 59. The spokes 54 a,b,c,d are attached to the dimples 60 on the felly wall 57 in an axially staggered and radially spaced relationship by outer spoke connectors 62 at spoke outer ends 61 a,b,c,d. The spokes 54 a,b,c,d extend radially inwardly and axially forwardly to spoke inner ends 63 a,b,c,d which are attached to the hub section 53. The hub section 53 includes a rear outer edge 65, a frusto-conical rear wall 66, a frusto-conical front wall 67 and a front edge 68 forming a coaxial hub opening 69. The spokes 54 a,b,c,d are attached in alternating, staggered layers at their inner ends 63 a,b,c,d to the hub section rear and front walls 66, 67 in radially spaced relation. The outer hub section 53 is attached adjacent to its rear outer edge 65 to the center section 2 adjacent to and radially outwardly from its first ridge 16. The lug bolt openings 11 are accessible through the hub opening 69. The reference numeral 71 generally designates a wheel comprising a first alternative embodiment of the present invention shown in FIG. 3 with a non-suspension spoke assembly 72. The spoke assembly 72 includes a coaxial spoke felly 52 substantially identical to that described in connection with the wheel 1. A plurality of spokes 73 a,b, c,d are connected at respective outer ends 74 a,b,c,d, to the spoke felly 52 by spoke connectors 62 in axially staggered and radially spaced relation. The spokes 73 a,b, c,d terminate at respective inner ends 75 a,b,c,d. A coaxial hub section 76 includes a coaxial outer edge 77, a forwardly-convex coaxial hub section ridge 78 positioned radially inwardly from the outer edge 77 and a coaxial lug bolt ring 79 positioned inwardly from the ridge 78. A plurality of radially spaced hub section lug bolt openings 82 extend through the lug bolt ring 79 in axially aligned relationship with the center section lug bolt openings 11. A cylindrical, coaxial inner wall 80 with a recessed intermediate portion 83 extends forwardly from the lug bolt ring 79 and terminates at a hub section front edge 81. Spoke inner ends 75a,b are connected to the hub section 76 between its outer edge 77 and its ridge 78. The remaining spoke inner ends 75c, d are connected to the hub section inner wall 80. A coaxial hub section opening 84 is defined by the hub section inner wall 80. The hub section 76 is attached (e.g. by rosette welding or adhesive) to the wheel center section 2 in two places: (1) between the center section 2 adjacent to its ridge 16 and the hub section 76 adjacent to its outer edge 77; and (2) between the center section front edge 6 and the hub section 76 between its lug bolt ring 79 and its inner wall 80. The center section 2 may be painted black between the spoke fellies 52 and the hub sections 53, 76 of the wheels 1 and 71 to provide a high contrast visual backdrop for the respective spokes 54a,b,c,d and 73a,b,c,d. With the center section transition portions 17 painted black the wheels 1 and 71 are similar in appearance to suspension-type wire wheels. FIGS. 4 through 7 show wheels 101, 181 and 191 comprising second, third and fourth alternative embodiments of the present invention with wheel covers or facias 152, 182 and 192 respectively. The wheel 101 comprising the second alternative embodiment (FIGS. 4 and 5) of the present invention includes a center section 102 integrally formed with a rear rim half 103. The center section 102 and the rear rim half 103 are substantially similar to the center section 2 and the rear rim half 3 of the wheel 1. A coaxial front rim half 104 is mounted on the center section 102 and the rear rim half 103 at an intersection 122 therebetween. The front rim half 104 is substantially identical to the front rim half 4 of the wheel 1, except that the former includes a coaxial front flange 145 which extends further to the front and forms an annular, inwardly-open facia recess 146. The circular facia 152 is slightly convex in a forward direction. The facia 152 includes a coaxial facia center opening 153 positioned in front of a hub opening 105 of the center section 102. A plurality (for example four, five or six) of facia bolt openings 154 are formed in the facia 152 in a concentric pattern at radially spaced intervals around the center opening 153. Each facia bolt opening 154 is defined by a respective rearwardly-extending flange 155. The facia bolt openings 154 correspond to and are coaxial with respective lug bolt openings 111 in lug embossments 110 stamped in the center section 102. The facia plate 152 terminates at an outer circumference with a rearwardly extending rim 160 which is captured within the annular facia recess 146 by the front flange 145. A plurality (for example, twelve) of decorative slots 164 extend through the facia 152 at a position radially inwardly from the facia rim 160. The slots 164 are arcuate-shaped and arranged in a pattern concentric with the facia 152 at radially spaced intervals. Each slot 164 includes a respective facia slot flange 165 extending rearwardly from the facia 152. A plurality of cylindrical spacers 166 are positioned between the center section 102 and the facia 152 coaxial with respective bolt openings 111 and 154. Each spacer 166 includes a rear end 167 engaging the center section 102 around a respective lug bolt opening 111 and a front end 168 engaging a respective facia bolt opening flange 155. Referring in more detail to FIG. 6, the wheel 181 comprises a third alternative embodiment of the present invention with a modified wheel cover or facia 182. The facia 182 includes a peripheral portion 183 which is canted rearwardly from an inner portion 184. The peripheral portion 183 includes a plurality of arcuate slots 186 positioned in a circular, radially spaced pattern. The slots 186 are substantially similar to the slots 164 of the second alternative embodiment. The peripheral portion 183 terminates at an outer edge 187 with a rim 188 captured in an annular recess 189 formed by a front rim half front flange 190. The configuration of the facia 182 with its canted peripheral portion 183 provides a deeper overall configuration for the wheel 181 comprising the third embodiment than the second alternative embodiment wheel 101. The wheel 191 comprising the fourth alternative embodiment of the present invention (FIG. 7) includes a wheel cover or facia 192 having a peripheral portion 193 which is canted even more sharply rearwardly than the corresponding peripheral portion 183 of the fourth embodiment. The peripheral portion 193 is canted rearwardly from an inner portion 184 of the facia 192 and includes a plurality of arcuate, radially spaced slots 196 in a circular pattern. The peripheral portion 193 terminates at an outer edge 187 with a rim 198 which is received in an annular recess 189 of a front rim half front flange 190. The facia 192 provides the wheel 191 comprising the fourth embodiment with an even deeper appearance yet than the wheel 181 comprising the third embodiment. A method of forming the wheels 1, 71, 101, 181, and 191 is provided. The steps of performing the method are shown in FIGS. 8 through 14. To begin with, a disc blank 301 is cut from a square, flat plate of aluminum alloy stock 302 (FIG. 8). A center opening 303 is punched in the disc 301 and corresponds to the hub openings 5, 105. The disc 301 is centered on a first mandrel 304 of a primary punch press 305 wherein it is drawn into a primary drawn blank 306 (FIG. 9). In a second punch press operation the drawn blank 306 is placed over a second mandrel 309 and formed in a second punch press 310 to a formed blank 308 comprising a more final configuration as shown in FIG. 10. In the forming operation the rear flange 31 or 131 is completed and the lug embossments 10 and 110 are formed. In a third punch press operation the hub openings 5, 205 and the lug bolt openings 11, 211 are stamped in a final formed blank 311 (FIG. 11). Also, in the third operation a factory identification may be stamped in the final formed blank 311. The three-step draw, form and stamp operation described thus far completes the integrally formed center sections 2, 102 and the rear rim halves 3, 103. A second final formed blank 312 is drawn, formed and stamped from a second disc (not shown) according to the above methods and provides a front rim half 4, 104 and other parts of the wheels as will be described hereinafter. The second final formed blank 312 is separated at a first cut line 315 into a front rim half 4, 104, and a remaining scrap portion 316 which may be referred to as a "drop" (FIG. 13). The drop 316 is employed to form additional parts of a wheel 1, 71, 101, 181 or 191 as desired. In the formation of wheels 1 and 71, the drop is separated at a second cut line 317 into a spoke felly blank 321 and a hub section blank 322 (FIG. 14). The spoke felly and hub section blanks 321, 322 are drawn, formed and stamped as required on punch press equipment to form completed spoke fellies 52 and hub sections 53, 76. In the formation of the wheels 101, 181 and 191 the facias 152, 182 and 192 are produced in their desired configurations from the drop 316. The method of producing the wheels 1, 71, 101, 181 and 191 is relatively fast because the parts are drawn, formed and stamped on punch presses. In fact, punch presses capable of performing the draw, form and stamp procedures are available which operate in cycles of approximately 20 seconds for each operation. Thus, labor and energy costs are minimized. Such punch pressing equipment is also not nearly as expensive as the equipment necessary for spinning and casting vehicle wheels. Finally, the disclosed production method is relatively efficient in its use of material since the drop 316 from the second final formed blank 312 is utilized to form additional parts and the resulting amount of scrap material is thus kept to an absolute minimum. In summary, the manufacturing method according to the present invention is particularly advantageous because of its aforementioned efficiencies in the areas of energy consumption, labor, capital investment and material. The material (preferably aluminum alloy) for the wheels 1, 71, 101, 181 and 191 tends to work harden during the punch press operations and therefore generally does not require heat treating, which further saves energy and labor costs. The plate 302 is formed of aluminum sheet material 0.220 inches thick and in the manufacturing process is tapered to desired configurations as required for different parts of the wheel. For example, at the center sections 2, 102 the thickness may be 0.220 inches and at the rear rim halves 3, 103 the thickness may taper to 0.180 or 0.190 inches. At the rear flange 31, 131 the material is again full thickness of 0.220 inches. It is to be understood that while certain forms of the present invention have been illustrated and described herein, it is not to be limited to the specific forms or arrangement of parts described and shown.
A vehicle wheel including a center section integrally formed with a rear rim half by a method including the steps of drawing, forming and stamping a first lightweight metal alloy bank. A front rim half is drawn, formed and stamped from a second blank and is attached to the front rim half. A drop comprising excess material from the second blank is used to form an additional part or parts of the wheel.
8
FIELD [0001] Embodiments of the present invention relate to an image display apparatus. BACKGROUND [0002] There is a conventional image display apparatus that displays an image which appears to be differently depending on the direction a person sees the image, so that the image appears to be stereoscopic, and for example, in order to display parallax images which are shown in multiple directions and which can be seen in multiple directions, a composite image obtained by composing parallax images is recorded onto a recording medium such as a sheet by means of printing, and the image is displayed through a lenticular lens. The composite image is made by arranging multiple parallax images in a rectangular form, and the same parallax image is displayed in the same direction by many cylindrical lenses constituting the lenticular lens. [0003] In this case, when the position of the composite image printed on the recording medium does not match the position of the lenticular lens, the image displayed is corrupted in a conventional image display apparatus. In the conventional image display apparatus, the positional deviation includes horizontal positional deviation and inclination deviation, but it is difficult to independently adjust both of them, and it has not been easy to adjust the positions. BRIEF DESCRIPTION OF THE DRAWINGS [0004] FIG. 1 is a configuration diagram illustrating an image display apparatus according to a first embodiment. [0005] FIGS. 2( a ) and 2 ( b ) are transverse sectional views illustrating the image display apparatus according to the first embodiment. [0006] FIG. 3 is a longitudinal sectional view illustrating a lenticular lens unit of the image display apparatus according to the first embodiment. [0007] FIGS. 4( a ) to 4 ( c ) are figures illustrating a method for forming a recording medium for the image display apparatus according to the first embodiment. [0008] FIG. 5 is a first flowchart illustrating a method for assembling the image display apparatus according to the first embodiment. [0009] FIG. 6 is a second flowchart illustrating a method for assembling the image display apparatus according to the first embodiment. [0010] FIG. 7 is a longitudinal sectional view illustrating an image display apparatus according to a second embodiment. [0011] FIG. 8 is a longitudinal sectional view illustrating an image display apparatus according to a third embodiment. [0012] FIG. 9 is a longitudinal sectional view illustrating an image display apparatus according to a fourth embodiment. [0013] FIG. 10 is a longitudinal sectional view illustrating an image display apparatus according to a fifth embodiment. [0014] FIG. 11 is a longitudinal sectional view illustrating an image display apparatus according to a sixth embodiment. [0015] FIG. 12 is a longitudinal sectional view illustrating an image display apparatus according to a seventh embodiment. DETAILED DESCRIPTION [0016] Embodiments will be hereinafter explained with reference to drawings. First Embodiment [0017] An image display apparatus according to a first embodiment will be hereinafter explained with reference to drawings. [0018] First, overview of the image display apparatus of the first embodiment will be explained with reference to FIG. 1 . FIG. 1 is a configuration diagram illustrating the image display apparatus according to the first embodiment. [0019] As shown in FIG. 1 , a recording medium 1 is formed with a recorded image 2 , and, for example, the recording medium 1 is attached to a medium attachment unit 3 which is a flat plate. A lenticular lens unit 4 is attached so that it is in contact with the recording medium 1 attached to the medium attachment unit 3 . [0020] The image display apparatus according to the first embodiment before and after the assembly will be explained with reference to FIG. 2 . FIG. 2 is a transverse sectional view illustrating the image display apparatus according to the first embodiment. [0021] FIG. 2( a ) schematically illustrates the image display apparatus according to the first embodiment before the assembly, and as shown in FIG. 2( a ), the recording medium 1 is formed with the recorded image 2 , and the recording medium 1 is attached to the medium attachment unit 3 , and thereafter, the lenticular lens unit 4 is attached to the recording medium 1 . [0022] Therefore, while a lenticular lens 5 is brought into contact with the recorded image 2 , a position adjustment mechanism 6 is adjusted. In this case, the lenticular lens 5 is configured in such a manner that many inverted U-shaped cylindrical lenses 14 are arranged side by side. In FIGS. 2( a ), 2 ( b ), the vertical direction of the drawings is a direction substantially in parallel with the border lines between the cylindrical lenses 14 , like the subsequent drawings. In FIGS. 2( a ), 2 ( b ), the horizontal direction of the drawings is a direction substantially perpendicular to the border lines between the cylindrical lenses 14 , like the subsequent drawings [0023] The position of the recording medium 1 is somewhat determined by a medium abutment surface 7 , but antislip processing is applied to the medium attachment surface of the medium attachment unit 3 , or a antislip sheet is pasted to the medium attachment surface of the medium attachment unit 3 , whereby it is made into an antislip surface 8 , so that the recording medium 1 does not move together with the lenticular lens 5 when the lenticular lens 5 moves on the recording medium 1 . [0024] FIG. 2( b ) schematically illustrates the image display apparatus according to the first embodiment after the assembly, and as shown in FIG. 2( b ), the medium attachment unit 3 and the lenticular lens unit 4 are fixed with screws or hooks, not shown, so as to maintain such state as to press the lenticular lens 5 and the recorded image 2 having been adjusted. [0025] In this case, the lenticular lens unit 4 has the position adjustment mechanism 6 . FIG. 3 is a longitudinal sectional view illustrating a lenticular lens unit of the image display apparatus according to the first embodiment. [0026] As shown in FIG. 3 , the lenticular lens 5 is connected via a rotation center screw 11 with a slide mechanism 10 provided at an upper portion of FIG. 3 with respect to a frame 9 . [0027] In this case, horizontal adjustment knobs 12 (hereinafter referred to as a horizontal adjustment unit) are provided to connect with the slide mechanism 10 , and for example, in a case where the slide mechanism 10 is of a direct-acting method, a user grabs one of or both of the knobs and moves the knobs in a horizontal direction (which will hereinafter refer to a direction substantially perpendicular to the border lines of the cylindrical lens 14 constituting the lenticular lens 5 ), so that the slide mechanism 10 connected with the lenticular lens 5 can be adjusted in the horizontal direction of FIG. 3 . In a case where the slide mechanism 10 is of a feed screw method, a user rotates one of or both of the knobs, so that the slide mechanism 10 connected with the lenticular lens 5 can be adjusted in the horizontal direction of FIG. 3 . In a case where the horizontal adjustment knobs 12 are of a screw method, the position in the horizontal direction is less likely to deviate from the adjusted state because of the friction of the screw even if the user releases his or her hand from the horizontal adjustment knobs 12 after the adjustment. [0028] Further, inclination adjustment knobs 13 (which will be hereinafter also referred to as an inclination adjustment unit) are provided to be in contact with a component connected with the rotation center screw 11 of the slide mechanism 10 , and for example, in a case where the inclination adjustment knobs 13 are a direct-acting method, a user grabs one of or both of the knobs of the inclination adjustment knobs 13 at the right and the left and moves the knobs in the vertical direction (which will hereinafter refer to a direction substantially in parallel with the border lines of the cylindrical lens 14 constituting the lenticular lens), and pushes or pulls the contact portions at the right and the left of the inclination adjustment knobs 13 , so that the user can adjust the inclination of the component connected with the rotation center screw 11 of the slide mechanism 10 connected with the lenticular lens 5 with respect to the rotation center screw 11 serving as the center of rotation. In a case where the inclination adjustment knobs 13 are of a feed screw method, a user rotates one of or both of the knobs of the inclination adjustment knobs 13 , and pushes or pulls the contact portions at the right and the left of the inclination adjustment knobs 13 , so that the user can adjust the inclination of the component connected with the rotation center screw 11 of the slide mechanism 10 connected with the lenticular lens 5 with respect to the rotation center screw 11 serving as the center of rotation. When the inclination adjustment knobs 13 are of a screw method, the inclination is less likely to deviate from the adjusted state because of the friction of the screw even if the user releases his or her hand from the inclination adjustment knobs 13 after the adjustment. [0029] In this case, the position adjustment mechanism 6 of the image display apparatus according to the first embodiment refers to the horizontal adjustment knobs 12 and the inclination adjustment knobs 13 . [0030] Therefore, in the image display apparatus according to the first embodiment, when the horizontal adjustment knobs 12 and the inclination adjustment knobs 13 are adjusted, the lenticular lens 5 can be independently adjusted in the horizontal direction and in the inclination direction of FIG. 3 with respect to the frame 9 . Since the horizontal adjustment knobs 12 and the inclination adjustment knob 13 are arranged in proximity to each other, the horizontal adjustment knobs 12 and the inclination adjustment knobs 13 can be easily adjusted at a time. [0031] On the other hand, the recorded image 2 is formed by printing of a print apparatus. FIGS. 4( a ) to 4 ( c ) are figures illustrating a method for forming a recording medium of the image display apparatus according to the first embodiment. [0032] As shown in FIG. 4( a ), for example, while a recording medium 22 which is a recording sheet such as paper is conveyed in a conveying direction 23 in a printer main body 21 , and a print apparatus uses a printer head 24 to print the recorded image 25 of a composite image made by composing multiple images parallaxes. As shown in FIG. 4( b ), the recorded image 25 is formed on the printed recording medium 22 . [0033] Further, as shown in FIG. 4( c ), this recording medium 22 is attached to a medium attachment unit 26 . In this case, as an indication of the position where the recording medium 22 is attached to the medium attachment unit 26 , a medium abutment surfaces 27 are provided on three sides of four external peripheral sides of the medium attachment unit 26 , and the external periphery of the recording medium 22 is brought into abutment with the medium abutment surfaces 27 , so that the recording medium 22 can be easily positioned with respect to the medium attachment unit 26 . [0034] Subsequently, a method for producing the image display apparatus according to the first embodiment will be explained with reference to FIGS. 5 , 6 . FIG. 5 is a first flowchart illustrating a method for assembling the image display apparatus according to the first embodiment. FIG. 6 is a second flowchart illustrating a method for assembling the image display apparatus according to the first embodiment. [0035] In this case, as shown in FIG. 5 , first, the recorded image is printed on the recording medium 22 (step S 1 ). Subsequently, the recording medium 22 having the recorded image 25 printed thereon is attached to the medium attachment unit 26 (step S 2 ). Further, the lenticular lens unit 4 is attached to the medium attachment unit 26 attached to the recording medium 22 (step S 3 ). While a user sees the recorded image 2 through the lenticular lens 5 , the user adjusts the inclination adjustment knobs 13 of the position adjustment mechanism 6 of the lenticular lens unit 5 (step S 4 ). [0036] In this case, if the inclination of the recorded image 2 seen through the lenticular lens 5 is correct (YES in step S 5 ), the user adjusts the horizontal adjustment knobs 12 of the position adjustment mechanism 6 of the lenticular lens unit 4 while the user sees the recorded image 2 through the lenticular lens 5 (step S 6 ). If the inclination of the recorded image 2 seen through the lenticular lens 5 is not correct (NO in step S 5 ), step S 4 is performed again so that the user adjust the inclination adjustment knobs 13 again. [0037] Further, if the horizontal position of the recorded image 2 seen through the lenticular lens 5 is correct (YES in step S 7 ), the processing is terminated. When the horizontal position of the recorded image 2 seen through the lenticular lens 5 is not correct (NO in step S 7 ), step S 6 is performed again, and the user adjusts the horizontal adjustment knobs 12 again. [0038] FIG. 5 shows the procedure for adjusting the inclination adjustment knobs 13 first then adjusting the horizontal adjustment knobs 12 , but the embodiment is not limited to this procedure. For example, in the procedure, the horizontal adjustment knobs 12 may be adjusted first, and then the inclination adjustment knob 13 may be adjusted. [0039] As shown in FIG. 6 , first, the recorded image 25 is printed on the recording medium 22 (step S 11 ). Subsequently, the recording medium 22 having the recorded image 25 printed thereon is attached to the medium attachment unit 26 (step S 21 ). Further, the lenticular lens unit 4 is attached to the medium attachment unit 26 attached to the recording medium 22 (step S 13 ). While the user sees the recorded image 2 through the lenticular lens 5 , the user adjusts the inclination adjustment knobs 13 of the position adjustment mechanism 6 of the lenticular lens unit 5 (step S 14 ). [0040] In this case, if the inclination of the recorded image 2 seen through the lenticular lens 5 is correct (YES in step S 15 ), the user adjusts the horizontal adjustment knobs 12 of the position adjustment mechanism 6 of the lenticular lens unit 4 while the user sees the recorded image 2 through the lenticular lens 5 (step S 16 ). [0041] Further, if the horizontal position of the recorded image 2 seen through the lenticular lens 5 is correct (YES in step S 17 ), the user checks whether the inclination of the recorded image 2 through the lenticular lens 5 is correct or not (step S 18 ). [0042] If the horizontal position of the recorded image 2 seen through the lenticular lens 5 is not correct (NO in step S 17 ), step S 16 is performed again, and the user adjusts the horizontal adjustment knobs 12 again. [0043] In this case, if the inclination of the recorded image 2 seen through the lenticular lens 5 is correct (YES in step S 18 ), the processing is terminated. [0044] If the inclination of the recorded image 2 seen through the lenticular lens 5 is not correct (NO in step S 18 ), this means that the inclination in the recorded image 2 is deviated, which was once correctly adjusted while the horizontal adjustment knobs 12 were adjusted, and therefore, step S 14 is performed again, and the inclination adjustment knobs 13 are adjusted again and the horizontal adjustment knobs 12 are adjusted again (step S 14 to step S 18 ). [0045] Therefore, according to the flowchart of FIG. 6 , whether the inclination adjustment knobs 13 are correct or not is checked again, and therefore, more accurately positioned adjustment state can be attained as compared with the flowchart of FIG. 5 . [0046] Like FIG. 5 , FIG. 6 shows the procedure for adjusting the inclination adjustment knobs 13 first and the adjusting the horizontal adjustment knobs 12 , but the procedure is not limited thereto. For example, in the procedure, the horizontal adjustment knobs 12 may be adjusted first, and then the inclination adjustment knob 13 may be adjusted. [0047] As described above, according to the image display apparatus of the first embodiment, the user can easily adjust the position of the lenticular lens 5 while the user sees the displayed recorded image 2 with the recorded image of the recording medium 1 . Second Embodiment [0048] An image display apparatus according to a second embodiment will be hereinafter explained with reference to FIG. 7 . The second embodiment is different from the first embodiment only in a lenticular lens unit 31 , and the second embodiment is the same as the first embodiment except the description of the lenticular lens unit 31 , and therefore, the same portions are denoted with the same reference numerals, and detailed explanation thereabout is omitted. FIG. 7 is a longitudinal sectional view illustrating a lenticular lens unit of the image display apparatus according to the second embodiment. [0049] As shown in FIG. 7 , a lenticular lens 5 is connected via a rotation center screw 11 with a slide mechanism 10 provided at a lower portion of FIG. 7 with respect to a frame 9 . The lenticular lens 5 is configured in such a manner that many inverted U-shaped cylindrical lenses 14 are arranged side by side. Further, horizontal adjustment knobs 12 are provided to connect with the slide mechanism 10 , and for example, in a case where the slide mechanism 10 is of a direct-acting method, a user grabs one of or both of the horizontal adjustment knobs 12 and moves the knobs in a horizontal direction, so that the slide mechanism 10 connected with the lenticular lens 5 can be adjusted in the horizontal direction of FIG. 7 . In a case where the slide mechanism 10 is of a feed screw method, a user rotates one of or both of the horizontal adjustment knobs 12 , so that the slide mechanism 10 connected with the lenticular lens 5 can be adjusted in the horizontal direction of FIG. 7 . In a case where the horizontal adjustment knobs 12 are of a screw method, the position in the horizontal direction is less likely to deviate from the adjusted state because of the friction of the screw even if the user releases his or her hand from the horizontal adjustment knobs 12 after the adjustment of the horizontal adjustment knobs 12 . [0050] Further, inclination adjustment knobs 13 are provided to be in contact with a component connected with the rotation center screw 11 of the slide mechanism 10 , for example, in a case where the inclination adjustment knobs 13 are a direct-acting method, a user grabs one of or both of the knobs of the inclination adjustment knobs 13 at the right and the left and moves the knobs in the vertical direction, and pushes or pulls the contact portions at the right and the left of the inclination adjustment knobs 13 , so that the user can adjust the inclination of the component connected with the rotation center screw 11 of the slide mechanism 10 connected with the lenticular lens 5 with respect to the rotation center screw 11 serving as the center of rotation. In a case where the inclination adjustment knobs 13 are of a feed screw method, a user rotates one of or both of the knobs of the inclination adjustment knobs 13 , and pushes or pulls the contact portions at the right and the left of the inclination adjustment knobs 13 , so that the user can adjust the inclination of the component connected with the rotation center screw 11 of the slide mechanism 10 connected with the lenticular lens 5 with respect to the rotation center screw 11 serving as the center of rotation. When the inclination adjustment knobs 13 are of a screw method, the inclination is less likely to deviate from the adjusted state because of the friction of the screw even if the user releases his or her hand from the inclination adjustment knobs 13 after the adjustment of the inclination adjustment knobs 13 . [0051] In this case, the position adjustment mechanism of the image display apparatus according to the second embodiment refers to the horizontal adjustment knobs 12 and the inclination adjustment knobs 13 . [0052] Therefore, in the image display apparatus according to the second embodiment, like the first embodiment, when the horizontal adjustment knobs 12 and the inclination adjustment knobs 13 are adjusted, the lenticular lens 5 can be independently adjusted in the horizontal direction and in the inclination direction of FIG. 7 with respect to the frame 9 . Since the horizontal adjustment knobs 12 and the inclination adjustment knob 13 are arranged in proximity to each other, the horizontal adjustment knobs 12 and the inclination adjustment knobs 13 can be easily adjusted at a time. Third Embodiment [0053] An image display apparatus according to a third embodiment will be hereinafter explained with reference to FIG. 8 . The third embodiment is different from the first embodiment only in a lenticular lens unit 41 and inclination adjustment knobs 42 , and the third embodiment is the same as the first embodiment except the description of the lenticular lens unit 41 and the inclination adjustment knobs 42 , and therefore, the same portions are denoted with the same reference numerals, and detailed explanation thereabout is omitted. FIG. 8 is a longitudinal sectional view illustrating a lenticular lens unit of the image display apparatus according to the third embodiment. [0054] As shown in FIG. 8 , a lenticular lens 5 is connected via a rotation center screw 11 with a slide mechanism 10 provided at a lower portion of FIG. 8 with respect to a frame 9 . The lenticular lens 5 is configured in such a manner that many inverted U-shaped cylindrical lenses 14 are arranged side by side. Further, horizontal adjustment knobs 12 are provided to connect with the slide mechanism 10 at the lower portion of FIG. 8 , and for example, in a case where the slide mechanism 10 is of a direct-acting method, a user grabs one of or both of the horizontal adjustment knobs 12 and moves the horizontal adjustment knobs 12 in a horizontal direction, so that the slide mechanism 10 connected with the lenticular lens 5 can be adjusted in the horizontal direction of FIG. 8 . In a case where the slide mechanism 10 is of a feed screw method, a user rotates one of or both of the horizontal adjustment knobs 12 , so that the slide mechanism 10 connected with the lenticular lens 5 can be adjusted in the horizontal direction of FIG. 8 . In a case where the horizontal adjustment knobs 12 are of a screw method, the position in the horizontal direction is less likely to deviate from the adjusted state because of the friction of the screw even if the user releases his or her hand from the inclination adjustment knob 13 after the adjustment of the inclination adjustment knob 13 . [0055] However, inclination adjustment knobs 42 are provided to be in contact with the lenticular lens 5 at the upper portion of FIG. 8 , and where the user grabs one of or both of the knobs of the inclination adjustment knobs 42 at the upper and lower sides and moves the knobs in the vertical direction, so that the user can adjust the inclination of the component connected with the rotation center screw 11 of the slide mechanism 10 connected with the lenticular lens 5 with respect to the rotation center screw 11 serving as the center of rotation, and can adjust the lenticular lens 5 in the inclination direction of FIG. 8 . In order to prevent deviation from the adjusted state after the inclination has been adjusted with the inclination adjustment knobs 42 in the image display apparatus according to the third embodiment, the rotation center screw 11 may be loosened while the inclination is adjusted with the inclination adjustment knobs 42 , and the rotation center screw 11 may be tightened after the inclination has been adjusted. In this case, the position adjustment mechanism of the image display apparatus according to the third embodiment refers to the horizontal adjustment knobs 12 and the inclination adjustment knobs 42 . [0056] Therefore, in the image display apparatus according to the third embodiment, when the horizontal adjustment knobs 12 and the inclination adjustment knobs 42 are adjusted, the lenticular lens 5 can be independently adjusted in the horizontal direction and in the inclination direction of FIG. 8 with respect to the frame 9 . [0057] Further, in the image display apparatus according to the third embodiment, the lenticular lens 5 including the inclination adjustment knobs 42 can be inclined, and therefore, this allows the user to make adjustment in a more intuitive manner. Fourth Embodiment [0058] An image display apparatus according to the fourth embodiment will be hereinafter explained with reference to FIG. 9 . The fourth embodiment is different from the first embodiment only in a lenticular lens unit 51 and horizontal and inclination adjustment knobs 52 , and the fourth embodiment is the same as the first embodiment except the description of the lenticular lens unit 51 and the horizontal and inclination adjustment knobs 52 , and therefore, the same portions are denoted with the same reference numerals, and detailed explanation thereabout is omitted. FIG. 9 is a longitudinal sectional view illustrating a lenticular lens unit of the image display apparatus according to the fourth embodiment. [0059] As shown in FIG. 9 , a lenticular lens 5 is connected via a rotation center screw 11 with a slide mechanism 10 provided at a lower portion of FIG. 9 with respect to a frame 9 . The lenticular lens 5 is configured in such a manner that many inverted U-shaped cylindrical lenses 14 are arranged side by side. [0060] However, the horizontal adjustment knobs 12 and the inclination adjustment knobs 13 , 42 are not separately provided, and instead, the horizontal and inclination adjustment knob 52 is provided. The horizontal and inclination adjustment knob 52 has such structure that the horizontal adjustment knob 12 and the inclination adjustment knobs 13 , 42 are integrated. [0061] In this case, the horizontal and inclination adjustment knobs 52 are provided to connect with a component connected with the rotation center screw 11 and the slide mechanism 10 , and, for example, in a case where the slide mechanism 10 is of a direct-acting method, a user grabs one of or both of the knobs of the horizontal and inclination adjustment knobs 52 and moves the knobs in the horizontal direction, so that the user can adjust the slide mechanism 10 connected with the lenticular lens 5 in the horizontal direction of FIG. 9 . In a case where the slide mechanism 10 is of a feed screw method, a user rotates one of or both of the knobs of the horizontal and inclination adjustment knobs 52 , so that the user can adjust the slide mechanism 10 connected with the lenticular lens 5 in the horizontal direction of FIG. 8 . When the horizontal and inclination adjustment knobs 52 are of a screw method, the position in the horizontal direction is less likely to deviate from the adjusted state because of the friction of the screw even if the user releases his or her hand from the horizontal and inclination adjustment knobs 52 after the user adjusts the horizontal and inclination adjustment knob 52 . [0062] Not only the position in the horizontal direction is adjusted but also the user grabs one of or both of the knobs of the horizontal and inclination adjustment knobs 52 at the right and the left and moves the knobs in the vertical direction and inclines the component connected with the rotation center screw 11 of the slide mechanism 10 , so that the user can also adjust the lenticular lens 5 in the inclination direction of FIG. 9 with respect to the rotation center screw 11 serving as the center of rotation. In order to prevent deviation from the adjusted state after the inclination has been adjusted with the horizontal and inclination adjustment knobs 52 in the image display apparatus according to the fourth embodiment, the rotation center screw 11 maybe loosened while the inclination is adjusted with the horizontal and inclination adjustment knobs 52 , and the rotation center screw 11 maybe tightened after the inclination has been adjusted with the horizontal and inclination adjustment knobs 52 . [0063] In this case, the position adjustment mechanism of the image display apparatus according to the fourth embodiment refers to the horizontal and inclination adjustment knobs 52 . [0064] Therefore, in the image display apparatus according to the fourth embodiment, when the horizontal and inclination adjustment knobs 52 are adjusted, the lenticular lens 5 can be independently adjusted in the horizontal direction and in the inclination direction of FIG. 9 with respect to the frame 9 . [0065] Further, in the image display apparatus according to the fourth embodiment, the lenticular lens 5 including the horizontal and inclination adjustment knobs 52 can be inclined, and therefore, this allows the user to make adjustment in a more intuitive manner. In addition, in the image display apparatus according to the fourth embodiment, the lenticular lens 5 can be easily adjusted at a time in the horizontal direction and the inclination direction of FIG. 9 with respect to the frame 9 using the horizontal and inclination adjustment knobs 52 . Fifth Embodiment [0066] An image display apparatus according to a fifth embodiment will be hereinafter explained with reference to FIG. 10 . The fifth embodiment is different from the first embodiment only in a lenticular lens unit 81 and a horizontal and inclination adjustment knobs 82 , and the fifth embodiment is the same as the first embodiment except the description of the lenticular lens unit 81 and a horizontal and inclination adjustment knobs 82 , and therefore, the same portions are denoted with the same reference numerals, and detailed explanation thereabout is omitted. FIG. 10 is a longitudinal sectional view illustrating a lenticular lens unit of the image display apparatus according to the fifth embodiment. [0067] As shown in FIG. 10 , a lenticular lens 5 is connected via a rotation center screw 11 with a slide mechanism 10 provided at an upper portion of FIG. 10 with respect to a frame 9 . The lenticular lens 5 is configured in such a manner that many inverted U-shaped cylindrical lenses 14 are arranged side by side. [0068] However, the horizontal adjustment knobs 12 and the inclination adjustment knobs 13 , 42 are not separately provided, and instead, the horizontal and inclination adjustment knob 82 is provided. The horizontal and inclination adjustment knob 82 has such structure that the horizontal adjustment knob 12 and the inclination adjustment knobs 13 , 42 are integrated. [0069] In this case, the horizontal and inclination adjustment knobs 82 are provided to connect with a component connected with the rotation center screw 11 and the slide mechanism 10 , and, for example, in a case where the slide mechanism 10 is of a direct-acting method, a user grabs one of or both of the knobs of the horizontal and inclination adjustment knobs 82 and moves the knobs in the horizontal direction, so that the user can adjust the slide mechanism 10 connected with the lenticular lens 5 in the horizontal direction of FIG. 10 . In a case where the slide mechanism 10 is of a feed screw method, a user rotates one of or both of the knobs of the horizontal and inclination adjustment knobs 82 , so that the user can adjust the slide mechanism 10 connected with the lenticular lens 5 in the horizontal direction of FIG. 10 . When the horizontal and inclination adjustment knobs 82 are of a screw method, the position in the horizontal direction is less likely to deviate from the adjusted state because of the friction of the screw even if the user releases his or her hand from the horizontal and inclination adjustment knobs 82 after the user adjusts the horizontal and inclination adjustment knob 82 . [0070] Not only the position in the horizontal direction is adjusted but also the user grabs one of or both of the knobs of the horizontal and inclination adjustment knobs 82 at the right and the left and moves the knobs in the vertical direction and inclines the component connected with the rotation center screw 11 of the slide mechanism 10 , so that the user can also adjust the lenticular lens 5 in the inclination direction of FIG. 10 with respect to the rotation center screw 11 serving as the center of rotation. [0071] In order to prevent deviation from the adjusted state after the inclination has been adjusted with the horizontal and inclination adjustment knobs 82 in the image display apparatus according to the fifth embodiment, the rotation center screw 11 may be loosened while the inclination is adjusted with the horizontal and inclination adjustment knobs 82 , and the rotation center screw 11 maybe tightened after the inclination has been adjusted with the horizontal and inclination adjustment knobs 82 . [0072] In this case, the position adjustment mechanism of the image display apparatus according to the fifth embodiment refers to the horizontal and inclination adjustment knobs 82 . [0073] Therefore, in the image display apparatus according to the fifth embodiment, when the horizontal and inclination adjustment knobs 82 are adjusted, the lenticular lens 5 can be independently adjusted in the horizontal direction and in the inclination direction of FIG. 10 with respect to the frame 9 . [0074] In addition, in the image display apparatus according to the fifth embodiment, the lenticular lens 5 including the horizontal and inclination adjustment knobs 82 can be inclined, and therefore, this allows the user to make adjustment in a more intuitive manner. Further, in the image display apparatus according to the fifth embodiment, the lenticular lens 5 can be easily adjusted at a time in the horizontal direction and the inclination direction of FIG. 10 with respect to the frame 9 using the horizontal and inclination adjustment knobs 82 . Sixth Embodiment [0075] An image display apparatus according to a sixth embodiment will be hereinafter explained with reference to FIG. 11 . The sixth embodiment is different from the first embodiment only in a lenticular lens unit 61 and horizontal adjustment auxiliary knobs 62 , and the sixth embodiment is the same as the first embodiment except the description of the lenticular lens unit 61 and the horizontal adjustment auxiliary knobs 62 , and therefore, the same portions are denoted with the same reference numerals, and detailed explanation thereabout is omitted. FIG. 11 is a longitudinal sectional view illustrating a lenticular lens unit of the image display apparatus according to the sixth embodiment. [0076] As shown in FIG. 11 , a lenticular lens 5 is connected via a rotation center screw 11 with a slide mechanism 10 provided at an upper portion of FIG. 11 with respect to a frame 9 . The lenticular lens 5 is configured in such a manner that many inverted U-shaped cylindrical lenses 14 are arranged side by side. [0077] In this case, the horizontal adjustment auxiliary knobs 62 (which may be hereinafter also referred to as horizontal adjustment auxiliary units) are provided at a lower portion of FIG. 11 in the image display apparatus according to the fifth embodiment. For example, when there is a high level of friction between the print surface of the recording medium 1 and the surface of the lenticular lens 5 , it is difficult to slightly move the lenticular lens 5 with only the inclination adjustment knob 13 and the horizontal adjustment knob 12 provided at an upper portion of FIG. 11 . [0078] In this case, in the image display apparatus according to the sixth embodiment, the horizontal adjustment auxiliary knobs 62 are adjusted at the same time, so that the adjusting force is applied to the lower portion of the lenticular lens 5 , and this allows the lenticular lens 5 to be slightly moved. [0079] It should be noted that the horizontal adjustment auxiliary knobs 62 are arranged to be in contact with the lenticular lens 5 , and, for example, when the horizontal adjustment auxiliary knobs 62 are of the direct-acting method, a user grabs one of or both of the knobs of the horizontal adjustment auxiliary knobs 62 at the right and the left and moves the horizontal adjustment auxiliary knobs 62 in a horizontal direction, and pushes or pulls the contact portions at the right and the left of the horizontal adjustment auxiliary knobs 62 , so that the adjusting force can also be applied to the lower portion of the lenticular lens 5 . Ina case where the horizontal adjustment auxiliary knobs 62 are of a feed screw method, a user rotates one of or both of the knobs of the horizontal adjustment auxiliary knobs 62 , and pushes or pulls the contact portions at the right and the left of the horizontal adjustment auxiliary knobs 62 , so that the adjusting force can also be applied to the lower portion of the lenticular lens 5 . When the horizontal adjustment auxiliary knobs 62 are of a screw method, the inclination is less likely to deviate from the adjusted state because of the friction of the screw even if the user releases his or her hand from the knobs of the horizontal adjustment auxiliary knobs 62 after the horizontal adjustment auxiliary knobs 62 have been adjusted. [0080] As described above, even when there is a high level of friction between the print surface of the recording medium 1 and the surface of the lenticular lens 5 in the image display apparatus according to the sixth embodiment, the horizontal adjustment auxiliary knobs 62 are adjusted at the same time, the adjusting force is also applied to the lower portion of the lenticular lens 5 , so that the user can slightly move the lenticular lens 5 . [0081] In this case, a single set of horizontal adjustment auxiliary knobs 62 are provided, but two or more sets of horizontal adjustment auxiliary knobs 62 may be provided. The horizontal adjustment auxiliary knobs 62 are combined with the slide mechanism 10 , the rotation center screw 11 , the horizontal adjustment knobs 12 , and the inclination adjustment knobs 13 , like the first embodiment. Alternatively, the horizontal adjustment auxiliary knobs 62 may be combined with the image display apparatuses according to the second embodiment to the fifth embodiment, and a position adjustment mechanism 6 according to another embodiment. Seventh Embodiment [0082] An image display apparatus according to a seventh embodiment will be hereinafter explained with reference to FIG. 12 . The seventh embodiment is different from the first embodiment only in a lenticular lens unit 71 , a lenticular lens 72 , a slide mechanism 73 , a rotation center screw 74 , horizontal adjustment knobs 75 , inclination adjustment knobs 76 , and the seventh embodiment is the same as the first embodiment except the description of the lenticular lens unit 71 , the lenticular lens 72 , the slide mechanism 73 , the rotation center screw 74 , the horizontal adjustment knobs 75 , and the inclination adjustment knobs 76 , and therefore, the same portions are denoted with the same reference numerals, and detailed explanation thereabout is omitted. FIG. 12 is a longitudinal sectional view illustrating a lenticular lens unit of the image display apparatus according to the seventh embodiment. [0083] As shown in FIG. 12 , the image display apparatus according to the seventh embodiment is an image display apparatus in which many inverted U-shaped cylindrical lenses 14 constituting the lenticular lens 72 are arranged side by side in the horizontal direction of FIG. 12 . Therefore, the slide mechanism 73 , the rotation center screw 74 , the horizontal adjustment knobs 75 , and the inclination adjustment knobs 76 of the lenticular lens 72 are arranged at the left side of the lenticular lens 72 . [0084] Therefore, the horizontal adjustment knobs 75 do not adjust the position, in the horizontal direction of FIG. 12 , of the lenticular lens 72 connected via the rotation center screw 74 with the slide mechanism 73 , but adjust the positions of the lenticular lens 72 in the vertical direction of FIG. 10 . Likewise, the inclination adjustment knobs 76 make adjustment in the inclination direction of FIG. 12 with respect to the rotation center screw 74 of the slide mechanism 73 serving as the center of rotation. [0085] As described above, the image display apparatus according to the seventh embodiment is an image display apparatus in which many inverted U-shaped cylindrical lenses 14 constituting the lenticular lens 72 are arranged side by side in the horizontal direction of FIG. 12 . A user can adjust the position of the lenticular lens 72 in the vertical direction of FIG. 12 by using the horizontal adjustment knobs 75 . In addition, the user can make adjustment in the inclination direction of FIG. 12 by using the inclination adjustment knobs 76 . [0086] In the image display apparatus according to the seventh embodiment, the slide mechanism 73 , the rotation center screw 74 , the horizontal adjustment knobs 75 , and the inclination adjustment knobs 76 may not be arranged at the left side of the lenticular lens 72 but may be arranged at the right side thereof. In the image display apparatus according to the seventh embodiment, the slide mechanism 73 , the rotation center screw 74 , the horizontal adjustment knobs 75 , and the inclination adjustment knobs 76 are arranged at the left side or the right side of the lenticular lens 72 like the first embodiment. Alternatively, the position adjustment mechanism 6 of the image display apparatuses according to the second to sixth embodiments and other embodiments may be arranged at the left side or the right side of the lenticular lens 72 . [0087] According to the image display apparatus of at least one of the embodiments explained above, the recorded image 25 and the lenticular lens 5 can be positioned with a simple structure. [0088] It should be noted that the present invention is not limited to the embodiments explained above, and it is to be understood that the present invention may be modified in various manners. [0089] For example, the number of lenticular lenses 5 in the lenticular lens unit 4 , 31 , 41 , 51 , 61 , 71 , 81 has not been particularly mentioned, but the present invention is not limited to a single lenticular lens 5 . It should be understood that two or more lenticular lenses 5 may be provided. [0090] In short, the present invention is not limited to the embodiments as they are. When the present invention is carried out, it can be embodied upon modifying constituent elements without deviating from the gist thereof. Multiple constituent elements disclosed in the embodiments can be combined appropriately, and various modes may be formed. For example, some of constituent elements may be omitted from all the constituent elements disclosed in the embodiments. Further, constituent elements in different embodiments may be appropriately combined.
An image display apparatus according to an embodiment includes a recording medium on which a composite image obtained by composing a plurality of images corresponding to respective parallaxes is printed by a print apparatus, a lenticular lens having a plurality of cylindrical lenses arranged side by side, and configured to display the composed image separately for each direction of parallax, and a position adjustment mechanism configured to adjust relative position of the recording medium and the lenticular lens, and the position adjustment mechanism includes an inclination adjustment unit capable of changing an inclination angle of at least one of the recording medium and the lenticular lens, and a horizontal adjustment unit capable of moving at least one of the recording medium and the lenticular lens in a substantially perpendicular direction to a border line of the cylindrical lens, and the inclination adjustment unit and the horizontal adjustment unit can make adjustment independently, and a rotation center of the inclination adjustment unit is provided at a portion of the horizontal adjustment unit, and the inclination angle can be changed on the basis of the rotation center which is a reference.
6
FEDERAL RESEARCH STATEMENT [0001] The U.S. Government has a paid-up license in this invention and the right in limited circumstances to require the patent owner to license others on reasonable terms as provided for by the terms of contract F0863798C6002 awarded by the United States Department of the Air Force, Air Training and Education Command. FIELD OF THE INVENTION [0002] The present invention relates to providing a universal decontaminating solution for the rapid neutralization of chemical and biological warfare (CBW) agents. More specifically, a method is described for use of an in situ generated dioxirane formulation by mixing a monopersulfate compound in the presence of a ketone in water, buffered with a carbonate-type buffer, to produce a pH neutral solution that is effectively reactive towards CBW agents over a wide range of temperatures. BACKGROUND OF THE INVENTION [0003] Recent world events involving terrorist activities have increased the need to develop an environmentally friendly universal decontaminating solution that possesses non-corrosive and non-toxic properties for the rapid neutralization of lethal chemical and biological warfare (CBW) agents. This need is particularly apparent in military operations in which large area decontamination would be required for aircraft, tanks, carrier ships, facilities, equipment, and terrain, as well as related civilian or homeland defense operations that would involve decontamination efforts by first-responder personnel. [0004] Decontamination solutions presently available for the destruction of CBW agents include Super Tropical Bleach (STB), a highly corrosive hypochlorite-based alkaline solution, and DS2, which possesses highly toxic ingredients of diethylenetriamine and ethylene glycol monomethyl (EGM) ether. These decontaminants have the drawbacks in that they present hazards to the handler(s) and surface materials, as well as adversely impacting the environment, and generate significant waste that requires unique disposal. [0005] Efforts to develop more user-friendly decontaminants have focused on using strong oxidant applications such as ozone, titanium dioxide catalyzed photolysis, organic and inorganic peracids, activated hydrogen peroxide, and peroxygen compounds. For example, U.S. Pat. No. 4,850,729 discloses a decontaminating formulation utilizing “per-salts” such as percarbonate, perborate, persilicate or perphosphate, in dry or aqueous forms, for the purpose of rendering active hydrogen peroxide species. Iron bearing clays were also incorporated to serve as activators for hydrogen peroxide to create reactive radical species, as well as providing thickening properties to the formulation. Similarly, U.S. Pat. No. 6,245,957 describes a formulation in which potassium bicarbonate is mixed with urea hydrogen peroxide to create a peracid of percarbonate to effectively degrade chemical warfare agents. Although both inventions make use of peracid oxidants, neither reveals effectiveness toward biological agents. [0006] The uses of either hydrogen peroxide, or a peroxygen compound such as monopersulfate, have been described as the reactive oxidative species within other multi-component formulations that target decontamination of both chemical and biological agents. U.S. Pat. No. 6,369,288 discloses a surfactant system that contains a peroxygen compound in conjunction with a detergent bleach activator for the purpose of generating peroxycarboylic acid as an active ingredient. Another surfactant based formulation disclosed in U.S. Pat. No. 6,566,574 is the combination of a water-soluble polymer, a corrosion inhibitor, a fatty alcohol, and a catalyst together with the reactive oxidative component, but functions under slightly alkaline pH conditions. [0007] Similar to the chemistry found in U.S. Pat. No. 4,850,729, U.S. Pat. No. 6,569,353 utilizes a ferrous iron bearing salt as an activator for hydrogen peroxide to generate powerful hydroxyl radicals in conjunction with the use of a monopersulfate compound. However, this particular formulation is prepared under acidic conditions in the presence of phosphate and is based in fumed silica media. [0008] As reported by Yang et al. Chem. Rev. 92, 1729 (1992), monopersulfate alone has been shown to be reactive towards the chemical agents of mustard gas (HD) and VX, but only under aggressive acidic conditions. A significant amount of a dissolving agent was also needed in this case to solubilize mustard in solution. U.S. Pat. No. 5,186,946 described the use of monopersulfate for biological disinfection for viruses, bacteria, and spores, by combining with sulfamic and malic acids and polyethylene glycol, but also under acidic conditions. [0009] Overall, the particular formulations described above fail to disclose the inclusion of a ketone-containing compound in the presence of monopersulfate to generate dioxirane oxidative species. [0010] Montgomery J. Am. Chem. Soc. 96, 7820 (1974) is credited with the first observation of in situ generation of dioxirane species, in which ketones were shown to catalyze the decomposition of monopersulfate in solution, as well as enhance oxidative reactivity towards select chemical substrates. Murray Chem. Rev. 89, 1187 (1989) and Adam et al. Acc. Chem. Res. 22, 205 (1989) since provided an extensive cross-reference list on the synthetic transformations of numerous substrates from both preparations of in situ generated dioxiranes and dioxiranes isolated in neat ketone solvents, thereby demonstrating unique and powerful oxidative selectivity and reactivity. [0011] Related dioxirane patents include U.S. Pat. Nos. 5,437,686 and 4,001,131, from the textile industry. Each discloses different formulations comprising a peroxygen compound and a diketone for the generation of dioxirane. The diketones for these particular applications were required as opposed to monoketones in that they demonstrated superior inhibition of dye transfer between fabrics during the cleaning process. [0012] More relevant is U.S. Pat. No. 5,403,549 which discloses a method and composition for disinfecting matter or materials contaminated with bacteria, consisting of a mixture of monopersulfate and a carbonyl-containing compound, identified as either a ketone or aldehyde, for producing dioxirane. Carbonyl-containing compounds tested in the patent included acetone, 2-pentanone, 4-hydroxy-4-methyl-2-pentanone, and camphorsulfonic acid. The '549 patent is limited in its disclosure and application, specifically stating that the use of phosphate buffer within a neutral pH range actually inhibits the biocidal activity of a dioxirane solution towards substrates, and discloses formulations only in room temperature conditions (20°-25° C.) to effectively sterilize equipment. Rather, the '549 formulation requires a buffer utilized within an acidic range of about pH 4 to achieve effective disinfection. Application towards toxic chemical substrates was also not described. [0013] To date, dioxirane-producing formulations have not been utilized in an effective manner under non-corrosive, neutral conditions in the presence of carbonate-type buffers to facilitate degradation of viscous CBW agents. The novelty of the disclosure herein is that powerful oxidative species of dioxirane can be generated rapidly in a cost-effective manner with the main by-products of reaction consisting of environmentally benign carbonate and sulfate salts, thereby aiming to provide an effective CBW agent decontaminating formulation that eliminates, or greatly minimizes the impacts of toxicity and corrosiveness to materials. SUMMARY OF THE INVENTION [0014] Accordingly, it is an object of the present invention to provide a universal decontaminating solution for the rapid neutralization of lethal CBW agents at a range of temperatures and neutral conditions based on the generation of dioxiranes. [0015] Dioxiranes are readily produced by mixing alkali metal monopersulfate (hereafter referred to as monopersulfate or monopersulfate compound) with a ketone-containing compound in water buffered with a carbonate-type compound, also preferably with the addition of co-solvent and surfactant, to produce an effective neutral-based decontaminating solution within a range of pH 5 to 9. The use of a carbonate-type buffer in our formulation is an improvement of prior art in that U.S. Pat. No. 5,403,549 teaches that the dioxirane formulation was unsuccessful at effective sterilization of biologicals in the presence of buffer within the aforementioned pH range, and that acidic pH was required to effect sterilization. [0016] The solution of the present invention preferably comprises at least one co-solvent to facilitate solvation of the reagents in the formulation, and/or at least one surfactant to increase the adhesion properties of the solution upon contact with contaminated surface materials, thereby enhancing the effectiveness of the dioxirane against viscous and/or thickened CBW agents. Application of the present invention thereby provides rapid neutralization of agents through oxidative and hydrolysis mechanisms enhanced through solvation and wetting properties of the solution when placed in contact with surfaces contaminated with agents. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [0017] The water-based composition of this invention includes monopersulfate and a ketone-containing compound in the presence of a carbonate-type buffer, and preferably includes at least one co-solvent and at least one surfactant. [0018] Alkali metal monopersulfate is formed by the neutralization of Caro's acid (H 2 SO 5 ), and can be found in the form of potassium monopersulfate (KHSO 5 ), and in the form of a triple salt with formula 2KHSO 5 ·KHSO 4 ·K 2 SO 4 , manufactured and sold by Dupont under the trademark Oxone®. [0019] Alkali metal salts of bicarbonate, such as sodium bicarbonate, are preferred for use in the formulation of the invention to buffer the monopersulfate and water to a neutral pH; however, other alkali metal salt forms of carbonate are also suitable for use in the composition of the present invention. Suitable ketones for use in the generation of dioxirane in combination with the monopersulfate include, but are not limited to, acetone, 2-butanone, 2-pentanone, 2-hydroxy-4-methyl-2-pentanone, hexafluoroacetone, trifluoroacetone, acetophenone, camphorsulfonic acid, and levulinic acid. Acetonitrile, propylene carbonate, propylene glycol, polypropylene glycol and/or tert-butanol are preferred co-solvents to facilitate solvation of the reagents, and surfactants tetrabutylammonium hydrogen sulfate (TBAHS), Triton-X, and/or cetyltrimethylammonium (CTMA) chloride are preferred to facilitate wetting properties of the formulation. [0020] All reagents of the present invention are commercially available and can be readily formulated with tap water. [0021] To begin preparation of the dioxirane decontaminant of the present invention, a solution of about 0.05-20% w/v carbonate-type buffer, dissolved in water, is prepared to which 0.1-40% w/v monopersulfate is added such that the resulting solution is in the range of pH 5 to 9. After mixing for 1-20 minutes, 0.1-40% v/v of a ketone is added for generation of the dioxirane. One or more co-solvents at a concentration within the range of 0.01-40% v/v, and 0.01-15% w/v of one or more surfactants, may be added to the formulation either prior to or after addition of the ketone(s), providing the additional solvation and surfactant wetting properties to the preferred formulation. [0022] More preferably, the monopersulfate is added at a concentration range of about 1-20% w/v, the carbonate-type buffer within a range of 0.05-20% w/v, the ketone is present at a concentration range of 0.1-20% v/v and, when present, the co-solvent(s) are present in a concentration range of 0.5-20% v/v and the surfactant(s) are present at a concentration range of 0.01-5% w/v. Solubility of each element will vary according to temperature and presence of other solvents in solution. [0023] The dioxirane-producing formulations of this invention are effective over a wide range of temperatures that would be encountered in field operations. Although some dioxirane of the formulation could volatilize upon initial contact with a hot surface, the cooling effect occurring between the CBW contaminated material and application of the dioxirane solution will allow the decontamination process to effectively continue. [0024] Dioxirane can be generated and collected within a contained system, with a slight diminishing of effectiveness towards CW simulant degradation over time. With regards to the monopersulfate component, only <1% active oxygen content is lost per month upon storage of the solid compound, whereas stability declines over time when placed in a bicarbonate buffered aqueous solution slightly above neutral conditions and up to about pH 9 where the minimum stability exists. For this reason, to minimize instability and degradation of the active monopersulfate and dioxirane components, the decontaminating solution of the present invention is therefore meant to be generated on-site within a short time (less than 1 hour) prior to use. [0025] Specific equipment will be required to mix and deliver sufficient volumes of the decontaminating solution within a short period of time, similar to basic fire-fighting equipment outfitted with a spray delivery device that can dispense a significant volume of decontaminant over a large surface area. Examples include the U.S. Army ABC-M12A1 skid-mounted decontamination apparatus, which is capable of supporting foam, aqueous or deicing-like solutions; and the M17 transportable decontaminating system that can draw water from a nearby source to dispense a spray to equipment and vehicles. The availability of a water source, or to transport carbonated-like buffered water, will be a requirement for use of the present invention, as well as separate containments of solid monopersulfate and ketone. [0026] The following specific examples are intended to illustrate the effectiveness of the invention. EXAMPLE 1 [0027] A dimethyldioxirane (DMDO) formulation was compared against control systems, as well as to a bicarbonate-buffered monopersulfate (Oxone®) system, to test effectiveness in degrading a VX agent stimulant, Demeton (175 nmols). The components utilized for corresponding 15 mL batch systems at pH 7 and 22° C. were based on concentrations in tap water of 1.45% w/v Oxone®, and/or 0.9% w/v sodium bicarbonate, and/or 5% v/v acetone, as applicable. The test systems consisted of Acetone in water (ACE), Acetone & bicarbonate in water (ACEBICARB), minimum and maximum amounts of potassium sulfate in bicarbonate buffer (minSALT & maxSALT), a bicarbonate buffered Oxone® (OXONE) and the formulation of the present invention (DMDO), generated by combining acetone with Oxone®. Time Simulant Mass (nmols) (mins.) ACE ACEBICARB minSALT maxSALT OXONE DMDO 0.333 170 177 184 145 0.16 bd 0.83 161 171 209 159 0.22 bd 1.5 166 161 180 149 0.53 bd 3 159 145 181 150 0.27 bd 5 171 161 181 150 0.23 bd Control Avg. 165 163 187 150 — — Std. Dev. 5 12 13 5 — — Rel. Std. Dev (%) 3 7 7 3 — — bd = below detection [0028] As expected, controls were unreactive towards the agent simulant. The buffered Oxone® solution, with ketone absent, was not as effective at achieving degradation of the simulant below limits of detection as compared to reactivity observed by the DMDO formulation described by the present invention. EXAMPLE 2 [0029] A highly concentrated level of VX simulant, Demeton (140 umols) was tested in the presence of a DMDO-producing formulation that contained co-solvent and surfactant, and compared similarly against controls. Components for the corresponding 5.6 mL test systems were used at concentrations of 10% w/v Oxone®, 7% w/v sodium bicarbonate, and/or 20% v/v acetone, as applicable, all at pH 7.6 and 22° C. Test systems were ‘SULFATE’ containing maximum amounts of potassium sulfate in bicarbanate buffer, ‘OXONE’ present in bicarbonate buffer, and ‘DMDO’ generated as described in the present invention. Each test system included 10% v/v acetonitrile as co-solvent and 0.1% TBAHS as surfactant. Time Simulant Mass (mmol) (mins.) SULFATE OXONE DMDO  2 0.151 0.113 0.001  5 0.144 0.065 0.001 10 0.128 0.062 0.003 20 0.137 0.052 0.001 Control Avg. 0.140 — — Std. Dev. 0.010 — — Rel. Std. Dev. (%) 7 — — Again, DMDO was considerably more effective at degrading the simulant as compared to buffered Oxone®. [0030] The inventors also noted other observations at different sampling times with real agents of HD, VX, and GD (Soman) using a dilute DMDO formulation. At 20 minutes sampling time, HD indicated complete degradation mainly to the corresponding sulfone derivative as the main product, with minor divinyl mustard products. At 40 minute sampling, VX and degradation products consisting of non-toxic ethyl-methyl phosphoric acid (EMPA) and N-oxide were observed. GD (Soman) in the presence of the dioxirane solution of the present invention resulted in the formation of the non-toxic GD-acid degradation product. The examples provided of agent tests were conducted in which dioxirane in the buffered monopersulfate solution of the present invention was significantly limited compared to the amount of agent spiked into the system. [0031] Biological viruses and bacteria have been demonstrated to undergo rapid kill (up to 7-logs, i.e. 99.99999%) within seconds in the presence of the DMDO formulation of the present invention. Testing of a Bacillus anthracis ‘wet’ spore simulant, Bacillus thuringiensis , was shown to undergo nearly 7-log kill in 10 minutes when exposed to DMDO. In comparison, a ‘dry’ preparation of these highly resistant spores also achieved 7-log kill within 20 minutes of exposure by DMDO. Bicarbonate-buffered Oxone® alone was only capable of achieving 40% kill at 20 minutes reaction time. EXAMPLE 3 [0032] A DMDO formulation was tested against both a bicarbonate buffered (pH 7) and unbuffered (pH 2) Oxone® system for inactivating a 2×10 7 anthrax spore simulant, Bacillus globigii . Corresponding components for each 10 mL batch system were based on concentrations of 10% w/v Oxone®, 4.2% w/v sodium bicarbonate, and, in the case of the DMDO formulation, 10% v/v acetone, all in deionized water. Spores were placed into each system at different temperatures and exposed for 15 minutes. Temperature % Inactivation of Spores @ 15 Minutes ° C. DMDO, pH 7 OXONE, pH 7 OXONE, pH 2 −3 98.55 50 99.69 4 99.993 87.92 99.75 25 100 26.67 94.33 55 90 100 99.84 [0033] A virus simulant was also exposed to a dioxirane-producing formulation of the present invention between 4° C. and 50° C., demonstrating complete kill at each temperature examined.
A universal decontamination formulation and method is disclosed based on the in situ generation dioxirane(s) under non-corrosive neutral conditions for the neutralization of chemical and biological warfare (CBW) agents. The composition relates to the generation of dioxiranes by mixing a monopersulfate-containing compound in the presence of a ketone in water buffered with a carbonate-type buffer, producing a pH neutral formulation that provides effective reactivity towards CBW agents over a wide range of temperatures.
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